Molecular Origin of the Biologically Accelerated Mineralization of Hydroxyapatite on Bacterial Cellulose for More Robust Nanocomposites.

Biomineralization generates hierarchically structured minerals with vital biological functions in organisms. This strategy has been adopted to construct complex architectures to achieve similar functionalities, mostly under chemical environments mimicking biological components. The molecular origin of the biofacilitated mineralization process is elusive. Herein, we describe the mineralization of hydroxyapatite (HAp) accompanying the biological secretion of nanocellulose by Acetobacter xylinum. In comparison with mature cellulose, the newly biosynthesized cellulose molecules greatly accelerate the nucleation rate and facilitate the uniform distribution of HAp crystals, thereby generating composites with a higher Young modulus. Both simulations and experiments indicate that the biological metabolism condition allows the easier capture of calcium ions by the more abundant hydroxyl groups on the glucan chain before the formation of hydrogen bonding, for the subsequent growth of HAp crystals. Our work provides more insights into the biologically accelerated mineralization process and presents a different methodology for the generation of biomimetic nanocomposites.

Toxicity assessment of synthesized titanium dioxide nanoparticles in fresh water algae Chlorella pyrenoidosa and a zebrafish liver cell line.

This study aims to assess the toxicity of the commonly-spread titanium dioxide nanoparticles (TiO2 NPs) by evaluating the exposure impact of the particles on both freshwater algae Chlorella pyrenoidosa and zebrafish liver cell line (ZFL), the two common in vitro models in toxicological studies. To compare the toxic effects of TiO2 NPs with different physiochemical properties, three types of manufactured TiO2 were used: bulk TiO2, Degussa P25 TiO2, and ultrafine TiO2 NPs. Both short and long-term biological responses of green algae, such as the effect on the cell growth rate, pigment autofluorescence, and esterase activity were investigated. The dosage, physical property of TiO2 particles, and their interactions with algal cells affect cellular growth, especially after short-term exposure. The hydrodynamic size plays a critical role in determining the acute toxicity to C. pyrenoidosa in terms of autofluorescence and esterase activity, while all types of TiO2 NPs show toxic effects after exposure for 14 days. However, this observation is not seen when studying the effect of introduced particles in ZFL, for the precipitated Degussa P25 TiO2 showed the highest cellular inhibition. Interestingly, despite the obvious overall toxicity toward C. pyrenoidosa, the photocatalytical properties of TiO2 NPs may contribute to the enhanced photosynthesis in the low concentration range (<40 µg mL-1). Overall, we found that the physical interactions between TiO2 particles and the cells, particles' size and dispersibility play critical role in the cytotoxic effect for both algal and ZFL cells, while the photocatalytical properties of TiO2 particles may produce mixed effects on the cytotoxicity of green algae.

Improving the Catalytic Activity of Carbon-Supported Single Atom Catalysts by Polynary Metal or Heteroatom Doping.

Single atom catalysts (SACs) are widely researched in various chemical transformations due to the high atomic utilization and catalytic activity. Carbon-supported SACs are the largest class because of the many excellent properties of carbon derivatives. The single metal atoms are usually immobilized by doped N atoms and in some cases by C geometrical defects on carbon materials. To explore the catalytic mechanisms and improve the catalytic performance, many efforts have been devoted to modulating the electronic structure of metal single atomic sites. Doping with polynary metals and heteroatoms has been recently proposed to be a simple and effective strategy, derived from the modulating mechanisms of metal alloy structure for metal catalysts and from the donating/withdrawing heteroatom doping for carbon supports, respectively. Polynary metals SACs involve two types of metal with atomical dispersion. The bimetal atom pairs act as dual catalytic sites leading to higher catalytic activity and selectivity. Polynary heteroatoms generally have two types of heteroatoms in which N always couples with another heteroatom, including B, S, P, etc. In this Review, the recent progress of polynary metals and heteroatoms SACs is summarized. Finally, the barriers to tune the activity/selectivity of SACs are discussed and further perspectives presented.

An optimized mesoporous silica nanosphere-based carrier system with chemically removable Au nanoparticle caps for redox-stimulated and targeted drug delivery.

