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Palm leaf manuscripts (PLMs), venerable historical artefacts containing Buddhist scriptures, history, mathematics and literature, which are carried by palm leaves (Corypha umbraculifera) and are highly susceptible to microbial degradation during prolonged storage. This degradation results in significant alterations to both the appearance and material properties of PLMs, but the precise mechanism underlying this deterioration remains a mystery. To this end, the present study focused on ancient PLMs from Xishuangbanna Dai Autonomous Prefecture in Yunnan Province, China. The objective of present study was to isolate, culture and identify the microorganisms typically found in these manuscripts and to use them to biodegrade the carriers of PLMs. Detailed observations of the biodegradation behavior of these microorganisms on the carriers of PLMs were carried out, together with characterizations of the hierarchical structure and mechanical properties of the leaf fiber cell walls. This comprehensive analysis provided insights into the deterioration mechanisms of the carriers of PLMs. The study revealed the presence of the common fungus Aspergillus niger on ancient PLMs. Aspergillus niger can secrete cellulase, lipase, and acidic substances after colonizing on the carriers of PLMs. These substances sequentially damage the carrier's epidermal cells, mesophyll cells, and leaf fibers, leading to the separation of different tissue structures. At the molecular level, the lipids on the surface of the leaves were degraded initially, and sequential depolymerization of hemicellulose, amorphous cellulose, and crystalline cellulose occurred. Additionally, this study firstly applied nanoindentation technology in the research of PLMs. The mechanical properties of the cell walls underwent notable alterations due to the modifications in chemical and crystalline structure of the carriers of PLMs upon the biodegradation of Aspergillus niger. Specifically, the hardness and elastic modulus of leaf fiber cell walls showed an initial increasing and then decreasing trend, consistent with the trend of cellulose crystallinity, which also provided a new reference for assessing the degree of deterioration of PLMs. [ABSTRACT FROM AUTHOR]

Alcohols are important products in chemical industry, but separating them from their aqueous solutions is very difficult due to the hydrophilic nature of alcohols. Based on molecular dynamics simulations, we observe a striking nanoscale drying phenomenon and suggest an energy-saving and efficient approach toward alcohol/water separation by using single-walled carbon nanotubes (SWNTs). We use various common linear alcohols including C1-C6 1-alcohols and glycerol for demonstration (the phenol is also used as comparison). Our simulations show that when SWNTs are immersed in aqueous alcohols solutions, although the alcohols concentration is low (1 M), all kinds of alcohols can induce dehydration (drying) of nanotubes and accumulate inside wide [(13, 13)] and narrow [(6, 6) or (7, 7)] SWNTs. In particular, most kinds of alcohols inside the narrow SWNTs form nearly uniform 1D molecular wires. Detailed energetic analyses reveal that the preferential adsorption of alcohols over water inside nanotubes is attributed to the stronger dispersion interactions of alcohols with SWNTs than water. Interestingly, we find that for the wide SWNT, the selectivity for 1-alcohols increases with the number of alcohol's carbon atoms (Ncarbon) and exhibits an exponential law with respect to Ncarbon for C1-C5 1-alcohols; for narrow SWNTs, the selectivity for 1-alcohols is very high for methanol, ethanol, and propanol, and reaches a maximum when Ncarbon = 3. The underlying physical mechanisms and the implications of these observations for alcohol/water separation are discussed. Our findings provide the possibility for efficient dehydration of aqueous alcohols (and other hydrophilic organic molecules) by using SWNT bundles/membranes. [ABSTRACT FROM AUTHOR]

