international journal of bio-inorganic hybrid nanomaterials

International Journal of Bio-Inorganic Hybrid Nanomaterials

ABSTRACT

In this work, the effect of immobilization of bread yeast (Saccharomyces cerevisiae) by sol-gel technique combined

with functionalized nanoporous silica was investigated in different weight ratios of silica containing materials

(TMOS: LUS-1). The activities of immobilized yeast in days after immobilization were examined. The results

showed immobilization maintain the yeast life for a longer time. The functionalization by C18 functional group

improved the environmental conditions for yeast life. These results indicate that the immobilization technique in the

gel matrix and porous solid is a good system to develop industrial fermentations.

Keyword: Nanoporous silica, Sol-gel, Bread yeast, LUS-1, Fermentation, Immobilization, Mesopore.

(*) Corresponding Author - e-mail: [email protected].

Cells and Enzymes are immobilized by different meth-

ods including absorption, covalent linkage, entrapment,

cross linking and microencapsulation [1]. Produc-

ing ethanol through consuming glucose is one of the

-

ing yeasts through removing the ethanol, it is needed

to stabilize the yeasts leading to decrease the costs of

separation steps [2]. Immobilization of cells in a silica

metabolic activity, protection of environmental stresses

-

tion as a cellular storage systems in postponement of

reactions [3]. Saccharomyces Cerevisiae (SC), a type

of yeast bread, was utilized in this research. In order

to immobilizing the yeast, entrapping technique by

sol-gel method was used. Sol-gel method provides the

Improvement in Immobilization of Bread Yeasts by Sol-gel Meth-

od Combined with Functionalized Nanoporous Silica (LUS-1)

Alireza Badiei1*, Golriz Dadashi2, Hossein Attar3, Nastaran Hayati-Roodbari4

1 Associate Professor, School of Chemistry, College of Science, University of Tehran, Tehran, Iran

2 M.Sc. Student, Department of Chemical Engineering, Science and Research Branch,

Islamic Azad University, Tehran, Iran

3 Associate Professor, Department of Chemical Engineering, Science and Research Branch,

Islamic Azad University, Tehran, Iran

4 Ph.D. Student, School of Chemistry, College of Science, University of Tehran, Tehran, Iran

Received: 27 August 2013; Accepted: 6 November 2013

1. INTRODUCTION

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 471-476 ISSN: 2251-8533

472

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 471-476 Badiei A et al

-

Utilizing the sol-gel process commonly is accompa-

process includes solution formation, gelation, drying

and agglomeration [4].

Pope and co-workers investigated the immobiliza-

tion of SC into tetramethylortosilicate (TMOS) gel.

One day after of immobilization, the yeast did not

show any activity [5]. Fennouh et al immobilized the

of entrapping method [6]. Nassif et al investigated the

immobilization of Escherichia coli into TMOS and

after two weeks the yeast activity were reduced and

al compared the resistance of free and immobilized

The term “nanoporous materials” indicates the ma-

terials with pore diameters less than 100 nm [10].

LUS-1 is a type of silica with amorphous walls clas-

material was reported by Benneviot and Badiei in

2001 at Laval University [11]. Alvaro et al used nano-

porous silica to immobilize the Lipas Enzyme [12].

Jang and et al in 2006 immobilized Tripsin Enzyme

on SBA-15 (a type of mesoporous silica) with and

without functionalized by thiol group [13]. As the im-

mobilization into nanoporous silica leads to protection

of yeast from unwanted environmental factors and in

other side the functional group on surface of nanopo-

rous material, help to remove the unsuitable materials

such as ethanol.

In this work, the effect of immobilization of bread

yeast (Saccharomyces cerevisiae) by sol-gel tech-

nique combined with functionalized nanoporous

silica was investigated in different weight ratios of

silica containing materials (TMOS: LUS-1). The ac-

the measurement of produced CO2 by consumption

of glucose in days after immobilization and a sample

able to maintain the activity of yeast after one month

were determined. In comparison to the other methods

which were used before including Gas Chromatog-

raphy (GC) and High Performance Liquid Chroma-

tography (HPLC), this method is more practical and

convenient [15].

2. MATERIALS AND METHODS

2.1. Materials

SiO2, cetyl-trimethylammonium bromide (CTMABr),

-

-

Fala Company. P-toluenesulfonicacid monohydrate

(TSOH) obtained from Aldrich.

2.1.1. Characterizations

In order to characterize the functional groups on nano-

55Bruker were applied. The morphology and shapes

of synthesized materials were investigated by SEM

diameter, surface area and adsorption-desorption iso-

therms were measured at 77 K using a BELSORP-

miniII porosimeter. BET (Brunauer-Emmett-Teller)

area and BJH (Barret, Joyner and Halenda). The

low angle X-ray scattering spectrum was recorded

within a range of 2θ of 0.6 - 10 degree.

2.2. Methods

2.2.1. Synthesis of LUS-1

LUS-1 was synthesized according to the literature

[16], with a molar ratio of SiO2: 0.054 CTMABr:

2O. Prepared LUS-1 was washed

with a solution of HCl (2 M) and ethanol, with a

vacuum and dried in an oven overnight.

2.2.2. Functionalization of LUS-1

Acid washed LUS-1 was functionalized with Trichlo-

rooctadecylsilane. 1 g LUS-1 with 30 mL dried Tolu-

473

Badiei A et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 471-476

2.2.3. Immobilization of bread yeast on functionalized

LUS-1

Immobilization of yeast was performed through sol-

gel method. 5 gel samples were prepared by adding

different amounts of functionalized LUS-1 to 22.5 µL

-

-

ring, the Si-O-R bonds were created. Hydrolysis pro-

cess was catalyzed by HCl. The synthesized samples

-

tigate pore size effect on immobilization of yeast dif-

ferent ratios of different silica materials were utilized.

The silica amounts of TMOS were measured and then

LUS-1 was added in weight ratios of 1:1, 0.75, 0.5,

0.375 and 0.3125.

2.2.4. Measurement of immobilized yeast activity

To investigate the remained yeast activity, the amount

-

sumption by yeasts were measured. The yeasts con-

sume the Glucose through following reaction.

Glucose (C6H

12O

6 2H

5 2

were dissolved in 75 mL deionized water and were

-

ing 50 mL H2SO

4 0.1 M in one and Gel (fereman-

tor) in another were joint through a tube. The lid of

the system. The produced CO2 in gel container were

2SO

4 container. Thus the

weight in gel container reduced frequently. Its weight

was measure every 15 minutes. The reduced weight is

equal to produced CO2 [15].

-

ized LUS-1 and Free yeast.

3. RESULTS AND DISCUSSION

Figure 1 shows the functionalized LUS-1 X-ray dif-

fraction pattern. Three well-known and characteristic

θ

to diffraction peaks of (100), (110), and (200), are at-

LUS-1

236as (m2/g)

0.3010.1120.303Total pore

Volume (cm3/g)

2.72.32.4p (nm)

Table 1: Texture properties of samples.

Figure 1: Low angel X-Ray Diffraction pattern of the func-

tionalized LUS-1.

Figure 2: IR Spectrophotometer: (a) LUS-1 (b) functional-

ized LUS-1.

474


-

-

of LUS-1.

LUS-1, functionalized LUS-1and gel samples

(TMOS/LUS-1: 1:0.5) were investigated by nitrogen

-

eters and surface area are provided on Table 1.

Surface area and total pore volume in functional-

ized LUS-1 in comparison to LUS-1 illustrated a sig-

are on surface of silica and in some parts pore block-

ing happened. In gel sample, surface area and total

pore volume in comparison to functionalized one is

increased indicating the functionalized LUS were

placed inside gel structure and resulted data was at-

tributed to pores of gel.

The FTIR spectra (Figure 2) of LUS-1 based mate-

including a very strong band at 1110-1010 cm-1 rep-

Figure 3: Producing CO2 from free and immobilized yeasts at days 1, 2, 7, 21 and 31.

475

Badiei A et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 471-476

resenting stretching vibration of Si-O-Si, a very broad

band in the range of 3700-3200 cm-1 and a strong

-

2 vibrations may be assigned

-1. Vibratios of

H2O physisorbed onto the surface of silica appears at

around 1645 cm-1 in spectra of all LUS-1 based materi-

al. Functional group, Cetyloctadecylsilane, on surface

of LUS-1 was characterized by IR spectrophotometer

-1 and 1462 cm-1 are related to stretching vi-

bration of C-H bonds.

Vital activity of immobilized yeasts and free yeasts

were investigated at 0, 1, 2, 7, 21 days and one month

after immobilization (Figure 3). According to differ-

ent behaviour of gels illustrated in plots, Gels in com-

parisons to each other show different behaiviours. In

all samples by spending time the activity is reduced.

In comparison to free yeasts, this reduction of activ-

cell life was followed by a smaller slope. Because of

-

lized yeasts show less reduction of activity. In order

to achieve the yeasts, the substra should pass through

mass transfer resistances such as boundary layer of

(as an internal one). This fact reduces the amount of

level).

Because of environmental effects and inappropri-

ate conditions, the number of yeast was decreased.

Since Ethanol interefer with Fermentation ability

growth rate of SC and compete to Glucose transfer

which lead to slow and incomplete fermentation. As

LUS-1 possess outstanding chemical, thermal and me-

chanical stability is able to act as a microprotective

environment leading to avoid ethanols of prohibiting

on yeast activity.

According to the plots, the gel with TMOS: LUS-1

ratio of 1:0.5 provides the best conditions for yeast’s

-

ties, 21 days after immobilization the gel with 1:0.5

ratio maintains life and activity of yeasts for more

time rather than the other ratios. So this ratio of TMSO

and LUS-1 is selected as an optimum ratio.

By comparing immobilized yeast’s activity on func-

tionalized LUS-1 and LUS-1, the activity of yeasts

on functionalized LUS-1 was more protected. The

morphology of LUS-1 in Figure 5 shows its bush-like

structure. By functionalizing LUS-1, the functional

groups are placed into pores and LUS-1 scaffold.

Since the diameters of yeasts are greater than pores,

the yeasts were trapped into LUS-1 scaffold and im-

mobilized. By consuming Glucose, CO2 and H

2O are

produced. CO2

and remained H2O improves the yeasts lifetime. Bond

between functional groups and silica increase the hy-

drophobic, because the hydrophobic molecules are

nonpolar and show trend to similar molecules. In other

side, H2O molecules create hydrogen bonding and in-

crease the moisture of gel. Nonpolar molecules, like

CO2

4. CONCLUSIONS

The effect of immobilization of bread yeast (Saccharo-

myces cerevisiae) by sol-gel technique combined with

functionalized nanoporous silica was investigated in

different weight ratios of silica containing materials

(TMOS: LUS-1). The activities of immobilized yeast

-

sults showed immobilization maintain the yeast life

-

tional group improved the environmental conditions

for yeast life. These results indicate that the immobili-

Figure 4: SEM image of the functionalized LUS-1.

476


good system to develop industrial fermentations. The

REFERENCES

Immobilization of en-

zymes and cells, Humana Press.

The phys-

ics and chemistry of sol-gel processing, Academic

Press Limited.

Anal. Chem.,

78 (3) 2006, 646.

Progress in inorganic

chemistry: coordination complexes in Sol-Gel sil-

ica materials

5. Pope E. et al., J. Sol-Gel Science & Tech., 4

225.

J.

Sol-Gel Science & Tech., 19 (2000), 647.

7. Nassif N. et al., Nat. Mater., 1 (2002), 42.

Biotechnol. Lett., 24 (2002), 1557.

Pure Appl. Chem., 57

603.

Mulchandani, A.K. Singh, Biosens. Bioelectron,

20 (7) 2005, 1433.

11. Bonneviot M.M.L., Badiei A., Patent

01/55031 A1, 2001.

12. A. Mayoral, R. Arenal, V. Gascon, C.M. Alvarez,

Chem. Cat Chem., 5 (4)

J. Porous Ma-

ter, 13

Physicochem. Eng. Aspects, 229 (2003), 1.

JFSE, 4 (2005).

16. Bonneviot L., Morin M., Badiei A., US Patent

Chem. Mate., 12 (2) (2000), 275.

Adv. Mater., 15 (6) (2003), 511.


