Reversible Deacidification and Preventive Conservation of Paper-Based Cultural Relics by Mineralized Bacterial Cellulose.

Paper-based cultural relics experience irreversible aging and deterioration during long-term preservation. The most common process of paper degradation is the acid-catalyzed hydrolysis of cellulose. Nowadays, deacidification has been considered as a practical way to protect acidified literature; however, two important criteria of minimal intervention and reversibility should be considered. Inspired by the superior properties of bacterial cellulose (BC) and its structural similarity to paper, herein, the mineralized BC membranes are applied to deacidification and conservation of paper-based materials for the first time. Based on the enzyme-induced mineralization process, the homogeneous and high-loaded calcifications of hydroxyapatite (HAP) and calcium carbonate (CaCO3) nanoparticles onto the nanofibers of BC networks have been achieved, respectively. The size, morphology, structure of minerals, as well as the alkalinity and alkali reserve of BC membranes are well controlled by regulating enzyme concentration and mineralization time. Compared with HAP/CaCO3-immersed method, HAP/CaCO3-BC membranes show more efficient and sustained deacidification performance on paper. The weak alkalinity of mineralized BC membranes avoids the negative effect of alkali on paper, and the high alkali reserve implies a good sustained-release effect of alkali to neutralize the future generated acid. The multiscale nanochannels of the BC membrane provide ion exchange and acid/alkali neutralization channels between paper and the BC membrane, and the final pH of protected paper can be well stabilized in a certain range. Most importantly, this BC-deacidified method is reversible since the BC membrane can be removed without causing any damage to paper and the original structure and fiber morphology of paper are well preserved. In addition, the mineralized BC membrane provides excellent flame-retardant performance on paper thanks to its unique organic-inorganic composite structure. All of these advantages of the mineralized BC membrane indicate its potential use as an effective protection material for the reversible deacidification and preventive conservation of paper-based cultural relics.

Polyvinylidene Fluoride Based Piezoelectric Composites with Strong Interfacial Adhesion via Click Chemistry for Self-Powered Flexible Sensors.

Achieving relatively uniform dispersion in organic-inorganic composites with overwhelming differences in surface energy is a perennial challenge. Herein, novel eliminated polyvinylidene fluoride (EPVDF)/EPVDF functionalized barium titanate nanoparticles (EPVDF@BT) flexible piezoelectric nanogenerators (PENGs) with strong interfacial adhesion are developed via thermal stretching following sequential click chemistry. Thanks to the strong interfacial adhesion, the optimal PENGs containing ultra-high ß-phase content (97.2%) exhibit not only optimized mechanical and dielectric behaviors but also excellent piezoelectric properties with high piezoelectric output (V = 10.7 V, I = 216 nA), reliable durability (8000 cycles), ultrafast response time (20 ms), and good sensitivity (2.09 nA kPa-1 ), far outperforming most reported PVDF-based composites. Furthermore, COMSOL finite element simulations (FEM) confirm that the elevated stress transfer efficiency induced by the strong interfacial adhesion is the main driving force for enhanced piezoelectric performances. For practical applications, self-powered PENGs can simply but stably capture mechanical energy, drive tiny electronic devices, and serve as potential multifunctional and durable sensors for detecting human physiological motions. This work opens a pioneering avenue to break the trade-offs between piezoelectric and other properties, which is of great importance for developing self-powered flexible sensors.

Bacterially synthesized superfine tellurium nanoneedles as an antibacterial and solar-thermal still for efficient purification of polluted water.

Bacterial biosynthesis of nanomaterials has several advantages (e.g., reduced energy inputs, lower cost, negligible environmental pollution) compared with traditional approaches. Various nanomaterials have been produced by bacteria. However, reports on using the bacterial biosynthesis of nanomaterials for applications with solar-thermal agents are scarce due to their narrow optical absorption. Herein, for the first time, we proposed a bacterial biosynthesis of broad-absorbing tellurium nanoneedles and demonstrated their effectiveness for solar-thermal evaporation and antibacterial applications. By simple biosynthesis within bacteria (Shewanella oneidensis MR-1), tellurium nanoneedles achieved a superfine configuration with a length-to-diameter ratio of nearly 20 and broad-spectrum absorbance. After integrating tellurium nanoneedles into a porous polyvinyl-alcohol scaffold, a solar-thermal still named TSAS-3 realized a high evaporation rate of 2.25 kg m-2 h-1 and solar-thermal conversion efficiency of 81% upon 1-Sun illumination. Based on these unique properties, the scaffold displayed good performances in seawater desalination, multiple wastewater treatment, and antibacterial applications. This work provides a simple and feasible strategy for the use of microbial-synthesized nanomaterials in solar-driven water purification and antibacterial applications.