Huaguangjiao І is a Chinese ancient wooden shipwreck of South Song Dyansty (1127–1279 AD). Wood samples from Huaguangjiao І were analyzed in order to evaluate the preservation state of the waterlogged wood. Samples were studied from the anatomical, physical and chemical point of view. Thin slides of cross and longitudinal sections from samples were observed by optical microscope, micromorphological decay was classified into class 3 or class 4 according to the anatomical characters. Water content and basic density were measured. Maximum water content (MWC) of the wood samples is between 300% and 600%, residual basic density is about 50%. The proportion of the α-cellulose decreased to 25% of the normal value, and the content of the ash increased greatly. These results indicate the degradation of the wood is very high. In addition, there is a plenty of inorganic deposit in the wood structure. The inorganic compounds deposited in wood samples were analyzed by XRD and ICP qualitatively and quantitatively. The morphology and composition of the inorganic deposit was characterized through SEM-EDS, the majority were iron sulfide, including pyrite and marcasite (FeS 2 ), and fluorite (CaF 2 ). [ABSTRACT FROM AUTHOR]

Ethylene/ethane separation is a very important process in the chemical industry. Traditionally, this process is achieved by cryodistillation, which is extremely energy-intensive. The adsorptive separation is an energy-saving and environmentally benign alternative. In this study, we employ molecular dynamics simulations to study the competitive adsorption of an equimolar mixture of gaseous ethane and ethylene inside single-walled carbon nanotubes (SWNTs) of different diameters at room temperature. We find that for narrow SWNTs, i.e. the (6, 6) and (7, 7) SWNTs, the selectivities towards ethane, fselec, can reach values of 3.1 and 3.7, respectively. Such high selectivities are contrary to the opinion of many researchers that the adsorptive separation of an ethylene/ethane mixture by means of dispersion interaction is difficult due to the same carbon number of ethane and ethylene. The key for our observation is that the role of dispersion interaction of ethane's additional two hydrogen atoms with the SWNT becomes significant under extreme confinement. Interestingly, the (8, 8) SWNT prefers ethylene to ethane with fselec = 0.6. For wider SWNTs, fselec converges to ∼1. The mechanisms behind these observations, as well as the kinetics of single-file nanopore filling and kinetics of confined gas molecules are discussed. Our findings suggest that efficient ethane/ethylene separation can be achieved by using bundles/membranes of SWNTs with appropriate diameters. [ABSTRACT FROM AUTHOR]

Purpose – The aim of this study was to investigate the effectiveness of restoration of gold foils on Dazu Grottoes using different parylene coatings. Design/methodology/approach – The gold foil samples were applied with two types of parylene coating with six different thicknesses, C-10, C-15, C-20, N-10, N-20, N-25, respectively. Electrochemical impedance, surface morphology, and hydrophobicity properties were used to examine the behavior of the coatings. Findings – The results showed that an increase in electrochemical corrosion resistance was observed as the degree of coating thickness was increased for both C-parylene and N-parylene coatings. In addition, the surface morphology study, using 3D topography measurement, indicated that the surface roughness was decreased for all parylene coatings. Furthermore, the parylene-C coating was comparatively more effective than was the parylene-N coating. Originality/value – The results obtained from the three methods were in close agreement. This is an indication that the parylene-C coating can be used to restore the gold foils on Dazu Grottoes and to support future restoration and consolidation to be applied on site on the Grottoes. [ABSTRACT FROM AUTHOR]

Structural and chemical deterioration and its impact on cell wall mechanics were investigated for visually intact cell walls (VICWs) in waterlogged archaeological wood (WAW). Cell wall mechanical properties were examined by nanoindentation without prior embedding. WAW showed more than 25% decrease of both hardness and elastic modulus. Changes of cell wall composition, cellulose crystallite structure and porosity were investigated by ATR-FTIR imaging, Raman imaging, wet chemistry, 13C-solid state NMR, pyrolysis-GC/MS, wide angle X-ray scattering, and N2 nitrogen adsorption. VICWs in WAW possessed a cleavage of carboxyl in side chains of xylan, a serious loss of polysaccharides, and a partial breakage of β-O-4 interlinks in lignin. This was accompanied by a higher amount of mesopores in cell walls. Even VICWs in WAW were severely deteriorated at the nanoscale with impact on mechanics, which has strong implications for the conservation of archaeological shipwrecks. [ABSTRACT FROM AUTHOR]

