German Edition: DOI: 10.1002/ange.201709303Ancient MaterialsInternational Edition: DOI: 10.1002/anie.201709303

Paleo-inspired Systems: Durability, Sustainability, andRemarkable PropertiesLo"c Bertrand,* Claire Gervais, Admir Masic, and Luc Robbiola

ancient materials · archaeology · durability ·paleontology · redox chemistry

1. Introduction

From archaeological remains to fossils, historical andancient materials provide a fundamental window on our past,gathering materiality and function in an integrative manner.[1]

These materials are essential to elucidate the origin andevolution of life forms on Earth,[2] are tangible testimonies ofpast human activities,[3] and allow assessing anthropic impactson Earth climate and environment.[4] Less discussed is their

potential of inspiration for the designof novel chemical and material systemsor devices. Ancient materials haveoften undergone a high-level of se-quential selection and filtering overtime, leading to highly efficient prop-

erties, such as in the metallic luster finishes in ancientceramics.[5] They can be considered as a subcategory ofmaterials produced under extreme conditions, where extremevalues are attained in time instead of pressure or temperature.The time component is a fundamental characteristic of theirelaboration, evolution, and understanding.[6, 7] Long-termpreservation in natural contexts provides examples of phys-icochemical resilience (stability over time in a dynamicenvironment) to environmental conditions up to billions ofyears. We therefore argue that the added value of their historyendow ancient materials with chemical specificities that are ofgreat interest to conceive novel synthetic paleo-inspiredsystems incorporating functionalities, such as tailored opticalresponse or environmental resilience. In many cases, how-ever, precise knowledge on the raw materials, recipes, andconditions to produce ancient artefacts has been at leastpartly lost. Some knowledge can be retro-engineered fromdirect in-depth material studies. The whole process involvesthe steps of understanding the composition of the collectedmaterial with interesting functionalities, designing synthesisroutes to reproduce corresponding functionalities, and com-paring the properties of the newly produced material toexpected performances. This process contributes to a descrip-tion and fundamental understanding of long-term kinetic andthermodynamic behavior laws of material systems. ThisMinireview therefore discusses the exceptional potential ofidentifying properties of interest from direct harvesting inancient materials. We present a selection of examples fromthe literature and our works that illustrate the diversity ofthese properties and show how paleo-inspiration couldfurther be developed to design resilient materials, systems

The process of mimicking properties of specific interest (such asmechanical, optical, and structural) observed in ancient and historicalsystems is designated here as paleo-inspiration. For instance, recoveryin archaeology or paleontology identifies materials that are a posterioriextremely resilient to alteration. All the more encouraging is that manyancient materials were synthesized in soft chemical ways, often usinglow-energy resources and sometimes rudimentary manufacturingequipment. In this Minireview, ancient systems are presented asa source of inspiration for innovative material design in the Anthro-pocene.

[*] Dr. L. BertrandIPANEMA, CNRS, ministHre de la Culture, UVSQ,Universit8 Paris-SaclayUSR 3461, 91192 Gif-sur-Yvette (France)

Dr. L. BertrandSynchrotron SOLEILBP 48 Saint-Aubin, 91192 Gif-sur-Yvette (France)E-mail: loic.bertrand@synchrotron-soleil.fr

Prof. C. GervaisBern University of Applied Sciences, HKBFellerstrasse 11, 3027 Bern (Switzerland)

Dr. A. MasicMassachusetts Institute of TechnologyDepartment of Civil and Environmental EngineeringCambridge, MA (USA)

Dr. L. RobbiolaTRACES, CNRS, ministHre de la CultureUniversit8 Toulouse-Jean JaurHsUMR 5608, 31100 Toulouse (France)

The ORCID identification number(s) for the author(s) of this articlecan be found under:https://doi.org/10.1002/anie.201709303.

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with remarkable properties and novel chemical processeswith low environmental impact.

2. Durably Environment-Resilient Materials

With increasing environmental challenges, durability isa key parameter for the material design. Rising levels ofanthropogenic CO2 encourage the development of moresustainable materials. An observation of archaeological andpaleontological remains allows identifying a posteriori a rangeof unexpected preservation cases that have either resisted orbeen transformed to a new material able to survive thefiltering effect produced by changing environmental condi-tions over a long period of time.