ABSTRACT

Metal nanoshells consists of a dielectric core surrounded by a thin noble metal shell, possess unique optical

properties that render nanoshells attractive for use in different technologies. This paper reports a facile method

for growth of small gold nanoparticles on the functionalized surface of larger silica nanoparticles. Mono-dispersed

silica particles and gold nanoparticles were prepared by the chemical reduction method. The size of the shell

nanoseeds could be altered by repeating the stage of reducing HAuCl4 on Au/APTES/silica particles, and the time

for which they react. The nanocore-shell particles prepared were studied using scanning electron microscopy

(TEM), UV–Vis spectroscopy, Fourier transform infrared spectroscopy (FTIR) and PL spectrophotometer. The TEM

images indicated that by growing gold nano-seeds over the silica cores a red shift in the maximum absorbance

silica@Au NPs in comparison with that of bare silica NPs. But, the existence of gold nanoseeds on the silica

particles surfaces does not change the PL spectra peaks of these nanoparticles.

Keyword: Core-shell; Silica; Gold; Nanoparticle; Surface functionalized; Initial growth.

Much recent research has focused on the fabrication

of new types of nanoparticles, particularly those with

optical and electrical properties that can be controlled

with precision. There is increasing interest in the

design and synthesis of topological structures com-

posed of monocrystals of various size and shape. Such

materials may have unusual optical properties as a

Gradual Growth of Gold Nanoseeds on Silica for Silica@Gold

Core-Shell Nanoparticles and Investigation of Optical Properties

1*, Nasser Shahtahmasebebi2, Ahmad Kompany2, Elaheh

Kafshdargoharshadi3

1 M.Sc., Department of Physics, Faculty of Science, Ferdowsi University of Mashhad, Mashhad,

Iran & Centre of Nanoresearch, Ferdowsi University of Mashhad, Mashhad, Iran

2 Professor, Department of Physics, Faculty of Science, Ferdowsi University of Mashhad, Mashhad,

Iran & Centre of Nanoresearch, Ferdowsi University of Mashhad, Mashhad, Iran

3 Professor, Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad,

Iran &Centre of Nanoresearch, Ferdowsi University of Mashhad, Mashhad, Iran

Received: 31 August 2013; Accepted: 3 November 2013

1. INTRODUCTION


noble metals have received particular attention,because

of the stability and the ease of preparation of Nano-

particles derived from, Hal and co-workers have

recently reported a new hybrid nanoparticle system

that consists of a dielectric core surrounded by a thin

noble-metal shell [1-3]. These nanoparticles, termed

“nanoshells”, possess unique optical properties,

including a strong optical absorbance and a large

third-order nonlinear optical susceptibility [4]. More

importantly, the absorbance can be selectively tuned

to any wavelength across the visible and infrared

regions of the spectrum simply by adjusting the

ratio of the dielectric core to the thickness of the

metal overlayer. These features render nanoshells

attractive for use in technologies ranging from conducting

polymer devices to biosensing and drug delivery

[5-7].

At present, the most versatile nanoshell system is

bed on the coating of silica nanoparticles with a thin

dielectric cores not only because methods for the

functionalization of the surface of silica are well-known,

but also because colloidal silica particles can be prepared

with reproducibly spherical shapes and narrow size

To prepare these gold nanoshells,a silica

-

minated surface silanizing agent (e.g., 3-aminopro-

is used as the surface primer. The interaction between

the amines and the negatively charged THPC gold

nanoparticles might be electrostatic rather than coor-

amine groups act attachment points for small colloidal

gold particles, which then serve nucleation sites for

Of all possible strategies [10], the reduction of

phosphoniumchloride (THPC) affords relatively

small gold particles (e.g., 2 nm) with a net negative

particles can attach to APTMS-functionalized silica

cores by coordinating to the lone pairs of the termi-

nal amine groups, the attachment can be enhanced

perhaps several fold by electrostatic effects, where in

the negatively charged THPC gold nanoparticles are

attracted to the amine groups, which are positively

charged at the pH used for the attachment process.

This strategy leads to silica nanoparticles in which

25% of the surface is covered by colloidal gold

particles that can be used to nucleate the growth of the

gold overlayer.

In this work, we describe the preparation of

gold nanoshellsby the chemical reduction method

and characterize the nanoshells by using transmis-

sion electron microscopy (TEM), Fourier transform

infrared (FTIR) spectroscopy, ultraviolet visible

(UV-Vis) spectroscopy and photo luminescence (PL)

spectroscopy.

2. EXPERIMENTAL

2.1. Materials

All reagents were purchased from the indicated sup-

-

-

hydrogen tetrachloroaurate (III) (all from Merch Co.).

Similarly, all solvents were received from the indicat-

ed suppliers: HPLC grade water, and absolute ethanol

(Merch Co.).

2.2.Characterization methods

AB electron microscope operating at a bi voltage of

200 kV. Sample preparation involved deposition of

the nanoparticles dispersed in water onto a 200 mesh

copper grid. The grid was then set aside to allow for

evaporation of any residual water before analysis.

The FTIR data were collected using an AVA-TAR-

370-FTIR THERMONICOLET spectrometer using

two separate procedures. The sample was impacted

into a tablet shape and put onto a polished silicon

wafer before analysis. UV-Vis spectra were collected

-

trometer over the range from 400 to 1100 nm. All

samples were dispersed in water into a quartz cell for

analysis.

2.3. Preparation of silica nanoparticles

An aliquot (3.0 mL) of ammonia (30% NH3 NH

4OH

say) was added to 50.0 mL of absolute ethanol. The

aliquot (1.5 mL, 6.7 mmol) of Si(OC2H

5)

4 (tetra-

ethyl orthosilicate, TEOS) was added dropwise.

Previous studies have shown that there is usually a

concentrationdependent induction period required

to form the SiO2 nucleus from the TEOS monomer.

For the concentrations employed here, the induction

change of the solution from clear to opaque white. On

the basis of previous work from our laboratories, the

concentration of the resultant silica nanoparticles was

7×1012 particles / mL. Analysis by TEM indicated that

the silica nanoparticles were spherical in shape with

115 nm diameters.

2.4. Functionalization ofsilica nanoparticlesurfaces

with APTES

The silica nanoparticles were then surface function-

alized by grafting them with 12 mM APTES in vol-

ume ratio of 3:7 under constant heating and vigorous

group on their surface. Under this condition, the

-

plete surface functionalization. The amine grafted

silica particles were then cooled to room temperature

and washed with at least 2 cycles of centrifugation and

redispersion in absolute ethanol and distilled water at

10,000 rpm for 15 min each to remove residual reac-

tants before resuspending them in 1 mL of water for

every 0.3 g of silica used for surface functionalization

with amine.

2.5. Preparation of colloidal gold nanoparticles

To a 45 mL aliquot of HPLC grade water was added

0.5 mL of 1 M NaOH and 1 mL of THPC solution

(prepared by adding 12 µ

THPC in water to 1 mL of HPLC grade water). The

(27 mmol) of HAuCl4 1% in water was added quickly

to the stirred solution, which was stirred further for

30 min. The color of the solution changed very quickly

from colorless to dark reddish yellow (Figure 1),

which we call “THPC gold nanoparticles”. Although

the size of the THPC gold nanoparticles can be varied,

our gold seeds were consistently 2-3 nm in diameter.

The solution of THPC gold seeds was stored in the

samples of the gold nanoparticles were dark brown in

color. The particles were near the detection limit of

our TEM.

2.6. Attachment of colloidal gold nanoparticles to

APTMS functionalized silica cores

An aliquot of APTES-functionalized silica nanopar-

ticles dispersed in ethanol (6.7 mL, 2.4×1013 particles/

mL) was placed in a centrifuge tube along with an

solution, 3.5×1014 particles/mL). The centrifuge tube

was shaken gently for a couple of minutes and then

fuged at 2000 revolutions/min, and a red-colored pel-

let was observed to settle to the bottom of the tube.

After drying, a red-colored pellet was left, which was

redispersed and sonicated in HPLC grade water. The

redispersed in 5 mL of HPLC grade water and used

described in the following subsection (Figure 2 b).

2.7. Growth of gold nanoshells

To grow the gold overlayer on the Au/APTES/sili-

solution containing a reducible gold salt. In a reac-

-

sium carbonate (K2CO

3) in 100 mL of HPLC grade

water. After 10 min of stirring, 1.5 mL (20 mmol) of a

Figure 1: THPC gold nanoparticles solution

solution of 1% HAuCl4 in water was added. The

solution initially appeared transparent yellow and

slowly became colorless over the course of 30 min. To

a vigorously stirred 4 mL aliquot of the colorless solu-

tion, we injected 200 µL of the solution containing the

Au/APTES/silica nanoparticles.

µL (0.36 mmol) aliquot of

formaldehyde. Over the course of 2-4 min, the solu-

tion changed from colorless to blue, which is charac-

teristic of nanoshell formation. The nanoshells were

centrifuged and re-dispersed in HPLC grade water

until use.


3.1. Imaging by TEM

spherical silica nanoparticleswith a size of about

120 nm, and then attached small colloidal particles

of gold to APTES-functionalized silica nanoparticles

cores and then used the attached gold particles to tem-

plate the growth of a gold overlayer. NH3 is the most

effective parameter in thespherical shape of silica

nanoparticles [11].

By increasing theconcentration of TEOS and

H2O, the size of the nanoparticles increases. It

-

ate of condensation and hydrolysis reactions [12].

Figure 2 shows TEM images of the different stages

of our synthesis of gold nanoshells produced us-

ing this strategy. Figure 2(a) displays single silica

nanoparticles. Figure 2(b) shows the desirable

arrangement of the small THPC gold nanoparticles

with a narrow size of <3 on functionalized silica cores.

This improves our success in properly functionalizing

silica particles with a layer of bifunctional APTES

molecules, and also in preparing THPC gold

nanoparticles in narrow size of <3 nm and good aged.

Figure 2(c) demonstrates growth of monodispersed

gold seedsto a narrow size of <10 nm and thus, a

homogeneous shell would be obtained by repeating

the last process of reducing HAuCl4 on SiO

2@Au

nanoparticles as seen in Figure 2(a-c). Therefore, we

also did this last part of coating for one time more on

the nanoparticles of Figure 2(c), whichhas shown as

the resultant shell growth in Figure 2(d). Thus as it

is seen, the used method in this paper for the fabri-

cation of SiO2@Au core/shell nanoparticles has some

-

cal size for silica nanoparticles and also uniform

attachment of colloidal gold nanoparticles to APTES-

functionalized silica cores.

3.2. XRD analysis

In order to indicate identity of the particles, X-ray dif-

pattern of the resultant nanoparticles (corresponding

-

the (111), (200) and (220) planes of the standard cubic

phase of Au.

(a) (b) (c) (d)

Figure 2: TEM images of different stages of preparing gold shell, (a) bare silica nanoparticles, (b) small colloidal THPC

of (the resultant) shell growth.

3.3. FTIR analysis

The structure study, i.e.bonding of these core-shell

particles was also done using Fourier transform infra-

red spectroscopy (FTIR). The results are shown in

Figure 4. The Figure shows the FTIR spectrum of sili-

ca, functionalized silica and silica-gold core-shell par-

ticles. It indicates an intense characteristic absorption

band between 3300 and 3500 cm-1 assigned to O–H

stretching in H-bonded water. Also this band can be

cross checked through the 1635 cm-1 band due to the

scissor bending vibration of molecular water. For SiO2

and SiO2@Au particles peak 1105 cm-1 can be signed

-1

-1

relates to symmetric vibration of Si–O. For function-

alized silica particles peaks at 3215 cm-1 is signed to

NH bond. –1

have been described as a superimposition of vari-

ous SiO2 peaks, Si–OH bonding and peaks due to

the residual organic group’s one. After coating these

particles with gold, the intensity of Si–O–Si and

indicates the presence of gold seeds on silica particles.

3.4. UV-Vis analysis

Optical absorption was recorded at various stages of

addition of gold nanoparticles in every method using

UV–Visible absorption spectroscopy. Optical absorp-

in Figure 5(a). The singly attached Au NPs have a sim-

ilar spectrum shape to that of free gold nanoparticles

Figure 3: XRD spectra of the resultant silica-gold nanopar-

ticles.

(a)

(b)

Figure 5: (a) UV-Vis spectra of attached THPC gold NPs/

APTES/silica has no noticeable plasmon peak shift in com-

parison with THPC gold pure NPs, (b) By growing gold

nanoseeds on the silica cores, in the stage of gold nanoseed

growing to obtain a complete gold nanoshell, a red shift in

the maximum absorbance is observed.