Thermogravimetry (TG) is used to measure the change of sample mass versus temperature or time under a program controlling temperature. It is a common thermal analysis tool with a precise built-in balance, and accurate data can be obtained through a small amount of sample at the level of milligrams. The feasibility of the TG method for determining maximum water content (MWC) measurement of waterlogged archaeological wood was studied. Simulated waterlogged wood and waterlogged archaeological wood were used to determine the test condition for the TG method. MWC data obtained through the oven-dry and TG methods with different mass gradients from 0–10 mg to >50 mg were analyzed statistically. Deviation, error bar, and coefficient of variation were evaluated. According to the results, when sample mass is no less than 30 mg, and holding time at 105°C is no less than 40 min, data deviation between these two methods is less than 5%. Effect of sampling depth and presence of inorganic deposits were also investigated. Specimens were taken from an archaeological wood with a sampling depth from 2 to 6 mm, then MWC was measured through the TG method. The results indicate MWC of the samples taken from a depth of 2–4 mm is higher than that taken from a depth of 0–2 mm and is lower than that taken from a depth of 4–6 mm, which is related to inorganic deposits. The presence of deposits was verified through SEM-EDX. MWC of three archaeological wood samples from China and five archaeological wood samples from Italy were measured to verify the effectiveness of the TG method when wood species and degradation degree are different. [ABSTRACT FROM AUTHOR]

Understanding the interaction between carbon nanotubes (CNTs) and biomolecules is essential to the CNT-based nanotechnology and biotechnology. Some recent experiments have suggested that the π-π stacking interactions between protein's aromatic residues and CNTs might play a key role in their binding, which raises interest in large scale modeling of protein-CNT complexes and associated π-π interactions at atomic detail. However, there is concern on the accuracy of classical fixed-charge molecular force fields due to their classical treatments and lack of polarizability. Here, we study the binding of three aromatic residue analogues (mimicking phenylalanine, tyrosine, and tryptophan) and benzene to a single-walled CNT, and compare the molecular mechanical (MM) calculations using three popular fixed-charge force fields (OPLSAA, AMBER, and CHARMM), with quantum mechanical (QM) calculations using the density-functional tight-binding method with the inclusion of dispersion correction (DFTB-D). Two typical configurations commonly found in π-π interactions are used, one with the aromatic rings parallel to the CNT surface (flat), and the other perpendicular (edge). Our calculations reveal that compared to the QM results the MM approaches can appropriately reproduce the strength of π-π interactions for both configurations, and more importantly, the energy difference between them, indicating that the various contributions to π-π interactions have been implicitly included in the van der Waals parameters of the standard MM force fields. Meanwhile, these MM models are less accurate in predicting the exact structural binding patterns (matching surface), meaning there are still rooms to be improved. In addition, we have provided a comprehensive and reliable QM picture for the π-π interactions of aromatic molecules with CNTs in gas phase, which might be used as a benchmark for future force field developments. [ABSTRACT FROM AUTHOR]