Understanding the application of covalent adaptable networks in self-repair materials based on molecular simulation.

Covalent adaptable networks (CANs) are widely used in the field of self-repair materials. They are a group of covalently cross-linked associative polymers that undergo reversible chemical reactions, and can be further divided into dissociative CANs (Diss-CANs) and associative CANs (Asso-CANs). Self-repair refers to the ability of a material to repair itself without external intervention, and can be classified into self-adhesion and self-healing according to the utilization of open stickers. Unlike conventional materials, the viscoelastic properties of CANs are influenced by both the molecular structure and reaction kinetics, ultimately affecting their repair performance. To gain deeper insight into the repair mechanism of CANs, we conducted simulations by using the hybrid MC/MD algorithm, as previously proposed in our research. Interestingly, we observed a significant correlation between reaction kinetics and repair behavior. Asso-CANs exhibited strong mechanical strength and high creep resistance, rendering them suitable as self-adhesion materials. On the other hand, Diss-CANs formed open stickers that facilitated local relaxation, aligning perfectly with self-healing processes. Moreover, the introduction of crosslinkers in the form of small molecules enhanced the repair efficiency. Theoretically, it was found that the repair timescale of Asso-CANs is slower than that of Diss-CANs with identical molecular structures. Our study not only clarifies the similarities and differences between Diss-CANs and Asso-CANs in terms of their self-repairing capabilities, but more importantly, it provides valuable insights guiding the effective utilization of CANs in the development of self-repair materials.

Bacterial polyynes uncovered: a journey through their bioactive properties, biosynthetic mechanisms, and sustainable production strategies.

Covering: up to 2023Conjugated polyynes are natural compounds characterized by alternating single and triple carbon-carbon bonds, endowing them with distinct physicochemical traits and a range of biological activities. While traditionally sourced mainly from plants, recent investigations have revealed many compounds originating from bacterial strains. This review synthesizes current research on bacterial-derived conjugated polyynes, delving into their biosynthetic routes, underscoring the variety in their molecular structures, and examining their potential applications in biotechnology. Additionally, we outline future directions for metabolic and protein engineering to establish more robust and stable platforms for their production.

Effect of Bletilla Striata Polysaccharide on the Pasting, Rheological and Adhesive Properties of Wheat Starch.

A combination of starch and hydrocolloids is a facile method for physically modifying native starch. Bletilla striata polysaccharide (BSP) is a glucomannan with various applications in the food and cosmetic industries as a thickening agent. This study focused on investigating the impact of BSP on the pasting, rheological and adhesive properties of wheat starch (WS). Results from a Rapid Visco-Analyzer (RVA) revealed that the addition of BSP (below 0.2%) resulted in increases in peak viscosity, breakdown and setback values. However, for the addition of BSP at a higher concentration (0.3%), the opposite trend was observed. Rheological measurements indicated that the presence of BSP increased the viscoelastic properties of WS-BSP gels. TGA results demonstrated that the presence of BSP promoted the thermal stability of starch. FTIR results indicated the short-range order structure decreased at low addition concentrations of BSP (0.05% and 0.1%) and increased with higher BSP addition concentrations (0.2% and 0.3%). SEM observation showed that the BSP improved the hydrophilic property of starch gels and decreased the size of pores in the starch gels. Further, the mechanical properties of paper samples unveiled that the present of BSP in starch gels obviously increased its bonding strength as an adhesive.

A Stable Open-Shell Conjugated Diradical Polymer with Ultra-High Photothermal Conversion Efficiency for NIR-II Photo-Immunotherapy of Metastatic Tumor.