Figure 4: FTIR spectra of silica, silica@THPC attached Au

and the resultant silica@Au particles prepared.

the plasmon resonance region. In contrast, the absorp-

tion spectrum for gold nanoparticles attached in clus-

ters to silica nanoparticles shows an enhanced absorp-

tion in the plasmon resonance region. This result is

interpreted as a collective effect of the gold nanopar-

ticles in the cluster which would indicate the presence

of gold nanoparticle clusters on the silica nanoparti-

cles and the effect of plasmon-plasmon interactions on

the absorption of the group of gold nanoclusters on a

the UV–Visible spectra of silica-gold core-shell parti-

cles that after two coatings (in SiO2@Au1 and SiO

2@

Au2) the Plasmon peak demonstrated more spreading

and red shift from 622 to 662 nm respectively (Figure

5(b)). So it reveals that as more gold chloride has re-

duced on the attached gold particles and the particles

has begun to grow and merge, Their aspect ratio has

increased and this has leaded to a red shift of the ab-

electron mean free path in the metal shell [15].

3.5. PL analysis

Figure 6 shows the PL emission spectra under 540

silica@Au NPs. The silica@Au NPs prepared by

two methods in water display one strong emis-

does not shift the emission peak position.

4. CONCLUSIONS

Silica@gold core-shell particles were synthesized

by reducing gold chloride on THPC attached silica

nanoparticle cores for several stages. The morphology

of these particles was also studied using TEM. TEM

images demonstrated the growth of monodispersed

gold seeds in narrow sizes up to 10 nm and making

a whole shell by their linkage. Therefore, a uniform

shell was obtained by repeating the last process of

reducing HAuCl4 on these particles on the nanometer

scale. UV–Vis absorption spectroscopy shows a red

-

mon resonance peak position of gold depends upon

the sizes of gold shell seeds. Therefore, by chang-

ing the sizes of gold seeds on core surfaces and thus

by changing shell thicknesses; it is possible to de-

sign a material with desired optical properties.The

spectroscopy.

ACKNOWLEDGEMENTS

-

REFERENCES

Nano-

technology, 21

2. Huang F., Baumberg J.J., Nano Lett., 10 (2010),

J. Phys. Chem. B, 105

Principles of Colloid and

Surface Chemistry

T.R., Hal N.J., Appl. Phys. Lett., 78 (2001), 1502.

Curr. Opin. Biotechnol, 11

(2000), 215.

J.

Biomed. Mater. Res., 51

Pramana J.

Phys., 69 (2007), 277.

Figure 6: PL spectra of silica and silia@Au in comparison

with each other.

An Introduction to Ultrathin Or-

ganic Films

Recent. Patents. Biomed.

Eng., 1

J. Colloid Interface Sc., 26

ACS Appl. Mater. Interfaces, 3

Chem. Mater, 18

(2006), 4115.

JPCS, 188

102.

15. Park J., Estrada A., Sharp K., Sang K., Schwartz

Opt. Express, 16


ABSTRACT

water. In the next step, an ultrasound generator was usedwith an intensity of 24 kHz for 120 seconds to prepare nano-

measured and emulsion droplet size was examined by a particle size analyzer. The microstructures of the powders were

analyzed by scanning electron microscopy (SEM). The results showed that the type and concentration of the compounds

used as the wallare effective on the properties of nano-emulsion. Comparing the two compounds and their concentrations

higher concentrations of casein showed much less wrinkle and depression compared to the samples containing higher

concentrations of inulin, because of the smaller size of the nano-emulsions containing higher concentrations of casein.

properties and their concentrationsaffecting droplet size and morphology ofmicrocapsules.

Keyword: Casein; Inulin; Fish oil; Nano-emulsion; Scanning electron microscope.


Fish oil is inherently functional and possesses many

components that are good for human health. There is

diet due to the many associated health of omega-3

fatty acids [1]. Encapsulation has been used to mask

unpleasant taste in food sciences as well as to protect

technology, small solid particle, liquid or gaseous as

Evaluation of Casein and Inulin Effects on Droplet Size and pH

of Nano-emulsion, Morphology and Structure of

Microcapsules of Fish Oil

Mahnaz Hashemiravan1*, Maryam Saberi2, Nazanin Farhadyar3

1 Assistant Professor, Department of Food Science and Technology, Varamin-Pishva Branch,

Islamic Azad University, Varamin, Iran

2 M.Sc., Department of Food Science and Technology, Varamin-Pishva Branch, Islamic Azad University,

Varamin, Iran

3 Assistant Professor, Department of Chemistry, Varamin-Pishva Branch, Islamic Azad University, Varamin, Iran

1. INTRODUCTION


Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 485-490 Hashemiravan M et al

core materials are packaged within wall materials to

form microcapsules [3].

-

als studied were Pectin, Sodium alginate and chitosan

starch and whey protein were used as wall material by

and Casein combined with Inulin were used as the

wall material. A casein micelle is, in effect, a natural

-

polysaccharides consisting of a chain of fructose mol-

ecules. It is a polymer of β

units, constituting chains of different lengths each of

them with a terminal glucose unit [10].

two different type of wall material (Casein and Inulin)

on microcapsule morphology and properties of nano-

emulsion.

2. MATERIALS AND METHODS

2.1. Materials

-

ents, Brisbane, Australia) was used as the core materi-

al (ρ 3, η

wall material was Casein and Inulin. Casein (Casein

soluble in alkali with bulk density 450 kg/m3 and solu-

-

pany and Inulin was obtained from Sigma Chemical

-

used for the preparation of all solution.

2.2. Methods

2.2.1. Preparation of emulsions

All emulsion produced in two stages. In pre-emul-

sion, Casein with various concentrations (5,10,15,

20 g/100g) and Inulin (5, 10, 15, 20 g/ 100g) con-

centration were solved in distilled water with heat-

added to the pre-emulsion. The solution was placed in

2.2.2. Particle size determination

The mean particle size and the size distribution of

the nano-emulsions were measured by dynamic light

(German). The nano-emulsion was diluted 40-fold in

deionized water before measurement.

2.2.3. pH determination

The pH Measurement bypHmeter (Swiss, Metrohm

2.2.4. Spray-drying

The emulsions prepared were spray dried with a labo-

Switzerland) equipped with 0.7 mm diameter nozzle.

Spray drying conditions were similar for all samples.

600(l/h), 2(mL/min) and 100%, respectively. The inlet

and 65 ±

were collected from the collecting chamber and

-

ysis.

2.2.5. Scanning electron microscopy of encapsulated

powders

Themorphology were evaluated with a scanning elec-

tron microscope (Model TESCAN//VEGA, England).

The samples were placed on the SEM stubs using a

two-sided adhesive tape. The specimens were subse-

quently coated with a thin layer of gold using a mag-

netron sputter coater (Model Emitech, England).

2.2.6. Statistical design

The independent variables were the ratio of core ma-

terial to coating material (1:5; 2:5) and the concentra-

tion of wall material [Casein, Inulin]. Statistical de-

signs are presented in Table 1.The dependent variables

were the emulsion size, the pH of emulsion and the

size of nano-emulsion.

Hashemiravan M et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 485-490


3.1. pHofNano-emulsion

According to the Table (2), the results show that the-

kindand concentration of combination of Casein and

(p<0.05) on the pH of nano-emulsions.

kind of wall material, when nano-emulsion was pre-

pared at 20%wt inulin had the least pH of nano-emul-

sion on the other hand pH of Nano-emulsion had in-

that have relatively high electric charged and it is the

result of the presence of phosphate groups bonded to

serine [11].

3.2. Size of nano-emulsion

The results show that thekind and concentration of-

combination of Case in and Inulin have very signif-

Figure (2) shows that the sample which contains 20%

Formulation Casein (%) Inulin (%) Fish oil (%)

F1

0 20 4 1 75

F2

20 0 4 1 75

F3

10 10 4 1 75

F4

15 5 4 1 75

F5

5 15 4 1 75

F6

0 20 1 71

F7

20 0 1 71

F 10 10 1 71

F 15 5 1 71

F10

5 15 1 71

Table 1:

Nano emulsion

F1

b

F2

5.756 ± 0.60a

F3

5.773±0.011a

F4

a

F5

a

F6

a

F7

4.520±0.070b

F 5.750±0.070a

F a

F10

a

Table 2: pH nano-emulsion of casein at various con-

centration (5, 10, 15 and 20%wt) mixed with inulin 5,

-

ues in the same column shown with similar letters are

Figure 1:

concentration on the pH of nano-emulsion.


higher pH from it is Isoelectric point change between

the shared level of oil and water, it creates repulsion of

electrostatic and also space prevent that avoids water

closing each other [12].

the Figure (3) that between the pH and the size of

(p<0.01). It means that the size of emulsion droplet

was reduced by pH increasing. It mentioned on the

Table (2) sample contain 20% inulinhad the least pH

value (pH = 4.52) while it has themost size of emul-

study reducing of the pH from neutral to acidic caused

increasing the size distribution of emulsion droplet

[12].

The size distribution of emulsion depends onsever-

pH [13]. So we investigate these items. Some agents

Table 3: The mean size of nano-emulsion droplet of

casein at various concentration (5, 10, 15 and 20%wt)

mixed with inulin 5, 10, 15 and 20%wt, containing 4

Nano emulsion Size of nano emulsion

F1

a

F2

cd

F3

bc

F4

ab

F5

111.100±5.707bcd

F6

115.100±4.371bcd

F7

d

F cd

F cd

F10

bcd

Figure 2:

concentrationon the size of nano-emulsion.

Figure 3: Relationship between emulsion size (d43

) and pH

of the emulsion.

Figure 4: Scanning electron microscope (SEM) of encapsu-

Hashemiravan M et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 485-490

single samples. The only agents that changed was pH,

it is because of kind of wall materials and different

concentration so we use this factor in analyzing the

result. According to results that we mentioned on the

drops belong to sample that contain 20% case in and

sample had the most pH so these results shows that

is increased.

3.3. Morphology and structure of microcapsules of

The SEM images (Figure 4) show that microcapsules

containing 20% case in have much less shrinkage and

structure of the powder particles containing inulin was

porous and has depression and some cracks shown

in Figure 5. Adding Inulin to Casein had a profound

impact on the structure and morphology of microen-

capsulated powders. Casein combined with high lev-

els of inulin particles produces particles with rough

surfaces, but combined with low doses of inulin had

no tangible impact, though the uniformity of micro-

capsule sizeswas affected. It showed the slower rate of

material properties and their concentration saffecting

the structure and morphology of microcapsules by the

presence of cracks in the microcapsules containing

greater amounts of inulin.

4. CONCLUSIONS

The study revealed that ultrasonic waves can be used

of nano and also energy of the waves can be used to

produce food nano-emulsions and products in which

the particle size as a parameter has an important role

in the product quality. Results showed that the small-

est particle size was related to the sample containing

size was related to the sample containing 20% inulin

-

sein) from 1:5 to 2:5, the droplet size as the important

characteristic of nano-emulsion decreased, thus the

product quality improved. The lowest pH belonged

to the treatment containing 20% inulin which was

the pH and the emulsion droplet size as by increasing

pH the emulsion droplet size was reduced.

REFERENCES

E., Pedroza R., Am. J. Food Technol., 6

Food Res. Int., 41

3. Loksuwan J., Food Hydrocolloid, 21

Eur. Food Res Tech-

nol., 222 (2006), 336.

Figure 5: -

cally the pores formed, which could explain the relatively

powder containing 20% Inulin.


Food Hydrocolloid, 18 (2004),

Korean J. Food Sci.

Technol., 32 (2000), 132.

7. Klinkesorn U., Sophanodora P., Chinachoti P.,

Food Hydro-

colloid, 19 (2005), 1044.

Ann. Fac. Medic., 21

Food Hydrocolloid, 21

Petrovsky N., J. Exc. Food Chem., 1 (2010), 27.

Dairy Science and Technology

Handbook, VCH Publisher; Eurika, California,

USA.

Food

Hydrocolloid, 16 (2003), 153.

Langmuir,

1 (2002), 26.


ABSTRACT

Synthesis of BaFe12

O19

magnetic nano particles via precipitation in different pH conditions have been reported. The

certain molar ratio of Fe/Ba = 12 selected and sodium hydroxide was used as a precipitant agent. X-ray Diffraction

(XRD), Scanning Electron Microscopy (SEM) and vibrating sample magnetometer (VSM) were used to consider

the structural, morphological and magnetic properties of barium hexaferrite nano-particles, respectively. Results

demonstrated that pH plays an important role in phase composition; so affected sample properties. The broad

hysteresis loop shows that the barium hexaferrite powder was in good crystalline nature.

Keyword: Barium Hexaferrite; Co-precipitaion; pH; Magnetic Properties; Nanoparticles; Hard Ferrites; XRD.