Roman concrete is an exemplary case of a long-lasting,resilient, and sustainable ancient inorganic material. In thehistory of concrete materials, it is a technological break-through. Ancient Roman structures have withstood millenniaof seismic events and environmental pressure, while modernconcrete structures constructed with ordinary Portland ce-ment have a predicted lifetime of about 100 years.[8] Additionof “pozzolana” (volcanic ash) provides binding mortar with5–8 times greater compressive strength than the pure limemortar previously used in Ancient Greece. Roman concretecould also set in aqueous environments. Despite advancesmade on the understanding of their resilience,[9, 10] the exactrecipe and physicochemical process leading to their environ-mental stability is still not well defined and is an activeresearch area in the cement industry (Figure 1A–C). The ironpillar in New Delhi, about 6 tons and over 7 m in height, isanother remarkable case of century-old durability.[11] Itslongevity is attributed to its composition, a phosphorus-richwrought iron with low carbon content.[12] The passive

protective surface remained unaffected by the importantmaterial heterogeneity linked to the forging process, includ-ing slag inclusions.[13]

An archetypal example of paleo-inspiration, from obser-vation to synthesis of novel compounds, comes from Mayablue (MB), one of the oldest synthetic pigments. Seen inCentral American wall paintings and sculptures from the 8thto the 15th century, MB exhibits remarkable durability andresilience to harsh environments (Figure 1D). MB resultsfrom boiling a clay (palygorskite, sepiolite) in the presence ofan organic dye (indigo). Its chemical resilience has beenattributed to the hydrogen-bonded organic–inorganic com-plex formed by indigo molecules in the channels of the claystructure.[19] Substitution of the indigo dye led to the design ofa range of paleo-inspired hybrid pigments of different hues(Figure 1E,F).[14, 15,20] The clay framework itself could besubstituted by zeolites.[21] Multifunctional MB-based materi-als could be synthesized such as superhydrophobic MB andfunctionalized so-called organoclays.[22–24]

In the three previous cases, the final goal is to reproducethe ancient materials or at least to transfer their environ-mental resilience into modern materials. Their study can leadto the design of innovative paleo-inspired materials. Ancientartefacts can also be used as analogues to assess the long-termevolution of modern materials in a range of environments. Forexample, buried archaeological iron and glass are used toevaluate solutions for the long-term containment of usednuclear fuel.[25, 26]

Several organic molecules constitutive of plant or animalremains have shown remarkable resilience to long-termchemical degradation. Polymeric materials involved in theexo- and endoskeleton, tegument, appendages of animals, andthe structural parts of plants (based on chitin, cellulose,keratins, fibroins, collagen, and sporopollenin) are particu-

Lo"c Bertrand is Director of the IPANEMAEuropean Research platform on Ancientmaterials. His research interests center onthe development of methods to study long-term ageing processes and exceptional pres-ervation of biological remnants and materi-als from archaeological and paleontologicalsites studied at microscale, manufacturingtechniques used in the past, and theprovenance of raw materials used to pro-duce archaeological artefacts.

Claire Gervais is Professor in materialschemistry at the Bern University of the Artsand leads a group dedicated to the analysisof ancient materials by synchrotron andsimulation techniques. Her research interestsfocuses on physicochemical processes innatural and cultural materials, with a focuson materials degradation and the develop-ment of innovative methods for investigat-ing composite, multiscale materials.

Admir Masic is Esther and Harold E.Edgerton Career Development Assistant Pro-fessor in the Department of Civil andEnvironmental Engineering at the MIT. Hisresearch focuses on the development of highperformance in situ and multiscale charac-terization techniques to investigate complexhierarchically organized materials. His groupexplores ancient technologies as a source ofinspiration for the development of a newgeneration of durable and sustainable build-ing materials.

Luc Robbiola is CNRS research engineerand expert in Cultural materials science atToulouse University. He is a specialist inmetallurgy and surface chemistry as well asin conservation-restoration of artworks. Hiswork mostly focuses on the corrosion andprotection of copper-based alloys in naturalenvironments, combining investigation onarchaeological and historic materials, andon synthetic alloys. His main researchapplications relate to the diagnosis of alter-ation and conservation-restoration, and au-thentication of ancient materials.