Waterlogged archaeological wood (WAW) undergoes biological deterioration during long-term immersion in microorganisms-rich aquatic environments. The consolidants are commonly applied to avoid wood deformation upon drying. It is urgent to develop a systematic evaluation method to study the impact of the consolidant distribution and the intermolecular interactions among consolidants and cell wall components on the improvement of wood mechanical traits. In order to evaluate the effect of consolidant distribution and intermolecular interactions between consolidants and cell wall components on the mechanical improvement, herein, we proposed in situ analysis methods involving Nanoindentation (NI) technology (without prior embedding) along with attenuated total reflection Fourier transform infrared imaging (ATR-FTIR imaging). Moreover, PEG, sucralose, and trehalose were chosen as representative consolidants to treat moderately deteriorated WAW because of their different molecular weights and different hydrophilic groups. Results showed that the mechanical improvement in consolidated WAW was significant. The elastic modulus and hardness of WAW after consolidation with PEG, sucralose and trehalose increased, with improvements of 15.3% and 34.8%, 43.9% and 49.5%, 31.9% and 6.4%, respectively, compared to untreated WAW. All three consolidants were found under scanning electron microscopy (SEM) to have filled wood cell lumens and mesopores in cell walls to different extents. ATR-FTIR imaging and thermogravimetric analysis (TGA) results further indicated that consolidants partly penetrated the wood cell walls. PEG was more concentrated near the fiber lumina. In addition, TGA revealed that the relative contents of PEG and trehalose in consolidated archaeological woods were 54.0% and 39.8%, and the maximum decomposition temperature (T d) of consolidated WAW all differed from the untreated WAW, which suggested non-covalent intermolecular interactions were probably presented between consolidants and WAW cell wall components. • Non-embedding sample preparation of Nanoindentation was developed for hydrophilic consolidants treated archaeological wood. • Nanoindentation method is feasible to characterize the mechanical property of consolidated archaeological wood. • ATR-FTIR imaging method proved distribution regularities of consolidants in cell wall of consolidated archaeological wood. • Consolidants PEG, sucralose and trehalose had interacted with cell wall components. [ABSTRACT FROM AUTHOR]

Multidisciplinary diagnostic methods were applied to evaluate the preservation state of waterlogged archaeological wood (WAW) from ancient Chinese shipwreck Nanhai No.1. The characterisation combines micromorphological, physical, and Fourier transform infrared (FTIR) analyses to overcome limitations of using a single analysis. The micromorphological analysis used the whole-slide imaging (WSI) method to identify wood species and determine the decay class. The collected samples were graded as Class 2 (moderate decay) or Class 3 (severe decay). Bacterial and fungal attacks on wood tissues were evident, and the decay pattern of erosion bacteria (EB) was verified. The maximum water content obtained from the oven-drying and freeze-drying methods confirmed that the micromorphological features can be used to grade the decay class. In tandem with hierarchical cluster analysis, FTIR measurements classified four clusters, including moderate and severe decay groups. FTIR also revealed that the chemical alteration of WAW was mainly due to the depletion of polysaccharides. Increased knowledge of WAW degradation and feasible diagnostic methods are beneficial for further conservation strategies. [ABSTRACT FROM AUTHOR]

Waterlogged archaeological wood (WAW) artifacts, made of natural biodegradable polymers, are important parts of many precious cultural heritages. It is of great importance to understand the hygroscopic behavior of WAW in different deterioration states for the development of optimal drying processes and choices of safe storage in varying conditions. This was investigated in a case-study using two Hopea (Giam) and two Tectona (Teak) WAW samples collected from the Xiaobaijiao No.1 shipwreck. The deterioration state of WAW was evaluated by the maximum water content (MWC) method and by the cell morphological structure. Both Hopea and Tectona WAW could be classified into moderately and less decayed WAW. The hygroscopic behavior of moderately and less decayed WAW was then comparatively investigated using Dynamic Vapor Sorption (DVS) measurements alongside two sorption fitting models. Compositional analysis and hydroxyl accessibility measurements of WAW cell walls were shown to correlate with the hygroscopicity of WAW in different deterioration states. It was concluded that moderately decayed WAW possessed higher hygroscopicity and hysteresis than less decayed WAW because of the lower relative content of polysaccharides and the higher relative content of lignin, including the slow hydrolysis of O-acetyl groups of xylan and the partial breakage of β-O-4 interlinks, accompanied by an increased hydroxyl accessibility. This work helps in deciding on which consolidation measures are advised for shipwreck restauration, i.e., pretreatments with specific consolidates during wood drying, particularly for wooden artifacts displayed in museums. [ABSTRACT FROM AUTHOR]