Massive efforts have been concentrated on the advance of eminent near-infrared (NIR) photothermal materials (PTMs) in the NIR-II window (1000-1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-II-responsive organic PTMs was explored, and their photothermal conversion efficiencies (PCEs) still remain relatively low. Herein, donor-acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-II window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-II absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-II light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-II window, without any side-effect. Moreover, by combining with PD-1 antibody, the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-II window, offering a new horizon in developing radical-characteristic NIR-II photothermal materials.

Integrated metabolomics and network pharmacology to reveal the mechanism of areca nut addiction.

As a chewing hobby, areca nut (Areca catechu L.) has become the most common psychoactive substance in the world, besides tobacco, alcohol and caffeinated beverages. Moreover, as a first-class carcinogen designated by International Agency for Research on Cancer, long-term chewing areca nut can result in oral mucosal diseases and even oral cancer. To clarify the potential mechanism of areca nut addiction, an integrated strategy of metabolomics and network pharmacology was adopted in this study. Network pharmacology study indicated that all the key targets related to areca nut addiction could be regulated by arecoline and pointed out the importance of G-protein coupled receptor signalling pathway. Analysis results of mice plasma metabolome and faeces metabolome intervened by arecoline suggested that the component may affect the dopamine system and 5-HT system by regulating phenylalanine, tyrosine and tryptophan biosynthesis, phenylalanine metabolism, primary bile acid biosynthesis, glycerophospholipid metabolism and intestinal flora structure. Moreover, the potential importance of bile acids in formation of addictive behaviour of chewing areca nut was investigated by integrative analysis of the relationships between metabolites and intestinal flora. The study can provide scientific basis for the addiction intervention and treatment of areca nut chewers.

Study on the Multimodal Anticancer Mechanism of Ru(II)/Ir(III) Complexes Bearing a Poly(ADP-ribose) Polymerase 1 Inhibitor.

A series of novel ruthenium(II) and iridium(III) complexes (Ru1-Ru3 and Ir1-Ir3) with different ancillary ligands and a PARP-1-inhibitory chelating ligand 2-(2,3-dibromo-4,5-dimethoxybenzylidene)hydrazine-1-carbothioamide (L1) were designed and prepared. The target complexes were structurally characterized by NMR and ESI-MS techniques. Among them, the crystal and molecular structures of Ir1 and Ir2 were also determined by X-ray crystallography. These complexes retained the PARP-1 enzyme inhibitory effect of L1 and showed potent antiproliferative activity on the tested cancer cell lines. The ruthenium(II) complexes Ru1-Ru3 were found to be more cytotoxic than the iridium(III) complexes Ir1-Ir3. Further investigations revealed that the most active complex Ru3 induced apoptosis in MCF-7 cells by multiple modes, inclusive of inducing DNA damage, suppressing DNA damage repair, disturbing cell cycle distribution, decreasing the mitochondrial membrane potential, and increasing the intracellular reactive oxygen species levels.

An Investigation into the Performance and Mechanisms of Soymilk-Sized Handmade Xuan Paper at Different Concentrations of Soymilk.

Invaluable paper relics that embody a rich traditional culture have suffered damage, requiring urgent restoration. In this context, the utilization of soymilk as a sizing agent holds great significance and reverence. This study investigates the use of soymilk as a sizing agent for Xuan paper and evaluates its effects on various properties and the long-term behavior of the paper. The findings reveal that the application of soymilk as a sizing agent for Xuan paper imparts distinct properties, including hydrophobicity, improved mechanical properties, and unique chromaticity. These characteristics-arising from the papillae on the surface of the Xuan paper, the protein folding of the soy protein, and hydrogen-bonding interactions between the soy protein and paper fibers-play a crucial role in shaping the paper's unique attributes. From a physicochemical perspective, the aging process leads to multiple changes in paper properties. These changes include acidification, which refers to a decrease in pH, as well as a decline in mechanical strength, an increase in chromaticity, and a decrease in the degree of polymerization (DP) of the paper. The Ekenstam equation is employed to predict the lifespan of the paper, showing longer lifespans for Sheng Xuan paper and a negative correlation between soymilk concentration and lifespan in soymilk-sized paper. Our work provides valuable insights for the preservation and maintenance of paper, highlighting the potential benefits and challenges of using soymilk for surface sizing.

