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The mineralization mechanism responsible for the fossilization of archaeological textiles in close proximity to metal artifacts presents a sophisticated preservation process at both macro and micro levels. This study examines archaeological textiles dating from 2200 BC to AD 1900, sourced from three distinct archaeological sites. The focus is on understanding the microstructural degradation of fibers within a specific burial environment and the preservation achieved through mineralization. These archaeological fibers of archaeological textiles exhibit morphological preservation in the immediate vicinity of copper-based objects. Utilizing tools such as a digital camera, scanning electron microscopy with energy dispersive spectroscopy (SEM–EDS), high-resolution synchrotron-based microtomography (μCT), and enzyme-linked immunosorbent assay (ELISA), we examined fiber morphology, conducted elemental analysis, identified fiber types, and analyzed fiber characteristics. Our findings reveal the presence of smooth-surfaced wools and silks, fibers covered with calculi, and fiber impressions—all subjected to mineralization. These mineralized fibers can be categorized into three distinct stages of mineralization, each exhibiting varying carbon content. We inferred a correlation between mineralization rate and carbon content while also identifying mineralization density distribution on these textiles. Lastly, this study provides insights into the preservation states of textiles across three different mineralization stages, enriching our understanding of the deterioration of organic archaeological material.

Precious organic cultural relics are easily affected by temperature, humidity, and harmful gases in the environment, resulting in embrittlement, fading, mildew, moth damage and other aging forms. An energy-saving and environmentally friendly material is needed to stabilize humidity and adsorb harmful gases in the environment. In this paper, with an intelligent adjustment function, functional paper containing sepiolite and tourmaline natural minerals was successfully prepared. The component of 80 % of wingceltis and 20 % of straw in dry pulp as main raw material was conducive to the desorption of water molecules. As favorable structure inside functional paper, the adsorption point and the adsorption contact area increased by the rough surface of fiber bundles, the addition of sepiolite and the ordered molecular chains of copolymers destroyed. So, the relative humidity could be adjusted to 55 % ± 3 within 2 hours and was stable with functional paper. At the same time, 1.11 ppm sulfur dioxide and 2.98 ppm ammonia could be effectively adsorbed in 10 and 12 h, respectively, by 1 g of paper in a 5 L container. The pH of the paper was adjusted to neutral with tourmaline, even if the pH was changed by acidic or alkaline gas absorption. Therefore, for long-term organic cultural relic preservation, preparing a constant-humidity and clean environment is of great significance. This is possible through this paper.

The identification of ancient wool is of great significance in archaeology; however, conventional methods are unwieldy or even ineffective when testing contaminated or severely degraded ancient samples. Therefore, it is highly desirable to develop an ultrasensitive detection method for ancient wool. In this study, an ultrasensitive electrochemical immunosensor is proposed and developed to detect ancient wool, where graphene oxide (GO), aldehyde-functionalized ionic liquid (AFIL) composites and gold nanoparticles (AuNPs) are synthesized as efficient signal amplifiers. With their large surface area and excellent electron transfer efficiency, the combination of GO-AFIL and AuNPs endows the immunosensor with excellent electrochemical properties. The fabricated immunosensor measures over a wide linear range of 0.01–100 ng mL−1with a low detection limit of 0.9 ± 0.2 pg mL−1. Moreover, the immunosensor demonstrates excellent performance for detecting ancient wool. The identification of wool fabrics unearthed from Xinjiang, Tibet and Kazakhstan supports the historicity of prosperous sheepherding and wool trade in Central Asia during the Bronze Age.

The extraction and identification of silk residues in tombs is of great significance for studying the distribution and spread of early silk. However, the complex organic matter in the tomb hinders the accurate identification of silk. In this study, a double-antibody sandwich enzyme-linked immunosorbent assay (ELISA) based on immunomagnetic beads (IMBs) was developed for the rapid enrichment and detection of silk residues. The double-antibody sandwich ELISA method established by pairing the IMBs prepared by the silk fibroin monoclonal antibody SF-3 and the silk fibroin monoclonal-labeled antibody bio-SF-1 had the highest detection sensitivity, with a linear detection range of 10 to 104ng mL–1and a detection limit of 5.12 ng mL–1. This method was excellent in the extraction and analysis of silk residues from archaeological imprints and soil samples and successfully identified silk residues in samples at the final stage of silk degradation (physical invisible silk). The proteomics analysis results demonstrated the feasibility and practicability of this method.