Barium ferrites are well known as a hard magnetic ma-

-

-

ties such as chemical stability, corrosion resistivity and

high coercive force. Because of these they could not be

-

and can be considered as a superposition of R and S

[3]. They have potential application in contrast agent in

magnetic resonance imaging (MRI), recording media,

radar absorbing material and as microwave absorber

materials [4-6]. Some of the other applications are ap-

barium ferrite nanoparticles, such as ball milling rout,

requires a high calcination temperature around 1200-

pH and Properties of Synthesized Barium Hexa-Ferrite

by Co-precipitation Method

Shaghayagh Marzban1*, Saeid Abedini Khorrami2

1 M.Sc. Student, Department of Chemistry, Tehran North Branch, Islamic Azad University, Tehran, Iran

2 Associate Professor, Department of Chemistry, Tehran North Branch, Islamic Azad University, Tehran, Iran

1. INTRODUCTION


Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 491-494 Marzban Sh. et al

-

sult in entrance of impurities into the compositions,

generation of lattice strains in the molecular structure

and made irregularity in the particle shape. The high

temperature insures the formation of barium ferrite;

-

ent chemical methods such as hydrothermal [10, 11],

sol-gel auto-combustion [12,13], co-precipitation [14-

17]. Among these methods, co-precipitation is one of

the simplest techniques. This method uses accessible,

environment-friendly and cheap precursors such as

This process accrues at lower temperature conditions

so, known as green synthesis methods. In the present

work, BaFe12

O powder has been prepared by co-

precipitation method using metallic nitrates of barium

and iron as precursors. Characterization of nano-parti-

cles showed the success process.

2. EXPERIMENTAL

2.1. Materials

Barium nitrate Ba(NO3)

2

nona hydrated Fe(NO3)

3 2-

solutions.

2.2. Synthesis of BaFe12

O19

Synthesis of nano-sized powder of magnetic barium

amounts of Fe(NO3)

3 2O, Ba(NO

3)

2 kept at a molar

ratio of 12:1. The salt solution was added dropwise

12 for each system, respectively. The red precipitates

-

ter. This process took about 6 hours. The sample was

for 3 hours. After attaining the powder by mortar and

2.3. Characterization process

30 mA. A “Philips XL-30” scanning electron micro-

scope was used to characterize the morphologies and

microstructure of the samples.


recorded by X-ray diffraction with Cu-Kα radiation

source in the range of the 2θ

The X-ray patterns of sample powders C1, C

2 and C

3

74-1121 picks show that BaFe12

O with miller plates

(1 1 4) and (1 0 7), is dominant phase in all of samples.

In Figure 1 the miller plates (1 1 0) and (1 0 4) refers

to the small amount of α-Fe2O

3 as sub phase in sample

C1

(2 1 2) demonstrates that BaFe2O

4 is impurity phase

at sample C2 (synthesized at pH 10). As shown in

Figure 1. the absence of any sub-picks demonstrates

that C3 (synthesized at pH 12) has a good BaFe12

O

Figure 1: X-ray diffraction pattern of BaFe12

O19

synthesis in

different pH.

Marzban Sh. et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 491-494

single phase composition.

The crystallite powders size was also measured by

X-ray line broadening technique using the Scherer’s

formula indicated in Equation (1):

(Eq. 1)

β is half-intensity width

of the relevant diffraction, λ is X-ray wavelength and

θ the diffraction angle.

The results revealed that the number of phases, par-

ticle size and percent cristallinity of BaFe12

O -

decrease with the pH rising. The effect of pH on the

average size and percent crystallinity of nanoparticles

is summarized in Table 1.

As shown in Figure 2 the synthesized BaFe12

O

nanoparticles at pH= 12 has nonregular shape

morphology at all. It was observed that individual

grains are not distributed homogenously, but rather

tend to agglomerate forming larger bundles. But an-

shapes at high level pH. The magnetic properties were

at room temperature. Plot of magnetization (M) as a

-

Sample Ba:Fe pH PhasesParticles size

(nm)Percent Crystallinity (%)

C1

1:10 Fe2O

3, BaFe

12O

C2

1:10 10Fe

2O

3, BaFe

2O

4,

BaFe12

O

C3

1:10 12 BaFe12

O

Sample Ba:Fe pH Ms(emu g-1) M

r(emu g-1) H

c(Oe)

C3

1:10 12

Table 1: Crystallinity percent, particle size and phases of samples prepare in different pH.

Table 2: Magnetic parameters of BaFe12

O19

nanopowders prepared at pH= 12.

Figure 2: SEM imagining of BaFe12

O19

nano-particles

synthesized in pH= 12.

Figure 3: VSM Loop of BaFe12

O19

nano-particles synthe-

sized in pH= 12.

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 491-494 Marzban Sh. et al

results demonstrated the formation of the pure barium

-

tion magnetization (Ms), remanent magnetization (M

r)

and cervicitis (Hc) of sample C

3, reported in Table 2.

Even though from the SEM analysis particles are not

uniformly distributed but the particle size and particle

morphology are the main reasons for the low coerciv-

ity (Hc

4. CONCLUSIONS

-

sized successfully by co-precipitation technique. Re-

sults demonstrate that pH plays an important role in

the phase formation process. As by pH value increas-

ing, the main phase composition growing up and at

last single phase obtained at pH= 12. Magnetic prop-

erties of sample C3 as a hard magnet, by single phase

REFERENCES

JAMME, 27

2 Valenzuela R., Phys. Res. Inter.

3. Pullar R.C., Prog. Mater. Sci., 57

Appl. Surf. Sci., 259

5. Ozah S., Bhattacharyya N.S., J. Magn. Mater.,

342

Zhai J., Adv. Powder Technol., 24

7. Aksit A.C., Onar N., Ebeoglugil M.F., Birlik I.,

Celik E., Ozdemir E., J. appl. Polym. Sci., 113

Materials, North-Holland, Amsterdam, 3

J. Magn. Mater., 301

Mater. Chem.

Phys., 127 (2011), 415.

11. Janasi S.R., Emura M., Landgraf F.J.G., Rodrigues

J. Magn. Mater., 238

Ind. Eng. Chem.

Res., 39

13. Mali A., Ataie A., J. Al. Com., 399 (2005), 245.

14. (a) Packiaraj G., Nital P., Jotania R.B., J. Biomed.

Bioeng., 1

Adv. Mater. Res., 3052 (2011),

J. Colloid. Inter f. Sci., 235

16. Mallick K.K., Shepherd Ph., Green R.J., J. Eur.

Ceram. Soc., 27 (2007), 2045.

17. Rashad M.M., Ibrahim I.A., J. Magn. Mater., 323


ABSTRACT

A organic-solution-processable functionalized-graphene (SPFGraphene) material has been studied on pre-

concentration and determination of trace Mo(II) ions. In this process, the effects of pH solution, elution conditions

on pre-concentration of trace Mo(II) were studied and the effect of interfering ions was also investigated. A

selective method for the fast determination of trace amounts of Mo(II) ions in water samples has been developed.

Method has been developed for preconcentration of Mo on organic-solution-processable functionalized-graphene

oxidation of bromopyrogallol red at λ

6.9×10-9 -9 M. This procedure has been successfully applied

to determine the ultra-trace levels of Mo in the environmental samples, free from the interference of some diverse

Keyword: Preconcentration; Micro crystalline; Nano graphene; Mo(II); SPE; FAAS; Organic-solution; Functionalized.


in which it is present. Mo(II) is a potentially carcino-

genic agent [1]. Mo(II) at trace concentrations acts as

water systems [2-5]. This element is needed by plants

At these levels, Mo(II) can bind to the cell membrane

and hinder the transport process through the cell wall.

Mo(II) at nearly 40 ng mL-1 is required for normal

metabolism of many living organisms [6]. On the other

hand, Mo(II) is an important element in many indus-

tries. Thus, the development of new methods for selec-

tive separation, concentration and determination of it in

Functionalized-Nano Graphene

Ali Moghimi

Associate Professor, Department of Chemistry, Varamin-Pishva Branch Islamic Azad University,

Varamin, Iran

Received: 14 September 2013; Accepted: 21 November 2013

1. INTRODUCTION


Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 495-502 Moghimi A

sub-micro levels in different industrial, medicinal and

environmental samples is of continuing interest.

The determination of Mo(II) is usually carried out

spectrometry (AAS) [7] as well as spectrometric

alternatives for traditional classic methods due to se-

lective removal of trace amounts of metal ions from

the most appropriative preformation features of SPE

is achieved by using octadecyl silica membrane disks.

The octadecyl silica membrane disks involves short-

er sample processing time and decreased plugging due

to the large cross-sectional area of the disk and small

channeling resulting from the use of sorbent with

smaller particle size and a greater mechanical stability

of the sorbent bed [13].

-

brane disks with suitable compounds for selective

determination of chromium [14] and lead [11]. Mean-

while, other investigators have successfully utilized

-

toring trace amounts of lead [15], copper [16], silver

Ce [22] and UO2 [12].

The used ligand is new and fairly selective and will

not interfere in the determination process of Mo(II).

Absorption spectrophotometry method (after precon-

centration) was applied for determination of Mo based

Various effective parameters have been evaluated,

and the developed procedure has been successfully

employed for the quantitation of ultra-trace amounts

of Mo in water sample.

2. EXPERIMENTAL

2.1. Apparatus

The glass column with 10 mm i.d. and 200 mm height

was used to make preconcentration column. An

-

ing the absorption spectra. A spectrophotometer (Per-

kin-Elmer model 35) with 10 mm glass cuvette was

Controlling the reaction temperature was done by a

and a stopwatch was used for recording the reaction

time. The synthesis of the TPP-NHCO-SPFGraphene

is illustrated in Scheme 1.

2.2. Reagents

chemicals were used throughout.

2.2.1. Synthesis of TPP-NHCO-SPFGraphene

-

ized-graphene (SPFGraphene) hybrid material with

porphyrins was prepared. The synthesis of the por-

phyrin-Graphene nanohybrid, 5-4 (aminophenyl)-10,

molecules covalently bonded together vi a an amide

bond (TPP-NHCO-SPFGraphene, Scheme 1 and 2)

was carried out using an amine-functionalized pro-

phyrin (TPP-NH2

-

-

25]. Results of atomic force microscopy characteriza-

which consists of almost entire single-layered Gra-

1) SOCl2, 24 hGrapheme oxide TPP-NHCO-SPFGraphene

2) TPP-NH2, EtN ,

TPP-NH2 =

Scheme 1: Synthesis scheme of TPP-NHCO-SPF Gra-

phene [26].

Moghimi A Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 495-502

phene sheets in H2O [24, 25]. TPP-NH

2 and Graphene

amide bond. Much care has been taken to make sure

all the unreacted TPP-NH2 has been removed using

-

ide has made TPP-NHCO- SPFGraphene soluble in

2.2.2. Standard Mo solution

A standard solution of Mo(II), 1.0×10-3 M was pre-

pared by dissolving 0.1111 g Mo nitrate (Merck) in

water containing a drop of concentrated HCl and

working solutions of Mo(II) were prepared by serial

dilution of the stock solution.

2.2.3. Standard bromopyrogallol red solution

An aqueous solution of (1.0×10-4 M) bromopyrogallol

red (Merck) was prepared by dissolving of 0.0140 g

bromopyrogallol red in water and diluting to the mark

-

tions in the range from 2.0 to 10.0 were prepared with

acetate, phosphate, and borate. Glycine/HCl buffer

was used for pH 1.0. Stock solutions (5.0×10-3 M) of

interfering ions were prepared by dissolving suitable

solutions.

2.3. General procedure

The column was packed with 3.0 g adsorbent and was

conditioned with 1.0-2.0 mL of pH 5.0. Then, 10.0 mL

of Mo solution (5.0×10-5 M) was passed through the

column at 0.1 mL min-1. The analyte was eluted from

the column by 1.0 mL of HCl, 1.0 M. A sample solu-

tion was prepared by pouring 0.5 mL of buffer solu-

of 1.0×10-4 M bromopyrogallol red was added. The

of Mo(II) (5.0×10-5 M) (eluted solution from column)

was added and the solution diluted to the mark with

-

propriate amount of the solution was transferred to the

spectrophotometric cell and variation in absorbance

of the reaction at 517 nm. A calibration graph was

plotted with absorbance change (∆A = A5 -A

0.5) versus

Mo concentration.


Organic-solution-processable functionalized-gra-

Scheme 2: Schematic representation of part of the structure of the covalent TPP-NHCO-SPFGraphene [26].


phene (SPFGraphene) with the following structure

(Scheme 1) is a new chelating agent which can form

-

dentate bisamide ligand on microcrystalline naphtha-

lene, Mo(II) can be adsorbed. Then desorption of Mo

is carried out by using a strong inorganic acid. The

Mo(II) concentrations were determined spectrophoto-

metrically after passing solution through the column.