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larly prone to exceptional preservation.[27–29] Beyond theirintrinsic molecular and folding properties, these moleculesare involved in supramolecular architectures that contributeto their long-term resilience.[30] DNA can remain amplifiable,although under a chemically altered form, after millennia,particularly in cold or humid micro-environments, or withinspecific compact bones.[31–34] A range of other organiccompounds or functional moieties where sufficiently wellpreserved to be used as markers of past biochemical activities,for example, heme compounds,[35, 36] quinones,[37] and severalproteins.[38, 39] Weak points in bioorganic molecules such as theamino acid side chains that are prone to long-term racemi-

zation or hydrolysis have been identified,[27] an essentialmilestone in the study of ancient proteomes.[40] Exceptionalpreservation of supposedly less stable molecules was alsoreported. Fatty acids, terpenic resins, or carbohydrates wereidentified in a variety of contexts from food-containingvessels to hydrophobic coatings in archaeological potsherds,adhesives, or ancient art objects.[28, 41] Frequent fine-scaleassociation with mineral phases suggests a general mechanismassuring long-term conservation of organic–inorganic com-plexes. Beside their invaluable help to understand the historyof life on Earth and past cultural practices, these examplessuggest routes to design organic or organometallic materials

Figure 1. Examples of paleo-inspiration. A)–C) The Markets of Trajan constructed in the early 1st century CE in Rome (credits: M. Vitti). A) Mortarof the Great Hall of the Trajan’s Markets, B) interfacial zone along scoria perimeter,[10] , and C) authigenic fibrous and platey str-tlingiteCa2Al2(SiO2)(OH)10·2.5 (H2O) crystals, which grow through the relict volcanic scoria and its interfacial zone, forming obstacles to microcrackpropagation within the cementitious binding matrix.[10] D)–F) Mural containing D) Maya Blue paint, E) the methyl red@palygorskite pigment,[14]

and F) optimized model structures for methyl red@palygorskite.[15] G)–I) As-cast bronze zoomorphic ornament (Late Iron Age, ca. 300 BCE, LaFosse-Cotheret, France). G) Detail of the central part corresponding to an animal head with a small muzzle and prominent eyes, H) synthetic as-cast Cu-Sn bronze (Sn 22.0 wt %), SEM-BS image of the d phase (in white) within the (a+ d) eutectoid, surrounding the primary solidifieda copper solid solution (in black, full image width: 190 mm), and I) representation of the octuple unit cell crystal structure of a g Cu-Zn brass(416 atoms) on which is based the d Cu-Sn structure (412 atoms, fcc lattice parameter a =1.798 nm.[16] J) Copper-based slab fragment covered bya mineralized cellulosic textile, Nausharo, Pakistan, IV mill. BCE, mus8e du Quai Branly, K) FEG-SEM image of artificially fossilized zirconiapaper,[17] and L) fabrication of hierarchical porous poly(vinyl alcohol) (PVA) from artificial fossilization of cellulose.[18]

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with exceptional resilience to the effect of time and to harshenvironments. For instance, the protection of nucleic acidswithin ancient fossils was recently mimicked by encapsulatingDNA into amorphous silica spheres, leading to nucleic acidswithstanding high temperatures and aggressive oxic environ-ments.[42]

3. Man-Made Materials with Remarkable Properties

Past societies have developed skills and technologies toproduce systems that address specific needs, while taking intoaccount available raw materials, local conditions, and knowl-edge. Invention and trial-and-error have led to culturalinnovation processes and products optimized towards specificfunctions, and therefore materials with remarkable proper-ties.

An extreme human chemical creativity has been exertedin producing pigments and dyes for colors where only rarestable compounds exist in nature. The search for alternativesto the expensive blue pigments lapis lazuli, indigo, and azuriteis particularly illustrative, and led to very early and innovativedevelopment of chemical syntheses: Egyptian,[43–46] Han[47,48]

and Maya blues, cobalt minerals and glasses (cobalt andcerulean blue, smalt), turquoise ivory,[49] and more recentlythe ferrocyanide Prussian Blue, phtalocyanins, up to thecontemporary International Klein Blue. A particular level of“perfection” was attained in term of optical propertiesthrough inspiring early chemical syntheses that are ofsignificant interest for current materials chemistry.[44, 47, 49,50]

A similarly appealing example is early Islamic lusters, whichare universally renowned for their golden shine obtained froman optimization of surface plasmon resonance effects fromcopper and silver nanoparticles nucleated at the glaze sur-face.[51] Verger et al. studied the ZnAl2@xCrxO4 phases em-ployed to color ceramics since the middle of the 19th centuryby the SHvres manufacture. These pink to green spinelcompounds were optimized for their optical response, as wellas for their physicochemical stability during cooling in themelt glaze.[52, 53] Improved refractory materials and assessmentof the impact of high chromium loading in nuclear glasswastes could benefit from a better understanding of suchdissolution/ crystallization behavior of these chromium com-pounds.[53]