The process and mechanism of silk degradation is still a bewildering mystery in the investigation and conservation of cultural relics, which rely on the development of accurate and tailored analysis technologies. Here, two advanced approaches, proteomics and immunology, were developed for determining the deterioration behavior of historic silk fabrics and artificially aged samples from the molecular to the holistic level. The surface morphology and secondary structure of silk were destroyed during degradation. Subsequently, the proteomics and immunology analysis demonstrated a new degradation model differing from previous reports. First, the amorphous region and the looser crystalline regions were destroyed together, and the macromolecular chains were broken randomly. Then, the tight β-sheet blocks in the crystalline region were exposed and deteriorated, which expedited the degradation of tight β-sheet blocks and relatively loose blocks in the crystalline domain as well as the amorphous domain, ultimately yielding small molecule polypeptides. However, the deterioration process of ancient fabrics could be accelerated by poor burial conditions, thus showing distinct destructive characteristics. Overall, the results gave us a more comprehensive and profound understanding of the degradation process of ancient silk.

The degradation behavior of silk fibroin (SF) is a significant and intriguing subject in the area of archaeological ancient silk research. In the present study, the immunological detection techniques combined with traditional characterization methods, jointly studied the degradation process of SF from Bombyx mori(B. mori) and Antheraea pernyi(A. pernyi) through exposure to alkaline proteinase, α-chymotrypsin, pepsin, and trypsin. Spectroscopic analysis revealed that different enzymes showed similar hydrolysis effects on the secondary structure, but the changes of B. moriSF and A. pernyiSF were mainly reflected in the decrease of β-sheet and the reduction of α-helical structure, respectively. In further research of immunology, two diagnostic antibodies were prepared corresponding to SF of B. moriand A. pernyi, respectively. The enzyme-linked immunosorbent assay (ELISA) and western blot indicated the enzyme-treated SF proteins still exhibited higher immunoreactivity because the epitopes on the surface of SF molecules are retained. Although α-chymotrypsin possesses the most cleavage sites among these enzymes, the α-chymotrypsin-treated SF did not exhibit significant changes in secondary structures and high antibody binding capacity. The results deepen our understanding of the SF degradation process during enzymatic hydrolysis, and show far-reaching guiding significance in trace detection of SF.

Species identification is of key significance for exploring the origin and transmission of ancient silks. In this study, two novel methods, i.e.western blot (WB) and proteomics analyses, were proposed and established to identify the differences between silks from Bombyx mori(B. mori) and two other distinctive species (Eri silkworm and Chestnut silkworm). Three diagnostic antibodies, a polyclonal anti-silk fibroin (anti-SF) antibody (pAb), a polyclonal anti-SF-specific peptide antibody (pAsb), and a monoclonal anti-SF antibody (mAb) were designed and prepared to distinguish silk species using the antibody-based WB technique. Proteomics analysis by liquid chromatography–tandem mass spectrometry was performed to further identify silk species at the protein level. WB results indicated that the three antibodies showed high specificity and affinity and could discern B. morisilk from Eriand Chestnutsilks. Biomarkers for each SF were obtained using proteomics analysis, and they have the potential to serve as standards for identifying silk species. Thus, combining WB and proteomics analyses with conventional methods can provide more accurate silk information and may be suitable for identifying other proteinaceous materials in archaeological field.

The use of wool from sheep is widespread in ancient and historic textiles. The detection of ancient wool can provide meaningful information for both archaeologists and academics. However, the efficacy of conventional methods is likely to be limited in the detection of ancient samples with severe degradation or contamination. This is also one of the main challenges in archaeological sites. In this study, a novel immunological approach was proposed to overcome this difficulty. Two diagnostic antibodies, the anti-K (keratin) antibody and the anti-P (peptide) antibody, were carefully designed and prepared through the immunization of animals with a complete antigen (keratin) and the conjugation product of hapten (diagnostic peptide) with a carrier protein, respectively. Next, an indirect enzyme-linked immunosorbent assay (ELISA) was established under the optimal binding concentration of the coating antigens and the antibodies. The results indicated that the antibody-based immunological method exhibited high sensitivity, specificity and reliability. The limit of detection in the ELISA for the anti-K and anti-P antibodies was 81.39 ng mL−1and 6.81 ng mL−1, respectively. The ELISA revealed a lower cross-reactivity (less than 0.01%) for the two antibodies with interference antigens. The recoveries of the two antibodies from standard soil samples were in the range of 80% to 100%, with a relative standard deviation (RSD) of lower than 9%. The coefficients of variation for the anti-K antibody and anti-P antibody were in the range of 3.27% to 12.40% and 9.48% to 10.31%, respectively. Moreover, both the anti-K and anti-P antibodies can positively identify ancient wool samples, even for wool traces in soil, verifying the validity and practicability of the immunological method in the detection of ancient wool.