-

photometric procedure should be studied.

3.1. Effect of variables on the determination of Mo

Bromopyrogallol red with following structure Figure

-

tion decreases with time, at λ = 517 nm. The change in

the signal is proportional to Mo concentration. Figure

3 shows the absorption spectra of bromopyr-ogallol

-

rophotometric determination) on eluted Mo solution

was done at different pH values (1.0-5.0). Figure 2

shows the effect of pH on the net absorbance (∆A).

higher pH values cause decreasing in the signal. At

-

rogallol red increases, thus the reaction rate and ∆A

decreased. Therefore the pH of 1.0 was selected for

-

centration on the reaction rate was tested at pH 1.0

with 1.0×10-5

seen that the best concentration for bromopyrogallol

Figure 1: Structure of Bromopyrogallol red structure.

Figure 2: Effect of pH on the reaction rate. Conditions: bro-

mopyrogallol red, 1.0×10-5 M; Mo(II), 1.0×10-5 M; tempera-

ture, 30°C; measuring time, 5.0 min from initiation of the

reaction.

Figure 3: Effect of bromopyrogallol red concentration on the

reaction rate. Conditions: pH 1.0; Mo(II), 1.0×10-5 M; tem-

perature, 30°C; measuring time, 5.0 min from initiation of

the reaction.

Figure 4: Effect of temperature on the rate of reaction. Con-

ditions: pH 1.0; Mo(II), 1.0×10-5 M; bromopyrogallol red,

3.0×10-5 M; measuring time, 5.0 min from initiation of the

reaction.


red is 3.0×10-5 M. At higher values the aggregation of

bromopyrogallol red causes the reaction rate to be de-

(∆ -

timum conditions otherwise as previously described.

Figure 4 shows that with increasing temperature up to

∆A signal or the rate of reaction increases. So

bromopyrogallol red can be decomposed.

3.2. Effect of variables on the preconcentration

-

amined in range of 1.0-10.0, and the results are shown

in Figure 5. The results show that in the pH range of

5.0-10.0, the analyte was adsorbed on microcrystal-

line naphthalene quantitate and the recovery was more

be formed on adsorbent (at acidic media, active sites

of ligand will be protonated) and at high pH values,

Mo will precipitate on the column (precipitating in-

stead of adsorption will occur). In order to obtain the

best conditions for determination after preconcentra-

tion and to prevent the precipitation of Mo (especially

at high concentrations), the most acidic pH from this

of analyte retention time was investigated by passing

10.0 mL of Mo(II) (5.0×10-5 M) solution in the pH 5.0

-

ment with the passed solution. The results show that

microcrystalline naphthalene quantitatively. The best -1. As the Mo

-

chloric acid was selected to desorb the adsorbed ana-

lyte. Figure 6 shows that Mo(II) can be desorbed from

the adsorbent by elution with 1.0 mL, HCl, 1.0 M.

For investigating the ability of microcrystalline naph-

thalene to adsorb Mo(II) after sequential elusions,

the preconcentration process was repeated for many

times. It was indicated that the results were satisfac-

tory, even by using one column for 10 times, with-

out changing the packing. The different volumes of

Mo solution, 1.0×10 M in the range of 10-1000 mL

were passed through the column and the signal of each

eluted solution was compared with calibration curve

data which is achieved from determination method.

The obtained signals of concentrated Mo solutions

presented that a preconcentration factor of 100 can be

achieved by this method. The effect of ionic strength

on the sensitivity was studied. The sensitivity would

be slightly changed with increasing the ionic strength

3.3. Retention capacity of the adsorbent

The retention capacity of organic-solution-process-

able functionalized-graphene (SPFGraphene) adsor-

bent was determined by a batch method. The 20 mL

solution of Mo(II) 1.0×10-4 M in pH 5.0 was trans-

ferred into a separating funnel and 3 g adsorbent was

Figure 5: Effect of pH on the preconcentration recovery.

Conditions: Mo(II), 5.0×10-6 -1;

optimum conditions for determination of Mo(II).

Figure 6: Effect of HCl concentration for elution conditions:

Mo(II), 5.0×10-6 M; Ph 1.0; HCl, 1.0 mL; optimum conditions

for determination of Mo(II).

500


added. The separating funnel was shaken vigorously

-

termined according to calibration curve data and then

adsorbed amount of Mo was calculated. The retention

capacity (mg adsorbed Mo/ g adsorbent) was obtained

to be 0.1672 mg g-1 of adsorbent or 2.01 mg g-1 of

ligand.

3.4. Calibration graph, reproducibility and detection

limit

A series of standard solutions of Mo(II) were treated

conditions. Mo concentration can be determined in the

to 2.7×10-5 M with linear equation;

∆

of r2 ∆A is absorbance signal after precon-

centration and C is molar concentration of Mo×106).

M

for 10 replicate measurements of 5.0×10 , 1.0

×10 , 1.0×10-7, 3.0×10-6 and 1.0×10-5 M of Mo(II)

various samples on the determination of 5.0×10-6 M,

Mo(II)was investigated. The tolerance limit was de-

relative error less than 3% (Table 1). Some metal cat-

ions can be adsorbed on microcrystalline naphthalene

at different pH values. This proposed adsorbent is not

only able to remove anions of the Mo(II) solution but

also can decrease the interference of some cations.

Some of important ions that can be found in the real

samples with Mo(II) such as Sn , Hg , Cd , Co ,

Ca , Pb and Tl do not have any interference on

the determination of Mo(II). Al and Fe can be trouble-

some in the determination procedure but with precon-

centration their interference decreases.

The reported method is selective and simple and it

methods in Table 2 stripping voltammetry has a good

-

tractions are not sensitive enough and they consume a

-

On the basis of the results obtained from the Mo(II)

standards, the recommended preconcentration method

has been successfully applied prior to spectrophtomer-

ic determination of low values of Mo in the tap water

SpeciesTolerance limit

ion Mo(II) )

NH4

, Na , K , H3BO

3, Hg ,

Ba , Cd , Co , Ca , Pb ,

Sn , Sr , Tl

100

Al , Mg , Cr , Cu

Fe , Fe25

Zn

Sb , Ag1

Method))Reference

1[21]

Potentiometric

stripping10.1–100 5–250

[22]

[20]

Microcrystalline naphthalene

Proposed method

4

20

0.3

5–20

2.1–2000

[23]

[24]

–

Table 1: Interferences effect on the determination of

5.0 × 10-6 M, Mo(II).

Table 2: Comparison of some methods for preconcentration and determination of thallium with

proposed method.

501


(Tehran, taken after 10 min operation of the tap), rain

water (Tehran, 22 January, 2013) samples. The analy-

sis was performed by using the standard addition tech-

nique. The results are summarized in Table 3. Good

recoveries in all samples were obtained. This method

was reliable through comparing with each other [24-

26]. Table 4 summarizes the analytical characteristics

of the optimized method, including linear range, limit

of detection, reproducibility, and enhancement fac-

tor. The calibration graph was linear in the range of

to 2.7×10-5 M of Mo. The limit of detection,

the limit of detection, standard deviation of the blank

and slope of the calibration graph, respectively), was

-

dard deviation of three measurements is better than

3.0%. The enhancement factor was obtained from

the slope ratio of calibration graph after and before

4. CONCLUSIONS

-

lene is an effective separation and preconcentration

technique for trace elements. The method has the ad-

this proposed preconcentration method has a high en-

Table 3: Spectrophotometric of Mo(II) in the real samples after preconcentration.

SampleAdded (×10 M)Found (×10 M)ICPRecovery %

––-–

1.0

5.0

10.010.41 ± 0.07

––––

1.0

River water5.0

10.010.47 ± 0.076

Analytical featureParameter

10 to 2.7×10 ×Linear range ( M )

r2

10 M×Limit of detection (ng L

3.0a, %) (n = 10)

122Enrichment factorb

100Enhancement factor

10.00Sample volume (mL)

<4

Table 4: Analytical characteristics of organic-solution-processable functionalized-gra-

phene (SPFGraphene) for determination of Mo(II).

(a) Mo(II) concentration was 20 nM for which R.S.D. was obtained; (b) Enhancement factor is the slope ratio of

calibration graph after and before extraction.

502


richment factor (100) which develops possibility of

determining concentration levels as low as sub micro

amounts of Mo with eliminating the interference of

some diverse ions. The selected determination proce-

dure (after preconcentration) is convenient, sensitive

and fairly selective.

ACHNOWLEDGMENTS

The authors wish to thank the chemistry department

of Varamin branch Islamic Azad University for

REFERENCES

1. Izatt R.M., Bradshaw J.S., Nielsen S.A., Lamb

Chem. Rev., 85

2. Izatt R.M., Pawlak K., Bradshaw J.S., Bruening

R.L., Chem. Rev., 91

3. Izatt R.M., Pawlak K., Bradshaw J.S., Bruening

R.L., Chem. Rev., 95

A., Isaia F., Lippolis V., Schroder M., Verani G., J.

Chem. Soc., Dalton Trans

-

lanova F.A., Garau A., Isaia F., Lippolis V., Kive-

kas R., Muns V., Schroder M., Verani G., J. Chem.

Soc., Dalton Trans

6. Gomes M.M., Hidalgo Garcia M.M., Palacio Cor-

villo M.A., Analyst, 120

Anal. Chem., 61

Talanta, 44

Talanta, 44

10. Mahmoud M.E., Talanta, 45

11. Mahmoud M., Anal. Chim. Acta, 398

In: Proceeding of the 25th

FACSS Conference, Austin, TX, USA, and 11–15

October.

Anal. Chim. Acta,

230

14. Moghimi A., Ghiasi R., Abedin A.R., Ghammamy

S., Afr. J. Pure Appl. Chem., 3

15. Moghimi A., Chin. J. Chem., 25 (10) (2007), 640.

Ma-

ter. Sci. Res. India, 3 (1a) (2006), 27.

17. Moghimi A., Abdouss M., Afr. J. Pure Appl.

Chem., 6

Talanta, 48

J.

Appl. Polym. Sci, 110

20. Tabarzadi M., Abdouss M., Hasani S.A., Shoush-

tary A.M., Matwiss U., Werkstofftech, 41 (4)

(2010), 221.

Ind.

Eng. Res., 43 (2004), 2060.

22. Nayebi P., Moghimi A., Orient. J. Chem., 22 (3)

(2006), 507.

-

mi A., Aghabozorg H., Ganjali M. R., Microchem.

J., 69 (2001), 1.

24. Ganjali M.R., Pourjavid M.R., Hajiagha Babaei

L., Niasari M.S., Quim Nova, 27 (2004), 213.

25. Moghimi A., Shabanzadeh M., JCHR, 2 (2)

(2012), 7.

26. Tang C., Tracz A., Kruk M., Zhang R., Smilgies

J. Am.

Chem. Soc., 127


ABSTRACT

The catalytic highly regio- diastereo-, and enantioselective synthesis of a small library of spiropyrrolizidineoxindoles

Keyword:

Three-component reaction; Proline; Sarcosine.


Catalytic asymmetric multicomponent reaction (CAM-

chirality economy and environmental benignity. In ad-

dition, this strategy has manifested as a powerful tool

diversity [1]. It is therefore desirable to utilize and de-

velop this method for the synthesis of important het-

[4] (Figure 1). Asymmetric multicomponent 1,3 dipo-

lar cycloaddition of azomethineylides with alkenes can

be a great interest and useful strategies for stereoselec-

tive synthesis and develop of these class of molecules

and compounds having similar structure [5].

Three-Component Procedure for the Synthesis Chiral

Spirooxindolopyrrolizidines via Catalytic Highly Enantioselective

1,3-Dipolar Cycloaddition of Azomethineylides

and 3-(2-Alkenoyl)-1,3-Oxazolidin-2-ones

Mohammad Javad Taghizadeh1*, Khosrow Jadidi2

1 Ph.D.Student, Department of Chemistry, University of Imam Hossein, Tehran, Iran

2 Ph.D., Department of Chemistry, University of Shahid Beheshti, Tehran, Iran

1. INTRODUCTION


504

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 503-510 Taghizadeh MJ et al

However, it requires the use of at least one equivalent

in continuation of our previous work on the synthesis

as a catalyst to synthesis of a small library of this im-

1,3-dipolar cycloaddition reaction of azomethiney-

dipolarophile by using bidendate bis(imine)-Cu(II)

-

a variety of suitable aldehyde precursors, in optimized

-

-

-

ined using 10 mol% [Cu(OTf)2] as catalyst in a typical

reaction of azomethineylide 2a with dipolarophile 3a

at room temperature in aqueous ethanol as a solvent

(Scheme 1). The results are summarized in Table 1.