Thermal, Rheological, Structural and Adhesive Properties of Wheat Starch Gels with Different Potassium Alum Contents.

Wheat starch (WS) is a common adhesive material used in mounting of calligraphy and paintings. Potassium alum (PA) has indeed been used for many centuries to modify the physicochemical properties of starch. Thermal analysis revealed that the presence of PA led to an increase in the gelatinization temperature and enthalpy of the starch gels. The leached amylose and the swelling power of the starch gels exhibited a maximum at the ratio of 100:6.0 (WS:PA, w/w). The rheological properties of starch gels were consistent with changes in the swelling power of starch granules. SEM observations confirmed that the gel structure became more regular, and the holes grew larger with the addition of PA below the ratio of 100:6.0 (WS:PA, w/w). The short-range molecular order in the starch gels was enhanced by the addition of PA, confirmed by FT-IR analysis. Mechanical experiments demonstrated that the binding strength of the starch gels increased with higher PA concentrations and decreased significantly after the aging process. TGA results revealed that PA promoted the acid degradation of starch molecules. This study provides a detailed guide for the preparation of starch-based adhesive and its applications in paper conservation.

NIR-II fluorescence and PA imaging guided activation of STING pathway in photothermal therapy for boosting cancer immunotherapy by theranostic thermosensitive liposomes.

Photothermal immunotherapy has shown great potential for efficient cancer treatment. However, the immunosuppressive tumor microenvironment forms a heavy barrier for photothermal-induced anti-tumor immunity by inhibiting dendritic cell (DC) maturation and cytotoxic T cell response. Moreover, the lack of reliable spatiotemporal imaging modalities makes photothermal immunotherapy difficult to guide tumor ablation and monitor therapeutic outcomes in real time. Herein, we designed a theranostic thermosensitive liposome (PLDD) as a versatile nanoplatform to boost the adaptive anti-tumor immunity of photothermal immunotherapy and to achieve multiple bioimaging modalities in a real-time manner. PLDD contains two major functional components: a multifunctional photothermal agent (DTTB) and an immune potentiator STING pathway agonist (DMXAA). Upon irradiation, the heat generated by DTTB induced the immunogenic cell death (ICD) of the tumor and dissociated the structure of thermosensitive liposome to release DMXAA, which ultimately activated the STING pathway and promoted the ICD-induced immune response by increasing DC cell maturation and T cell recruitment. Moreover, the DTTB in PLDD displayed excellent second near-infrared (NIR-II) fluorescence and photoacoustic (PA) dual-modal imaging, which provided omnibearing information on the tumor and guided the subsequent therapeutic operation. Therefore, this versatile PLDD with light-triggered promotion of anti-tumor immunity and multiple spatiotemporal imaging profiles holds great potential for the future development of cancer immunotherapy.

Naphthalene Diimide-Functionalized Half-Sandwich Ru(II) Complexes as Mitochondria-Targeted Anticancer and Antimetastatic Agents.

In this work, four naphthalene diimide (NDI)-functionalized half-sandwich Ru(II) complexes Ru1-Ru4 bearing the general formula [(η6-arene)RuII(N^N)Cl]PF6, where arene = benzene (bn), p-cymene (p-cym), 1,3,5-trimethylbenzene (tmb), and hexamethylbenzene (hmb), have been synthesized and characterized. By introducing the NDI unit into the N,N-chelating ligand of these half-sandwich complexes, the poor luminescent half-sandwich complexes are endowed with excellent emission performance. Besides, modification on the arene ligand of arene-Ru(II) complexes can influence the electron density of the metal center, resulting in great changes in the kinetic properties, catalytic activities in the oxidative conversion of NADH to NAD+, and biological activities of these compounds. Particularly, Ru4 exhibits the highest reactivity and the strongest inhibitory activity against the growth of three tested cancer cell lines. Further study revealed that Ru4 can enter cells quickly in an energy-dependent manner and preferentially accumulate in the mitochondria of MDA-MB-231 cells, inducing cell apoptosis via reactive oxygen species overproduction and mitochondrial dysfunction. Significantly, Ru4 can effectively inhibit the cell migration and invasion. Overall, the complexation with NDI and modification on the arene ligand endowed the half-sandwich Ru(II) complexes with improved spectroscopic properties and anticancer activities, highlighting their potential applications for cancer treatment.