Proteinaceous materials, such as ovabumin and collagen, were commonly used as binding media, and as adhesives and protective coatings. However, the identification of ancient proteinaceous binders is a great challenge for archaeologists, due to their limited sample size, complex combinations of various ingredients and reduced availability of the binder during the process of protein degradation. In this paper, an enzyme-linked immunosorbent assay (ELISA) provides to be a particularly promising method for the detection of proteinaceous binding materials in ancient relics. The present work focused on the specific identification of proteins in archaeological binders, which was brushed on the Tripitaka. Two samples, the adhesion area (S1) and the ink area (S2), were tested by ELISA. The results showed that both S1 and S2 reacted positively when treated with an anti-collagen-I antibody. It proved the existence of proteinaceous binders in Ancient Tripitaka, and the percentage of collagen in S1 and S2 was 61.44 and 15.4%, respectively. Compared with other conventional techniques, ELISA has advantages of high specificity, sensitivity, rapidity and low cost, making it especially suitable for the protein detection in the archaeological field.

Leather is one of the indispensable necessities in human daily life. However, the identification of ancient leather, especially species identification, is a great challenge for archaeologists and conservation scientists. Fortunately, the non-competitive indirect enzyme-linked immunosorbent assay (ELISA) offers a particularly promising approach for the analysis of ancient leather because of its advantageous properties such as high efficiency, low-cost, and high sensitivity and specificity. This study focuses on the use of a non-competitive indirect ELISA method to identify the species of ancient leather. Three ancient leather samples, which were unearthed from the desert in the Xinjiang area, were characterized using an analytical Oxford ISIS energy dispersive spectrometer (EDS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and ELISA. Two independent indirect ELISAs were established, and the results from the two methods were used in the determination of animal species. It was shown that all the three ancient leather samples were recognized by both anti-collagen-I antibody (ab23446) and anti-collagen-I antibody (ab117119), which indicates that the species of these leathers belong to cow. This is the first study to use an immunological method for the characterization of ancient leather. It is concluded that the ELISA method has the potential to become a powerful analytical tool in the identification of ancient proteinous materials.

The identification of ancient silk is of great importance in both archaeology and academia. In the present work, a specific antibody having the characteristics of low cost, easy operation and extensive applicability was developed directly through immunizing rabbits with complete antigen (silk fibroin, SF). Then, antibody-based immunoassays, i.e.enzyme-linked immunosorbent assay (ELISA) and immuno-fluorescence microscopy (IFM), were established and conducted in tandem to identify the corresponding protein in ancient silks. The anti-SF antibody exhibits high sensitivity and specificity for the identification of modern and ancient silks. The detection limit of the ELISA method is about 0.1 ng/mL, and no cross-reactions with other possible interference antigens have been noted. IFM makes it possible to localize target proteins in archaeological samples, and also ensure the reliability of the ELISA results. Based on these advantages, immunological techniques have the potential to become powerful analytical tools at archaeological sites and conservation science laboratories.

The origin of silks remains one of the most puzzling mysteries. However, the on-site identification of ancient silks usually becomes particularly difficult after thousands of years due to degradation and sample contamination. In this paper, a portable immunochromatographic strip (ICS) technique using colloidal gold-labelled polyclonal antibody was well designed and developed. This technique requires only 10 min to complete the qualitative detection of silks. The strip exhibits good sensitivity, specificity and thermal stability. The detection limit of the strip is 1.5 μg mL−1, and no cross-reactions with other possible interfering antigens were noted. Moreover, the strip can maintain the effectiveness after being treated at 60 °C for 30 days. These characteristics make the ICS assay especially suitable for the on-site detection in the archaeological field.

An investigation into the influence of ultraviolet-irradiation (UV) on wool fibers was performed using Electron Paramagnetic Resonance (EPR) Spectroscopy, Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (FTIR-ATR) and Scanning Electron Microscopy-Energy Dispersive Spectrometry (SEM-EDS). Using the SEM-EDS and FTIR-ATR spectra, it was determined that there are other components which precipitate out of the fibers and the precipitated elements were related to the S element, which indicated that cysteine residues were involved during the degradation procedure. The EPR spectra of the UV radiation exposed wool fibers and untreated wool fibers showed a characteristic absorption peak centered at the highly isotropic g= 2.0029 ± 0.0005 with the peak-to-trough width (∼1 mT) and without hyperfine structure, which turned out to be carbon radicals.

A consolidated method by EGDE (ethylene glycol diglycidyl ether) and Ala (alanine) was used for fragile ancient silk fabrics protection. Therefore, an investigation has been carried out to figure out the effect of consolidation material in the system. Silk fibers were dyed with madder and then exposed to UV light beams for accelerated aging. The aged madder-dyed samples were treated with EGDE aqueous solution by spraying, and then treated with Ala aqueous solution by the same way on 10 minutes later. The samples were investigated by colour measurement and scanning electron microscopy (SEM). It has been observed that there is an obvious change of colour of samples after consolidation material treatment. The surface of the aged madder-dyed silk fabric were covered with EGDE and Ala thus protecting the silk fibers.