The ligands 1b and 1c bearing the electron-withdraw-

ing and relatively bulky Cl substituents at the 2- or/

and 6-positions of the benzene ring resulted in con-

siderably higher yields and enantioselectivities in

NH

NMe

O

MeO

NH

NH

O

HO NH

N

O

HO

Et

OMe

CO2Me

(-) horsfiline ( ) elacomine richnophiline

Figure 1: Spiro pyrrolidineoxindole alkaloids.

NR1

X

O

O

+NH

CO2H

NR1

NX

O

R2H

H

HO

N

NR1

X

O

N

EtOHRT, h

- CO2

2

[ +2] OO

O

N

OO

H

HR2

Ligand 1

4

Figure 2: Cyclohexane-1,2-bis(arylmethyleneamine) li-

gands 1(a-f).

Scheme 1: Asymmetric synthesis of new chiral spirooxindolopyrrolizidines 4 with ligand of 1.

NN

RR R=

N

ClCl Cl

SO

1a 1b 1c

1e 1f 1d

505

Taghizadeh MJ et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 503-510

comparison with the other ligands [10]. The highest

-

itywere achieved by employing ligand 1b. The yields

and enantiomeric ratios of the products showed the

temperature dependence of this process. A decrease in

decreased the reaction yield and enantioselectivity

we tested the effect of Cu salts (Table 2). In all cases,

Cu(OTf)2 proved to be the best copper source while

and longer reaction times (entries 3-4 vs.2). The use

of Zn(OTf)2 instead of Cu(OTf)

2 gave worse result

in term of enantioselectivity (entry1). The effects of

catalyst loading were also investigated and the best

results were obtained when 10 mol % catalysts load-

ing was used in the reaction. The ligand-to-metal ratio

of 1.1:1 using 20 mol % of ligand was investigated

under the similar conditions and the isolated yields

-

spectively. Lowering the catalyst loading to less than

10 mol % led to a sharp decrease in the results. It

should be noted, the addition of additives such as MS

4A, 3A did not give any observable changes in the re-

sults of the reaction and even lead to decreasing yields.

Considering the optimized reaction conditions, we

-

tion with various types of azomethine ylides and nu-

-

Entry Ligand Time (h)4a

b Ee (%)c

1 1a 25 24 55

2 1b 25 22

3 1c 25 20 63

4 1d 25 Race

5 1e 25 73 Race

6 1f 25 32 Race

7 1b 0 35 35

1b -40 <10 n.d

Table 1: Asymmetric synthesis of new chiral spirooxindolopyrrolizidines with ligand of 1(a- f).

(a) -

ence of 10% catalyst [Cu(OTf)2 -1=1.0: 1.1], unless otherwise noted; (b) Isolated yield; (c) Determined by chiral HPLC

analysis.

Entry Lewis acid Time (h)4a

b Ee (%)c

1 Zn(OAc)2

12 Race

2 Cu(OTf)2

22

3 Cu(OAc)2

23 66

4 Cu(Cl)2

76 Race

5 Cu(OTf)2

d 22

Table 2: Dependence of reaction with Lewis acid.

(a)2Cl

2 at room tem-

perature in the presence of 10% catalyst [Lewisacid-1=1.0:1.1], unless otherwise noted; (b) Isolated yield;

(c) Determined by chiral HPLC analysis; (d) 20% catalyst is used.

506


lopyrrolizidines 4a-j (Table 3).

The structures of cycloadducts were assigned from

their elemental and spectroscopic analyses including

IR, 1H NMR, 13C NMR, and mass spectral data. The

observation of two characteristic triplets and one dou-

blet in the 1

unambiguously the formation of a new pyrrolizidine

-

reochemistry of products 4 that was carried out here

using several NMR spectroscopy techniques. The

ORTEP view of single crystal X-ray analysis of 4g

with atomic numbering is shown in Figure 3. On the

basis of X-ray structure of 4, we can now assign the

(C13). X-ray crystallographic analysis of compound

Because reactions of most non-stabilized azome-

HOMO (dipole)-LUMO(dipolarophile) controlled [11],

thus, in order to obtain an increased reaction rate, the

3-Cu(OTf)2

dipolarophileto form square planner geometry [12].

On the other hand, condensation of isatin derivative

-

dition of activated dipolarophileswithazomethineylide

-

rolizidine 4 which contain contiguous stereogenic

-

isomers could be prepared theoretically, only diaste-

Entry X R1

R2

Product

1 H H Me 4a

2 H H Ph 4b

3 H Me Me 4c

4 H Et Ph 4d

5 H Bn Me 4e

6 Br H Me 4f

7 Br Me Me 4g

Br Et Me 4h

10 Br Me Ph 4i

11 NO2

H Me 4j

Table 3: Asymmetric synthesis of new chiral spirooxindolopyrrolizidines de-

rivaitives 4.

Figure 3: ORTEP diagram of one of the four crystallograph-

ic independent molecules in the asymmetric unit of 4g. Ther-

mal ellipsoids are at 30% probability level.

507


reoisomer 4 was obtained in high yield in all the cases

that we present in this article (Scheme 2). Based on

-

troscopic techniques, the transition state and the reac-

tion pathway were proposed as below:

3. EXPERIMENTAL

General procedure: To a magnetically stirred solution

of an isatin derivatives (1 mmol), proline (1 mmol)

10 mL EtOH was added dropwise at room tempera-

The solvent was then removed under reduced pressure

and the residue was separated by recrystalization in

CHCl3.

4. CONCLUSIONS

-

lar cycloaddition reaction of azomethineylides with

-

optimized condition. The reaction was accomplished

with 10% catalyst at room temperature in environ-

mentally friendly aqueous ethanol. The structures of

the products were elucidated using IR, mass, one and

two dimensional NMR techniques, and X-ray single

discussed on the basis of the assignment of the abso-

-

α2Cl

2),

IR(KBr)(υ , cm-1

(C=O), 3430(NH); 13); 1.17

(3H, d, 3JHH

=6.3 Hz, CH3 2

),

(2H, m, CH2

NH

N

O

R

O

N

O

O

H

NH

HN

CO2H

O

OH

NH

N

O

NN

RRCu

OO

O N

R

NN

R RCu

OTfTfO

ON

OO

R

N

N

Cl

Cl

Cu

O

NO

O R

Re-faced attackRepulsive

Cl

Cl

NH

N

O

Si-faced attackfavorable

-CO2

Scheme 2: Propose of the transition state and the reaction pathway.


m, CH and CH2), 4.13-4.21 (1H, m, CH), 4.31 (1H, d,

3JHH

s, NH); 13

3 3),

2

3C=O); MS, 352 (M

-

α2Cl

2),

IR(KBr)(υ , cm-1

(C=O), 3430(NH); 1

3);

1.77-2.02 (4H, m, 2CH2), 2.67 (1H, m, CH), 3.15

OCH2

3JHH

13

3

(4C, 4CH2

OCH2

(M ,7), 200 (100), 131 (70).

α2Cl

2),

IR(KBr) (υ , cm-1

(C=O); 1

3); 1.16 (3H, d,

3JHH

=6.3 Hz, CH3), 1.72-2.13 (4H, m, 2CH

2), 2.57

3.16 (3H, s, NCH3

m, CH and CH2), 4.11 (1H, m, CH), 4.21 (1H, m,

3JHH

3JHH

(1H, m, CH), 7.14 (1H, d, 3JHH

m, CH); 13

3); 16.4 (1C,

CH3), 24.7, 26.4, 27.6, 43.1, 62.7 (5C, 5CH

2), 41.2

(1C, NCH3

,

α

(c 0.01, CH2Cl

2) IR(KBr) (υ , cm-1): 1613(C=O),

1HNMR (300.1 MHz,

3

3JHH

=7.2 Hz, CH3), 1.76-2.01 (4H,

m, 2CH2), 2.67 (1H, m, CH), 3.13 (1H, m, CH), 3.61

2), 4.46

3JHH

13

3

(1C, CH3 2

), 35.0

(1C, NCH2

OCH2

(M

α

0.01, CH2Cl

2), IR(KBr) (υ , cm-1): 1616(C=O),

1HNMR (300.1 MHz,

3); 1.15 (3H, d, 3J

HH=6.6 Hz, CH

3

(4H, m, 2CH2), 2.65(1H, m, CH), 3.16 (1H, m, CH),

2

4.11(2H, m, CH2), 4.52(1H, m, CH), 4.76 (1H, d,

3JHH

3JHH

5.13 (1H, d, 3JHH

Ar-H); 13

3); 15.5(1C, CH

3),

2

3CH), 54.3 (1C, NCH2 2

), 72.1(1C),

α

(c 0.01, CH2Cl

2), IR(KBr) (υ , cm-1): 1614(C=O),

1HNMR (300.1

3); 1.15 (3H, d, 3J

HH=6.7 Hz, CH

3), 1.76-

2), 2.07-2.17 (1H, m, CH

2), 2.57 (1H,

2), 3.56 (1H, dt, 2J

HH=12

Hz, 3JHH 2

),


4.16 (1H, dt, 2JHH

=12 Hz, 3JHH

=6 Hz, CH), 4.31 (1H, d, 3J

HH

3JHH

(1H, m, Ar-H), 7.47 (1H, d, 3JHH

(1H, s, NH); 13

3); 16.1(1C,

CH3), 24.2, 27.4, 41.2, 42.7, 62.5 (5C, 5CH

2

, M

α

(c 0.01, CH2Cl

2), IR(KBr) (υ , cm-1): 1614(C=O),

1HNMR (300.1 MHz,

3); 1.16 (3H, d, 3J

HH=5.1 Hz, CH

3), 1.76-2.17

(4H, m, 2CH2 2

),

3.14(3H, s, NCH3), 3.66 (1H, m, CH), 3.04 (3H, m,

CH and CH2), 4.17 (1H, m, CH), 4.37 (1H, d, 3J

HH

Hz, CH), 6.67 (1H, d, 3JHH

s, Ar-H), 7.43 (1H, d, 3JHH

13CNMR

3); 16.4(1C, CH

3), 24.5, 27.7, 41.3,

2), 42.4(1C, NCH

3

, M

(M , M

3-((1'S,2'S,3R,7a'R)-5-bromo-1-ethyl-1'-methyl-

α

(c 0.01, CH2Cl

2), IR(KBr) (υ , cm-1): 1611(C=O),

1HNMR (300.1 MHz,

3); 1.15 (3H, d, 3J

HH 3

3JHH

=7 Hz, CH3 2

(1H, m, CH2

CH2

3JHH

=7 Hz, CH2), 3.56 (1H, dt,

2JHH

=12 Hz, 3JHH

and CH2), 4.16 (1H, dt, 2J

HH=12 Hz, 3J

HH=6 Hz, CH),

4.31 (1H, d, 3JHH

3JHH

Hz, Ar-H), 7.27 (1H, m, Ar-H), 7.47 (1H, d, 3JHH

Hz, Ar-H); 13

3); 12.4 (1C,

CH3), 16.1(1C, CH3

5CH2), 35.1 (1C, NCH

2

MS, 462, 464 (M , M , M

60), 131 (100).

α

(c 0.01, CH2Cl

2), IR(KBr) (υ , cm-1): 1614(C=O),

1HNMR (300.1 MHz,

3); 1.77-2.02 (4H, m, 2CH

2), 2.67 (1H, m, CH),

3.15 (1H, m, CH), 3.24 (3H, s, NMe), 3.61 (1H, m,

2, 2CH), 4.46 (1H, m,

3JHH

m, Ar-H); 13

3); 24.4, 27.4,

2), 42.1 (1C, NCH

3

2), 72.1(1C), 110.6,

, M

, M

-

α

(c 0.01, CH2Cl

2), IR(KBr)(υ , cm-1): 1615(C=O),

1HNMR (300.1

3

3JHH

=6.6 Hz, CH3), 1.67-

2 2) 2.52 (1H,

m, CH), 2.66 (2H, m, CH2

CH2

3JHH

4JHH

3JHH

4JHH

=313CNMR (300.1 MHz,

3 3

(5C, 5CH2

,

REFRENCES

Angew. Chem. Int. Ed.,

510


44 (2005), 1602. (b) Catalytic Asymmetric Mul-

ticomponent Reactions.

Sons.