Template Design for Complex Block Copolymer Patterns Using a Machine Learning Method.

This study represents the first attempt to address the inverse design problem of the guiding template for directed self-assembly (DSA) patterns using solely machine learning methods. By formulating the problem as a multi-label classification task, the study shows that it is possible to predict templates without requiring any forward simulations. A series of neural network (NN) models, ranging from the basic two-layer convolutional neural network (CNN) to the large NN models (32-layer CNN with 8 residual blocks), have been trained using simulated pattern samples generated by thousands of self-consistent field theory (SCFT) calculations; a number of augmentation techniques, especially suitable for predicting morphologies, have been also proposed to enhance the performance of the NN model. The exact match accuracy of the model in predicting the template of simulated patterns was significantly improved from 59.8% for the baseline model to 97.1% for the best model of this study. The best model also demonstrates an excellent generalization ability in predicting the template for human-designed DSA patterns, while the simplest baseline model is ineffective in this task.

New insights into the characteristic skin microorganisms in different grades of acne and different acne sites.

Background: The increasing maturity of sequencing technology provides a convenient approach to studying the role of skin microorganisms in acne pathogenesis. However, there are still too few studies about the skin microbiota of Asian acne patients, especially a lack of detailed analysis of the characteristics of the skin microbiota in the different acne sites. Methods: In this study, a total of 34 college students were recruited and divided into the health, mild acne, and severe acne groups. The bacterial and fungal flora of samples were separately detected by 16S and 18S rRNA gene sequencing. The biomarkers of different acne grades and different acne sites [forehead, cheek, chin, torso (including chest and back)] were excavated. Results and Discussion: Our results indicated that there was no significant difference in species diversity between groups. The genera like Propionibacterium, Staphylococcus, Corynebacterium, and Malassezia, which have a relatively high abundance in the skin microbiota and were reported as the most acne-associated microbes, were no obvious differences between groups. On the contrary, the abundance of less reported Gram-negative bacteria (Pseudomonas, Ralstonia, and Pseudidiomarina) and Candida has a significant alteration. Compared with the health group and the mild group, in the severe group, the abundance of Pseudomonas and Ralstonia sharply reduced while that of Pseudidiomarina and Candida remarkably raised. Moreover, different acne sites have different numbers and types of biomarkers. Among the four acne sites, the cheek has the greatest number of biomarkers including Pseudomonas, Ralstonia, Pseudidiomarina, Malassezia, Saccharomyces, and Candida, while no biomarker was observed for the forehead. The network analysis indicated that there might be a competitive relationship between Pseudomonas and Propionibacterium. This study would provide a new insight and theoretical basis for precise and personalized acne microbial therapy.

Metabolomic Analysis Demonstrates the Impacts of Polyketide Synthases PKS14 and PKS15 on the Production of Beauvericins, Bassianolide, Enniatin A, and Ferricrocin in Entomopathogen Beauveria bassiana.

Beauveria bassiana is a globally distributed entomopathogenic fungus that produces various secondary metabolites to support its pathogenesis in insects. Two polyketide synthase genes, pks14 and pks15, are highly conserved in entomopathogenic fungi and are important for insect virulence. However, understanding of their mechanisms in insect pathogenicity is still limited. Here, we overexpressed these two genes in B. bassiana and compared the metabolite profiles of pks14 and pks15 overexpression strains to those of their respective knockout strains in culture and in vivo using tandem liquid chromatography-mass spectrometry (LC-MS/MS) with Global Natural Products Social Molecular Networking (GNPS). The pks14 and pks15 clusters exhibited crosstalk with biosynthetic clusters encoding insect-virulent metabolites, including beauvericins, bassianolide, enniatin A, and the intracellular siderophore ferricrocin under certain conditions. These secondary metabolites were upregulated in the pks14-overexpressing strain in culture and the pks15-overexpressing strain in vivo. These data suggest that pks14 and pks15, their proteins or their cluster components might be directly or indirectly associated with key pathways in insect pathogenesis of B. bassiana, particularly those related to secondary metabolism. Information about interactions between the polyketide clusters and other biosynthetic clusters improves scientific understanding about crosstalk among biosynthetic pathways and mechanisms of pathogenesis.