The chemistry of chromium is indeed not the only case ofa potentially highly toxic compound documented by ancientuses. Archaeology demonstrates advanced chemistry basedon heavy elements such as lead over more than fourmillennia. A range of Pb-based materials were found inancient Egyptian burials, as paint and cosmetic formulations.Along with well-known natural minerals such as black leadsulfide (from crushed galena PbS, still used today in tradi-tional make-up), other chemical compounds, for example,laurionite PbCl(OH) and phosgenite Pb2Cl2CO3, were iden-tified.[54, 55] Another typical case is the widespread use ofarsenic instead of tin as alloying element in early bronzes (upto 5 wt %). Arsenical bronzes have been widely used since thelate Chalcolithic in the Middle East[56, 57] as well as in ancientAmericas.[58] Beyond the undeniable toxicity and health

impact of these compounds, this reveals an in-depth knowl-edge in the specific processing of these toxic materials. Paleo-inspired chemistry could therefore bring innovative conceptstowards both a targeted use and processing of toxic sub-stances.

Intriguingly, a range of phases normally identified asthermodynamically metastable or unstable are identified inabundance in ancient systems. A typical example is the d

phase of tin bronze (Figure 1G–I), one of the earliest alloysproduced, which was widely used over five millennia.According to the Cu-Sn equilibrium phase diagram, thetemperature existence domain of this phase, hard and brittle,is very limited (621–863 K).[59–62] Although identified asmetastable at room temperature in low- or high-tin bronzes,as-cast or annealed ancient artefacts prove this intermetalliccubic phase to withstand millennia.[63, 64] This discrepancybetween full equilibrium and metallurgical steady state stillremains to be understood.[62, 65] A number of other metastableinorganic compounds were unexpectedly identified in ancientsystems, such as the ferrous hydroxychloride b-Fe2(OH)3Cl incorroded archaeological iron artefacts,[66] plumbonacrite Pb10-(CO3)6O(OH)6 in paints,[67] laurionite PbCl(OH) in cosmeticsfrom Ancient Egypt,[54] or pseudobrookite Fe2TiO5, which wasidentified as the main source of the yellow color in Romanmarbled sigillata slips.[68] In contrast to synthetized referencesobtained at a higher temperature, archaeological pseudo-brookite is characterized by the presence of magnesium andaluminum atoms within the crystal structure,[5] which couldaccount for their greater chemical stability and high reflectiveindex. This formulation could thus inspire new pigmentformulations. The particularly interesting metastable phase e-Fe2O3 was identified in the lustrous black glaze of ancient JianChinese potteries from the Song dynasty (960–1279 CE).[69] e-Fe2O3 is a rare ferric oxide polymorph, intermediate betweenhematite a-Fe2O3 and maghemite g-Fe2O3, the crystal struc-ture of which has only been described in the late 90s.[70] At theglaze surface of Jian ceramics, surface crystals of e-Fe2O3

form a 2D dendritic network micrometric in size,[70] which isremarkable, as only submicrometric e-Fe2O3 crystals could besynthesized so far in a laboratory environment.[70,71] Large e-Fe2O3 crystals show promise for fundamental solid-statephysics studies and for applications in new recording mediaand telecommunications owing to their magnetic proper-ties.[71, 72] A paleo-inspired synthesis of e-Fe2O3 could beproposed based on processing a high-iron-containing glass atelevated temperature in a reducing atmosphere.[69]

4. Materials Produced with Scarce Resources

Archaeology as ethnology provides numerous examplesof ingenious adaptation to specific environments and con-straints, including in the context of limited energy resources.In an essay, Molles and Flonneau described the creativitydeployed to circumvent the oil shortage during World War2.[73] Similarly, ancient technologies may inspire sustainablemodern practices, as well as system-level solutions locallyadapted to problems.