2. Jossang A., Jossang P., Hadi H.A., Sevenet T.,

Bodo B., J. Org. Chem., 56

Can. J. Chem.,

50

The Alkaloids, R.H.F. Man-

-

ford C.V., Scheidt K.A., Angew. Chem., Int. Ed.,

46

Lin G., Curr. Drug Metab., 12

Pharmazie, 66 (2011),

Pharmazie, 64

Adv. Food

Nutr. Res., 45 -

nor C.C.J., J. Nat. Prod., 44

J. Am. Chem. Soc., 127 (2005),

J. Med. Chem., 49

(2006), 3432. (c) Shangary S. et al., Proc. Natl.

Acad. Sci. U.S.A., 105

6. Taghizadeh M.J., Arvinnezhad H., Samadi S.,

Jadidi K., Javidan A., Notash B., Tetrahedron Let-

ters, 53

7. (a) Azizian J., Asadi A., Jadidi K., Synth. Com-

mun., 31 (2001), 2727. (b) Azizian J., Jadidi

Synth. Commun.,

30

M., Jadidi K., Indian J. Chem., Sect B, 39 (2000),

304. (d) Azizian J., Morady A.V., Jadidi K., Meh-

Synth. Commun., 30 (2000),

537. (e) Azizian J., Soozangarzadeh S., Jadidi

K., Synth. Commun., 31

K., Ghahremanzadeh R., BazgirA.,Tetrahedron,

65

R., Bazgir A., J. Comb. Chem., 11

(h) Mehrdad M., Faraji L., Jadidi K., Eslami P.,

Sureni H., Monatsh. Chem., 142

Jadidi K., Ghahremanzadeh R., Mirzaei P., Bazgir

A., J. Heterocycl. Chem., 48 (2011), 1014. (j) Mo-

emeni M., Arvinnezhad H., Samadi S., Tajbakhsh

M., Jadidi K., Khavasi H.R., J. Heterocycl. Chem.,

49

J.

Am. Chem. Soc., 127

Zhang X., Raghunath M., Org. Lett., 7 (2005),

4241. (c) Llamas T., Arrayas R.G., Carretero J.C.,

Org. Lett., 8

Angew. Chem. Int. Ed., 45

Org. Lett., 5 (2003),

5043. (f) Gothelf A.S., Gothelf K.V., Hazell R.G.,

Jorgensen K.A., Angew. Chem. Int. Ed., 41 (2002),

J.

Am. Chem. Soc., 124 (2002), 13400.

Termhedmn

Leuers, 34

Miyazaki S., and Otani T., Tetrahedron Lett., 45

10. (a) Jacobsen E.N., Kakiuchi F., Konsler R.G.,

Larrow J.F., Tokunaga M., Tetrahedron Lett., 38

J. Org.

Chem., 63

K.B., Jacobsen E.N., Angew. Chem. Int. Ed., 38

-

son S.R., Jacobsen E.N., J. Am. Chem. Soc., 112

Tetrahedron Asymmetry, 8 -

bauer R., Jacobsen E.N., Angew. Chem. Int. Ed.,

39 (2000), 3604.

11. Gothelf K.V., Jorgensen K.A., Chem. Rev., 98

Tetrahedron

Lett., 34


ABSTRACT

Skeletal muscle may develop adaptive chaperone and enhancementdefense system through daily exercise

stimulation. The present study investigated resistance and exhaustion training alters the expression of chaper

one proteins. These proteins function to maintain homeostasis, facilitate repair from injury and provide protection.

Exercise-induced production of HSPs in skeletal muscle and peripheral leukocytes and, it may provide insight into

the mechanisms by which exercise can provide increased protection against stressors. The aim of this study was

part in the intervention volunteered to give blood samples. Levels of chaperone proteins weremeasured in response

but decreased after resistance training. The data showed that human skeletal muscle responds to the stress of

a single period of Progressive trainingby up regulating and resistance training by down regulating expression of

Keyword:


Living cells are continually challenged by conditions

which cause acute and chronic stress. Heat shock pro-

teins (HSP) are a class of functionally related proteins

to elevated temperatures or other stress. Molecular

chaperones such as heat shock proteins (HSPs) are

known to contribute to reducing cellular damage. HSPs

havemultiple functions in maintaining intracellular in-

tegrity viaprotection, repair and even control of cell

death signaling [1-3]. They play an important role in

proteins interactions such as folding and assisting in the

establishment of proper protein conformation and pre-

The Effect of Resistance and Progressive Training on

HSP 70 and Glucose

Farah Nameni

Assistant Professor, Department of Physical Education, Varamin-Pishva Branch, Islamic Azad University,

Varamin, Iran

1. INTRODUCTION


512

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 511-515 Nameni F

vention of unwanted protein aggregation. Heat shock

proteins (HSP) are increasingly seen as important

players in the response of our biochemistry to stresses

and damage. Few data have been reported concerning

HSP70 is associated with the protection of stri-

ated muscle from injury and the attenuation of skel-

etal muscle atrophy. Therefore enhancementof poten-

HSP70 is reported to be enhanced by thermalstress

-

-

of molecular chaperone proteins may play important

roles in protection and repair of skeletal muscle

-

increased, but there was no change in the HSP70 pro-

tein content. HSP70 was selected because this pro-

tein typically demonstrates very large increases after

of HSP70 are present in the systemic circulation of

healthy individuals. Previous studies have shown that

the systemic concentration of HSP70 is elevated after

Several investigators have demonstrated the in-

response to hyperthermia [10], ischemia, and hy-

viewed as intracellular proteins with a vital role in

-

-

shown to induce the synthesis of HSP70 [11]. Prior

-

ercise. The acquisition of muscle tolerance to contrac-

-

ing appears to be partially associatedwith molecular

mechanisms including chaperone functions in addi-

tionto neuromuscular and morphological adaptations.

training increases several molecular chaperone pro-

teins in skeletal muscle, such as HSP25, HSP70 and

glucose-regulated protein (GRP) [2, 5 and 12]. HSPs

and helping protein formation [3]. These functions of

HSPs may potentially contribute to acquisition of a

muscledefense system with training [2]. HSPs are in-

creasingly seen as important players in the response of

our biochemistry to stresses and damage.

-

temic circulation of healthy individuals. Previous

studies have shown that the systemic concentration of

training attenuates contraction-induced injury in skel-

2. MATERIAL AND METHODS

on Progressive training group with mean age 23 ± 2

[±SEM], weight 57.3 ± 6.53, height 161.1± 3.21 cm,

uptake[VO ] 5.1 ± 0.4 L /min). Subjects were in-

formed as to the potential risks associated with par-

ticipation in the study before obtaining their written

informed consent to participate.The study was carried

out in accordance with the IAU and approved by the

-

ing on HSP70 and glucose in peripheral leukocytes

-

tometry and RT/PCR, respectively and glucocard 01.

Progressive training subjects performed Bruce

Resistance training Subjects performed 30 minute re-

sistance training. The laboratory temperature during

venous blood were collected in heparinized syringes

and kept on ice until analysis for hematocrit on ABL

700 apparatus.

To determine the serum HSP70 protein concentra-

513

Nameni F Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 511-515

tion were obtained and placed in a tube containing a

clot-inducing plug. This tube spun in a centrifuge at

immune sorbent assay method was used to determine

the concentration of HSP70 protein in serum. All sam-

means ± SEM. Statistical analysis was conducted by

using analysis of variance (ANOVA) repeated mea-

comparisons among means. A P value < 0.05 was con-

3. RESULTS

After Progressive, the anticubital serum HSP70

concentration was elevated but after resistance

training serum HSP70 concentration was decreased

(Table and Figure 1). Repeated Measurers test were sig-

-

-

4. DISCUSSION

-

evation in constitutive levels of this protective protein

-

teins (HSP) possibly have a systemic function, includ-

-

of HSPs will facilitate any cellular remodeling, that

and other stresses are an important component of the

cellular protective response. These proteins facilitate

successful repair from injury and to aid adaptation and

remodeling of the cell to prevent the damage [4].Ac-

Figure 1: Mean HSP70 before exercise and in recovery in

2 groups.

Variables Time N

Mean±Std. Deviation

(Ng/ml)

Glucose

(Mg/dl)

Progressive

training

before

9after

2h after

Resistance

training

before

10after

2h after

Table 1: Mean±Std. deviation HSP70 and glucose before exercise and in recovery.

514

Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 511-515 Nameni F

-

lar Hsp72 has potent immune regulatory effects [15].

-

to stimulate synthesis of HSPs in peripheral blood leu-

in blood immediately at the end of running, which

shows a positive function of HSP in leukocytes of ath-

-

glucose over produce a set of proteins called glucose-

regulated proteins (GRP). The functions of HSP, GRP

and OSP are incompletely understood, but evidence

suggests that many stress proteins are enzymes that

either provide immediate stress protection or conduct

cellular repair processes. Sustained physical activity

results in the progressive depletion of glucose and gly-

cogen stores, a phenomenon that is highly correlated

treated with agents that perturb calcium homeostasis,

synthesis GRP and HSP70 [17].

The elevation of body temperature and depletion

of glycogen [11] are all regarded as factors that induce

the treadmill running, as used in the present study,

-

ing level of peripheral leukocytes HSP70 and that

the resultant accumulation of HSP70 helps to protect

stress-loaded cells from injury due to the elevation of

However,comparison amongst studies is com-

intensity, durationand damage), muscle group, and

differences in subject characteristics (training and nu-

the down regulation of HSP-positive cells seems to

-

-

HSP70 can be released independently of necrotic cell

death in response to a number of stressful conditions

-

5. CONCLUSIONS

The data presented show that human leukocyte re-

Table 2: The results of (ANOVA) repeated measures

HSP70 and glucose in 2 groups.

Time Sig. F

before

after 0.099

2h after

Table 3: Table 3: The results of ANOVA HSP70 and

glucose in 2 groups.

Group Factor Sig. F

Progressive

training

0.04*

glucose .000*

Resistance

training

0.002*

glucose .000*

Figure 2: Mean Glucose before exercise and recovery in 2

groups.

515

Nameni F Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 511-515

training by up regulating and resistance training by

-

sue assayed (skeletal muscle, lymphocyte, venous

and arterial serum). The differences observed when

HSP70 in the present study may be related to the mode

-

ACKNOWLEDGEMENTS

-

ing study and we acknowledge the technical assistance

of Noor Lab. This study was supported by Varamin-

PishvaBranch Islamic Azad University.

REFERENCES

1. (a) Kregel K.C., J Appl. Physiol., 92 (2002), 2177;

Cardiovasc Res., 51 (2002),

637.

-

raoka I., Am J Physiol. RegulIntegr Comp Physiol.,

296

3. Sreedhar A.S., Csermely P., Pharmacol Ther., 101

(2004), 227.

4. Khassaf M., Child R.B., McArdle A., Brodie

J. Appl. Physiol., 90

(2001), 1031.

5. Gonzalez B., Hernando R., Manso R.,

Arch., 440 (2000), 42.

J. Appl. Physiol., 92 (2002),

7. Febbraio M., Koukoulas I., J. Appl. Physiol., 89

(2000), 1055.

Acta Physiol. Scand., 171 (2001),

P.L., Hargreaves M., Febbraio M.A., Cell Stress

Chaperones, 6 (2

Scarsella G., Mol. Cell Biochem., 204 (2000), 41.

-

las I., Van Hall G., Saltin B., and Pedersen B.K., J

Physiol., 53

12. Murlasits Z., Cutlip R.G., Geronilla K.B., Rao

Exp. Geron-

tol., 41

M.P., Noble E.G., Am. Physiol. Lung Cell Mol.

Physical, 293

Sports Med., 39

15. Lancaster G.I., Moller K., Nielsen B., Secher N.H.,

Febbraio M.A., Nybo L., Cell Stress Chaperson, 9

(3) (2004), 276.

-

[PubMed-indexed for MEDLINE], 2003.

17. Fehrenbach E., Passek F., Niess A.M., Pohla H.,

Med. Sci.

Sports Exerc., 32

J.

Appl. Physiol., 96 (5) (2004),1776.

Suzuki K.,

(2010), 7.


ABSTRACT

O4) nanoparticles/Ag-NaY

zeolite was synthesized by hydrothermal method (HM). Then, Ag-NaY zeolite was prepared from NaY zeolite by

ion-exchange method (IEM). In the next step, Fe O4 nanoparticles (NPs) were incorporation and deposited on the

Ag-NaY zeolite structure by using precipitation method (PM). The synthesized samples were characterized by SEM,

EDAX and XRD techniques. The GC-FID and IR analysis results demonstrated that about 99% of methamidophos

acetonitrile and methanol solvents were lower. It seems that a nonpolar solvent transfer to the reactive surface site

on the composite without occupying and blocking of these sites.