A Novel Phytogenic Formulation, EUBIO-BPSG, as a Promising One Health Approach to Replace Antibiotics and Promote Reproduction Performance in Laying Hens.

Gut microbiota play a key role in health maintenance and disease pathogenesis in animals. Dietary phytochemicals are crucial factors shaping gut bacteria. Here, we investigated the function and mechanism of a phytogenic formulation, EUBIO-BPSG (BP), in laying hens. We found that BP dose-dependently improved health and egg production in 54-week-old hens. Furthermore, BP was correlated with increased fecal Lactobacillus, decreased Escherichia coli and Salmonella enterica, and reduced antibiotic resistance (AR) and antibiotic resistance genes (ARG) in chicken stools. The 16S rDNA data showed that BP increased seven genera of probiotics and reduced 13 genera of pathogens in chicken feces. In vitro co-culture experiments showed that BP at 4 µg/mL and above promoted growth of L. reuteri while large 100- and 200-fold higher doses suppressed growth of E. coli and S. enterica, respectively. Mechanistic studies indicated that L. reuteri and its supernatants antagonized growth of E. coli and S. enterica but not vice-versa. Five short-chain fatty acids and derivatives (SCFA) produced from L. reuteri directly killed both pathogens via membrane destruction. Furthermore, BP inhibited conjugation and recombination of ARG via interference with conjugation machinery and integrase activity in E. coli. Collectively, this work suggests that BP promotes host health and reproductive performance in laying hens through regulation of gut microbiota through increasing probiotics and decreasing pathogens and spreading ARG.

The Bioaccessibility of Yak Bone Collagen Hydrolysates: Focus on Analyzing the Variation Regular of Peptides and Free Amino Acids.

The lack of a bioaccessibility test for yak bone collagen hydrolysates (YBCH) limits their development as functional foods. In this study, simulated gastrointestinal digestion (SD) and absorption (SA) models were utilized to evaluate the bioaccessibility of YBCH for the first time. The variation in peptides and free amino acids was primarily characterized. There was no significant alteration in the concentration of peptides during the SD. The transport rate of peptides through the Caco-2 cell monolayers was 22.14 ± 1.58%. Finally, a total of 440 peptides were identified, more than 75% of them with lengths ranging from 7 to 15. The peptide identification indicated that about 77% of the peptides in the beginning sample still existed after the SD, and about 76% of the peptides in the digested YBCH could be observed after the SA. These results suggested that most peptides in the YBCH resist gastrointestinal digestion and absorption. After the in silico prediction, seven typical bioavailable bioactive peptides were screened out and they exhibited multi-type bioactivities in vitro. This is the first study to characterize the changes in peptides and amino acids in the YBCH during gastrointestinal digestion and absorption, and provides a foundation for analyzing the mechanism of YBCH's bioactivities.

A systematic study on immiscible binary systems undergoing thermal/photo reversible chemical reactions.

In this work, we systematically study an immiscible binary system undergoing thermal/photo reversible reactions in theory. For the thermal reaction case, no dissipative structures can be formed and only uniform equilibrium states are observed but the dynamical evolution to these trivial states witnesses a new type of sophisticated phase amplification phenomenon-temporary phase separation (TPS). Linear analysis and light-scattering calculations confirm that TPS is predominated either by spinodal decomposition or nucleation and growth mechanism, or by both successively. For the photo reaction case, steady dissipative patterns exist and are maintained by the external energy input of lights. Linear analysis together with simulations reveals that the characteristic wavelength (ξ) of these structures shortens as the input energy density increases and they obey the relation of ln ξ∝ 1/Tb with Tb the effective temperature of lights. The TPS phenomenon and length-scale dependency of dissipative patterns observed in this simple binary system might have rich implications for the non-equilibrium thermodynamics of biological systems.