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Archaeology reveals reuse and recycling strategies ap-plied to a range of materials: glass, metals, constructionmaterials, and so on.[74, 75] Past societies developed advancedlifecycle management of materials that can be regarded asearly “design-for-recycling”. Ancient Roman builders usedrecycled construction materials (for example, brick or terracotta fragments) to enhance concrete, opus caementicium(from Latin opus—wall, caementa—aggregate).[76] This wassignificantly more economical than squared stone and pro-vided opus caementicium with improved static capacity. Theembodied energy of the ancient Roman cement formula issignificantly lower to that of ordinary Portland cement, andcould lead to more environmentally friendly constructionmaterials.[10, 77] Steel, aluminum, and cement, three majormodern construction materials, account for 47% of industrialCO2 emissions globally.[78] Opportunities across the lifecycleof these materials exist to reduce the environmental footprintof buildings and infrastructure. The resulting production ofnew material and demolition waste can take inspiration fromancient techniques to reduce material impact over the entireproduct lifecycle. Recycling generally reduces the environ-mental impact of construction materials. However, thisprocess is still being rediscovered. For instance, modernattempts to recycle concrete aggregate led to a decrease in thedurability and strength of the new material.[79]

Numerous other examples of soft physical and chemicalmanufacturing processes are provided by archaeologicalmaterials. In ancient worlds, many metallic artefacts wereproduced via a process involving annealing and hammering.This thermomechanical process had three functions: shaping,improving mechanical properties, as well as in some casesmodifying surface aspects, such as in Damascus steel.[80, 81] Inthis way, ancient production techniques may inform newprocessing methods for modern materials such as regardingthe transposition of the damasked approach to copper forproviding rich surface patterns.[82]

An insightful case of soft chemical conversion is thecorrosion of copper to cuprite identified in a very early lost-wax cast from the Chalcolithic site of Mehrgarh.[83] Preserva-tion of a submicrometric eutectic structure is observed overcentimeters, while about 39% of initial copper atoms left theoriginal copper metallic structure during oxidation.[83] Long-term pseudomorphic conversion of organic compounds is alsooften observed. Fossilization is the chemical transformationof an original material in organic imprints or pseudomorphminerals that retains the morphology of the original material.Typical pseudomorph minerals are apatites, pyrite, clayminerals, calcite, and silica (see Briggs[84] and referencestherein). Exceptional preservation of soft tissues throughauthigenic mineralization, for example, preservation of themorphology of muscle fibers,[85] can be observed up toa mineral grain size of a few tens of nanometers.[84] Inarchaeological sites, organic matter such as textile, leather, orother biological tissues sometimes mineralize in contact withiron or copper-based objects while preserving their micro-structure at a scale that allows identifying the animal or theplant of origin, yarn manufacturing methods, or weavingtechniques[86] (Figure 1J). Study of ancient cosmetic treat-ments led to the identification of an interesting reaction

product of archaeological wool with keratinous fibers. Nano-particles of galena (PbS) form from cleavage of disulfidebridges in keratin, with a local ordering controlled by theorganic matrix.[87] This offers an elegant synthesis route to theorganically templated nucleation, growth, and mesotextura-tion of PbS nanoparticles.[55] Similarly, Spadavecchia et al.observed the collagen-aided formation of Au nanoparticulesin ancient gold-plated ivories.[88]

Reproduction of fossilization and mineralization process-es at increased speed would allow the templated productionof mineral structures complex in shape at potentially nano-metric scales, in a sort of “chimie douce” nano-investmentcasting. Several successful attempts were carried out in thisdirection. Huang et al. report the nanoreplication of cellulosicfibers in titania (TiO2) by mimicking their permineralizationafter a functionalization of their surface comparable to thatpossibly involved in fossilization (Figure 1K,L).[17, 89] Mizutaniet al. synthesized porous titania, alumina, and zirconiaceramic woods using a similar approach of artificial orsynthetic fossilization.[90]

5. Towards New Paleo-inspired Material Design andProcessing

Apart from the traditional strategy that consists inidentifying new physicochemical behavior in pure materialsand optimizing their use in new systems, this Review suggeststhat harvesting physicochemical properties from paleonto-logical or archaeological systems can provide remarkablesolutions. Several key generic features of ancient materialshave been or could be further exploited in modern ones.Many durable ancient materials consist in inorganic matrixincorporating organic molecules, for example, exceptionallypreserved organics in fossil remains, alumina-supported lakepigments, or mineralized textiles. The chemistry of adjacentinorganic surfaces may play a lead role in stabilizing organicmolecules. Even in primarily organic systems, long-termageing appears to be driven by host–guest interactions. Forinstance, fading of Prussian Blue (used as dye in paintings,watercolors, and photography) upon anoxia or intenseillumination is significantly modified by the redox interactionwith the medium in which it is dispersed.[91] Many ancientmaterials are impure and built upon a multiscale organiza-tion, which may contribute to impeding the emergence ofgeneral failure mechanisms thereby further increasing theirresilience. Material heterogeneity creates multiple diversechemical micro-environments (atmosphere, percolating flu-ids, pressure, temperature) that could allow investigating thelink between local microstructure and reactivity.[92] This solid-state combinatorial probing of material properties agrees wellwith modern developments in high-throughput materialsciences.[93, 94] Retro-engineering can be considerably facili-tated by access to written or oral ethnological evidence.[95]