Keyword: O4)

nanoparticles/Ag-NaY faujasite molecular sieve zeolite (FMSZ); Composite.


O, S-dimethyl phosphoramidithioate or methamidophos

with molecular formula C2H NO

2PS is an organophos-

phorus insecticide (Figure 1), poses inevitable threat to

persons who make contact, thereby causing health haz-

ards. Its mode of action in insects and mammals is by

decreasing the activity of an enzyme important for ner-

vous system function called acetylcholinesterase. This

enzyme is essential in the normal transmission of nerve

dophos as an Organophosphorus

Insecticide on the Magnetite (Fe3O

4) Nanoparticles/Ag-NaY Fau-

jasite Molecular Sieve Zeolite (FMSZ) Composite

Meysam Sadeghi1*, Mirhassan Hosseini2

1 M.Sc., Young Researchers and Elite Club, Islamic Azad University of Ahvaz Branch, Ahvaz, Iran

2 M.Sc., Payame Noor University, Germi Moghan, Ardebil, Iran & Nano Center Research,

Imam Hossein Comprehensive University (IHCU), Tehran, Iran

1. INTRODUCTION


Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 517-524 Sadeghi M et al

impulses. Methamidophos is a potent acetylcholines-

terase inhibitor [1, 2]. Recently, there has been grow-

ing interest in the development of novel methods and

of organophosphorus pollutants (OPPs). Inorganic

industry as adsorbents, sensors, catalyst, etc. Because

of their unique morphological features and high sur-

adsorbents for decomposition or detection of variety

of pollutants and harmful substances, including or-

ganophosphorous compounds [3]. On the other hand,

zeolites are widely used in industry for water and

waste water treatment, waste gas treatment, as cata-

lysts, as molecular sieve, in the production of laun-

dry detergents, nuclear processing medicine and in

agriculture purposes for the preparation of advanced

materials and recently to produce the nanocomposites

-

to investigated the reactivity of the actual chemical

-

line aluminosilicates containing pores and channels of

molecular dimensions that are widely used in industry

catalysts. A representative empirical formula of a zeo-

lite is: M2/n

.Al2O

3.ySiO

2.wH

2

a Group I or II ion, although other metal, non-metal

and organic cations may also balance the negative

charge created by the presence of Al in the structure

(Figure 2). It has a 3-dimensional pore structure with

and z planes similar to LTA, and is made of secondary

building units 4, 6, and 6-6 [11, 12].

The methods for modifying zeolites are usually by

its compounds had been important in human life due

role in nature. Recently they have widely utilized in

material for the incorporation of Fe3O

4 as the guest

due to its three dimensional channels which limits the

particle size of Fe3O

4 during the growth. Then, the de-

by 14.7 wt% magnetite (Fe3O

4

faujasite molecular sieve zeolite (FMSZ) composite at

room temperature.

2. EXPERIMENTAL

All chemical are purchased from Merck and Alfa Ae-

sar German Fluka was used as received.

2.1. Preparation of NaY zeolite by hydrothermal

method (HM)

10 mL of distilled water until being dissolved.

-Figure 1: Structure of O, S-dimethyl phosphoramidithioate

(methamidophos).

Figure 2: Structure of type-Y faujasite zeolite.

Sadeghi M et al Int. J. Bio-Inorg. Hybd. Nanomat., Vol. 2, No. 4 (2013), 517-524

-

lution of 22 g of sodium silicate was slowly added to

-

ing dissolved (solution B). Solution A was slowly add-

min. The solution was transferred to a stainless steel

2.2. Preparation of Ag-NaY zeolite by ion exchange

method (IEM)

In a typical preparation procedure, 2 g of the synthe-

-

0.15 M silver nitrate (AgNO3

-

-

16 h. Finally, the clean and dry zeolite was calcined in

2.3. Preparation of Fe3O

4 nanoparticles/Ag-NaY ze-

olite composite by precipitation method (PM)

For the synthesis of Fe3O

4-

added to 40 mL of distilled water and slowly stirs for

10 min until homogenate suspension was obtained. Af-

ter that a desired quantity of FeCl3 and FeCl

2 solutions

with molar ratio of 2:1 was added into the suspension

stirred vigorously about 20 mL of 1 M NaOH solution

was slowly added and vigorous stirring was continued

for another 30 min. The synthesized product (Fe3O

4

2.4. Reaction procedure of Fe3O

4 nanoparticles/Ag-

NaY zeolite composite with methamidophos (com-

posite/methamidophos sample)

For the investigation of the reaction between Fe3O

4

-

amidophos. the samples were prepared according to

the following method: 5 mL of methanol, acetonitrile

µL of methamido-

phos, 10 µL of octane as internal standard and 0.35 g

of Fe3O

4

do a complete reaction between composite and or-

ganophosphorus compound, all samples were attached

to a shaker and were shaken for 10 h under N2 atmo-

sphere and in room temperature. Then, by micropipette

µL of solution and injected to GC

instrument.

2.5. Characterization of samples

The morphology and particle size of the crystalline

zeolites and composite were analyzed using SEM

images. Semiquantitative analysis were carried out

connected to LEO-1530VP XL30 Philips scan-

ning electron microscope. Prior to the measurement,

the samples were coated with a thin layer of gold.

-

corded at room temperature using a Philips X’Pert Pro

α1 ra-

θ with a scanning

-

actions. A Varian Star 3400CX series gas chromato-

thickness) was used to monitor the decontamination

reactions. The GC conditions used were as follows:

-1

13 min.

The injector, MS quad and source temperatures

-1. The IR spec-

trum was scanned using a Perkin-Elmer FTIR (Model

2000) in the wavelength range of 450 to 4000 cm-1

with KBr pellets method.

520


3. RESULT AND DISCUSSION

3.1. Scanning electron microscope (SEM) study

The morphology and crystallite size of the as-syn-

thesized samples were investigated by SEM images

(Figure 1). Comparison between the morphologies

morphology and crystalline size are retained with ion

(Figure 3a and 3b). On the other hand, as it is indicat-

ed by image with high resolution, the Fe3O

4 nanopar-

size for the Fe3O

4 nanoparticles was less than 100 nm.

Also, some particles aggregation has occurred due to

synthesize of nanoparticles of Fe3O

4 on the surface of

zeolite.

3.2. Energy-dispersive x-ray spectrometer (EDAX)

analysis

Figure 4 give the composition elements present in

Fe3O

4

-

-

dium (Na), aluminum (Al), silicon (Si) and silver (Ag)

the other hand, in this spectrum, the appeared two

to the binding energies of iron (Fe) which reveals the

in the prepared sample, respectively.

3.3. X-Ray diffraction (XRD) patterns

3O

4 nanoparticles/

(a)

(b)

(c)

Figure 3: The SEM images of the samples: (a) NaY, (b) Ag-

NaY, c) 14.7 wt% Fe3O

4 nanoparticles/Ag-NaY.

Figure 4: The EDAX analysis of the 14.7 wt% Fe3O

4

nanoparticles/Ag-NaY.

521


-

crystallinity is observed, associated with the lower in-

tensity of the peaks at 2Theta=10-34. This effect could

be related to a dealumination of its structure, possibly

and Fe3O

4

3O

4 depos-

new diffraction peak. The peaks of Fe3O

4 phase ap-

peared at 2θ

-

tively [13, 21]. These peaks are illustrated as the red

points in Figure 5c. The structures of prepared Fe3O

4

-

ment. The average particle size was calculated from

line broadening of the peak at 2θ

Scherrer equation:

(1)

λ is the wavelength

of X-ray source, β

θ is the angle of incidence for the select-

ed diffraction peak (Bragg diffraction angle). The av-

erage crystallite size of the Fe3O

4 nanoparticles were

calculated about 31 nm.

3.4. GC-FID analysis

between 14.7 wt% Fe3O

4-

lite composite and methamidophos was investigated

-

ciency, the effects of different solvents and time inter-

vals have been investigated. The GC chromatograms,

area under curve (AUC) data and results under dif-

ferent conditions are summarized in Figures 6 and 7

organo-phosphorous insecticide, the integrated area

under peak data of two samples, methamidophos and

octane as the internal standard have been given for all

solvents and times. Subsequently, the ratios of the in-

tegrated data (integrated AUC of methamidophos/in-

-

iments were performed at different time intervals from

then a slight increasing trend was observed. These re-

-

dcos

Figure 5: The XRD patterns of the samples, (a) Na-Y, (b) Ag-NaY, c) Fe3O

4 nanoparticles/Ag-NaY.

522


lower for acetonitrile and methanol as the solvents.

Notwithstanding the transition state must be involved

in the polar reaction, polar solvent hinders the reac-

tion's progress.

It could be construed from GC analysis that polar

solvent can compete with the reaction sites presented

on the surface of the composite including Bronsted

)

sites. In particular, the blocking of Lewis acid sites

would hinder the coordination of methamidophos.

Since methanol is considered as such a strong hin-

drance to the reaction, this points out to the fact that

isopropanol simply blocks access to the surface of the

catalyst.

3.5. FT-IR spectrum

The FT-IR spectrum of the 14.7 wt% Fe3O

4 nanopar-

Figure 6: The GC chromatograms for methamidophos-Fe3O4 nanoparticles/Ag-NaY sample.

Solvent SampleAUC/Octane

(1)

AUC/

methamidophos (2)

Ratio

(AUC 2/AUC 1) (%)

Methanola 356489 333567 100.00

b 356246 234605 70.34

Acetonitrilea 397726 332461 100.00

b

a 410687 405992 100.00

b 000000 000000 00.00

Table 1: The GC analysis results in the presence of different solvents, (a) zero time (the blank solution)

and (b) after 10 h.

523


with methamidophos is shown in Figure 7. The peak

at 463 cm-1 is corresponded to the structure insensitive

internal TO4 (T= Si or Al) tetrahedral bending peak

-1 is attributed to the

-

lite. The peaks at 676 and 754 cm-1 -

ternal linkage symmetrical stretching and internal tet-

-1 and 1070 cm-1 are

assigned to internal tetrahedral asymmetrical stretch-

--1 are

-1 regions are

corresponded to the synthesized Fe3O

4 nanoparticles.

On the other hand, the adsorption of methamidophos

on the 14.7 wt% Fe3O

4

was investigated by IR spectrum. The new peaks at -1 are seen. These ob-

served IR data lead to an understanding of the ad-

sorption reaction of methamidophos on the surface of

4. CONCLUSIONS

-

-

3O

4 nanopar-

of methamidophos on this composite was investigat-

-

-

vent after 10 h.

ACKNOWLEDGEMENTS

-

ports of Tehran Imam Hossein comprehensive Univer-

sity (IHCU), Iran.

REFERENCES

1. Antonious G.F., Snyder J.C., Bull. Environ. Con-

tam. Toxicol, 52

2. Hussain M.A., Bull. Environ. Contam. Toxicol, 38

J. Am. Chem. Soc., 122

J.

Nanomater. Bios, 7

-

nagdi M.H., Molecules, 17

6. Ibrahim H.M., Behbehani H., Makhseed S., El-

nagdi M.H., Molecules, 16 (2011), 3723.

7. Batista A.C.L., Villanueva E.R., Amorim R.S., Ta-

vares M.T., Campos-Takaki G.M., Molecules, 16

-

michi A., Niwa M., Molecules, 16

Langmuir, 15

10. Cundy C.S., Stud. Surf. Sci. Catal., 57 (2005), 65.

Atlas of Zeolite Structure Types, 5th edn. Elsevier.

12. Ghobarkar H., Schlaf O., Guth U., Prog. Solid. St.

Chem., 27

13. Jahangirian H. et al., Dig. J. Nanomater. Bios, 8

(2013), 1405.

J.

Ind. Eng. Chem., 13 (2007), 1142.

Int. J. Mol. Sci., 14 (2013),

Figure 7: The IR spectrum for adsorbed O, S-dimethyl

phosphoramidithioate (methamodophos) on the 14.7 wt%

Fe3O

4 nanoparticles/Ag-NaY zeolite composite.

524


16. Khandanlou R., Ahmad M., Shameli K., Kalantari

K., Molecules, 18

17. Granitzer P., Rumpf K., Materials, 4

-

Dig. J.

Nanomater. Bios, 7

US Pat. No. 3

US Pat. No. 25

(2006), 57.

21. Ghandoor H.E., Zidan H.M., Mostafa M.H., Ismail

I.M., Int. J. Electrochem. Sci., 7 (2012), 5734.

international journal of bio-inorganic hybrid nanomaterials

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