However, in many cases, synthesis has to be reinvented asknowledge has been lost. Lessons can be learned both fromthe study of aged materials and of ageing processes them-selves. Modelling of ancient materials opens a promising way

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to characterize and predict new structures and properties butis still in its infancy.[96]

The fundamental interest of the paleo-inspired approachrests in the “bottom-up” process of selecting systems in thearchaeological and paleontological record that already havedemonstrated properties of interest (Figure 2). Ancientsolutions have often been developed as a whole in integratedmultifunctional systems that synergistically connects materi-

als, material interfaces, and functions. For instance, MayaBlue “combines the color of the organic pigment and theresistance of the inorganic host, [and is] a synergic material,with properties and performance well beyond those ofa simple mixture of its components”.[97,98] Art materials mayhave been optimized jointly for a range of functionalities suchas optical reflectance, rheology, chemical compatibility, anddurability (see for instance Viguerie et al.[99]). Historicalprocess optimization and taphonomy filtering (literally bythe “laws of death”, which govern material behavior inarchaeological and paleontological burial settings) regard thesystems in a holistic manner. This goes along with the visionby P. Yang and J.-M. Tarascon, who emphasize on wholesystem optimization and interface design in materials sciencetowards functional properties and applications, rather than“revolv[ing] around single material component”.[1] As for bio-inspiration, paleo-inspiration provides an additional point ofview[100] that adds up to the toolbox of the material scientist,built on the considerable body of knowledge that can beextracted from the history and behavior of ancient systems.

6. Summary and Outlook

Ancient and historical systems are promising sources ofinspiration. Systems studied in archaeology, in paleontology,and in cultural heritage are observed a posteriori, afterprocesses of natural and/or cultural selection.[7] Systems that

have resisted this filtering exhibit enhanced resilience capaci-ties. A better understanding of their intrinsic properties mayboth suggest new materials and new route of synthesis toexisting ones. Contrarily to pure synthetic materials, ancientsystems are often very heterogeneous in chemical composi-tion and morphology. Even the purest ancient compoundsgenerally contain a range of defects and trace elements thatmay be unequally distributed in the material and often play

a lead role in their physicochemicalbehavior. There is therefore a greatinterest to increase our level of knowl-edge on the detailed multi-scale prop-erties of ancient systems, to developstrategies to model their behavior tak-ing into account their complexity, andto mimic the effects of selection pro-cesses towards the generation of novelmaterials and devices.

Acknowledgements

We are particularly grateful to Jean-Paul Iti8 (Synchrotron SOLEIL) andMathieu Thoury (IPANEMA) for dis-cussions regarding this work. L.B. ac-knowledges support from R8gion 6le-de-France/ DIM Mat8riaux anciens etpatrimoniaux, and the European Com-mission programs IPERION CH andE-RIHS PP (GA. 654028 and 739503).

C.G. acknowledges the Swiss National Science Foundation forher professorship grant (n. 138986). We thank ChristopheMoulherat (mus8e du quai Branly—Jacques Chirac) foraccess to the mineralized textile from Nausharo, and MartaBellato (IPANEMA) for the photograph of the textile. A.M.thanks Linda M. Seymour, Marc Walton, Heather Lechtman,Marco Nicola, Giacomo Chiari, John Ochsendorf, and MastroGilberto Quarneti for fruitful discussions. We are indebted toJianguo Huang (Zhejiang University, Hangzhou), RobertoGiustetto (Univ. Torino), Marie D. Jackson (Univ. Utah), andToyoki Kunitake for providing high-resolution images of theirwork.

Conflict of interest

The authors declare no conflict of interest.

How to cite: Angew. Chem. Int. Ed. 2018, 57, 7288–7295Angew. Chem. 2018, 130, 7408–7416

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Manuscript received: September 8, 2017Accepted manuscript online: November 20, 2017Version of record online: May 2, 2018

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