To date, numerous drug delivery systems based on mesoporous silica nanoparticles (MSNs) have been explored, but little has been done on optimizing the structure and composition of MSNs to achieve effective drug delivery for cancer cells. Ideal mesoporous drug carriers should incorporate drugs in a way that prevents pre-release in biological surroundings before reaching the targeted area, which usually requires the capping of the open ends on the surface and the incorporation of targeting ligands on the exterior of nanocarriers. In this study, an MSN-based drug carrier system was synthesized with biocompatible Au nanoparticles (NPs) as the 'hard caps', and folic acid conjugated to the surface for targeting folate receptor-overexpressed cancer cells. Disulfide bonds linking Au and MSN NPs were introduced to the MSN surface as the redox-sensitive and chemically removable components. To study the effect of structures of MSNs in drug release, three types of MSNs were compared, including hollow mesoporous silica NPs, large-pore hollow mesoporous silica NPs and typical nano-sized pores on the surface (MSN). To achieve optimal coverage of thiol groups, two methods of functionalization were compared in effecting drug loading and release in vitro. Finally, the effect of residual surfactant was also discussed in anticancer studies. Therefore, the appropriate MSN nanostructure for redox-sensitive and targeted drug delivery was optimized.

[Study of mycelial polysaccharide from Paraisaria dubia of Ophiocordyceps gracilis asexual].

In order to provide a foundation for the development and application of Ophiocordyceps gracilis and increase the new resources of cordyceps,an asexual Paraisaria dubia was isolated from an O. gracilis fruit body. After 10 days of liquid fermentation,white globular mycelium and clear transparent fermentation were produced. The mycelium was extracted by hot water and precipitated with ethanol to obtain intracellular crude polysaccharide. The protein was deproteinized to obtain deproteinized polysaccharide. The intracellular pure polysaccharide was purified by Sepharose 4 B column chromatography and were analyzed by UV,IR,1 H-NMR,and13 CNMR data,as well as GC and HPLC. The results showed that the intracellular polysaccharide of P. dubia was composed of glucose,galactose and mannose with a molar ratio of 25. 54 ∶2 ∶1. It was a ß-configuration glycosylic bond,containing pyranoside. The initial connection of polysaccharide was ß(1→2)(1→4)(1→6) connection. This experiment provides a theoretical basis for the development and application of P. dubia.

Mn3 O4 /N-Doped Graphite Catalysts from Wastewater for the Degradation of Methylene Blue.

The accelerating research interest in graphene involving the use of Hummers method has generated non-negligible amount of wastewater containing residual graphite as well as Mn2+ . In this paper, we report the first example of using this wastewater as precursor to prepare Mn3 O4 /N-doped graphite (NG) composites through a facile solvothermal process. The mass fraction of Mn3 O4 in the composites was manipulated by adding various amounts of extra Mn2+ . The conversion of Mn2+ to Mn3 O4 nanoparticles and the N atoms doping were achieved by adding hydrazine hydrate and ammonia into the system. The as-obtained Mn3 O4 /NG composites were well characterized by SEM, TEM, EDS, Raman, XPS, TGA, XRD and N2 adsorption-desorption experiments and showed excellent catalytic performances as well as stability in the degradation of a model organic pollutant methylene blue (MB). Theoretical simulation was also carried out to illustrate the structural features of the Mn3 O4 /NG composite. This work presents a novel idea of designing functional materials from waste precursors.

N-Doped Carbon Nanofibrous Network Derived from Bacterial Cellulose for the Loading of Pt Nanoparticles for Methanol Oxidation Reaction.

The large-scale, low-cost preparation of Pt-based catalysts with high activity and durability for the methanol oxidation reaction is still challenging. The key to achieving this aim is finding suitable supporting materials. In this paper, N-doped carbon nanofibrous networks are prepared by annealing a gel containing two inexpensive and ecofriendly precursors, that is, bacterial cellulose and urea, for the loading of Pt nanoparticles. An undoped analogue is also prepared for comparison. Meanwhile, the effect of the annealing temperature on the performance of the catalysts is evaluated. The results show that the N doping and higher annealing temperature can improve the electron conductivity of the catalyst and provide more active sites for the loading of ultrafine Pt nanoparticles with a narrow size distribution. The best catalyst exhibits a remarkably high electrocatalytic activity (627 mA mg-1 ), excellent poison tolerance, and high durability. This work demonstrates an ideal Pt supporting material for the methanol oxidation reaction.

Well-Combined Magnetically Separable Hybrid Cobalt Ferrite/Nitrogen-Doped Graphene as Efficient Catalyst with Superior Performance for Oxygen Reduction Reaction.

Catalysts with low-cost, high activity and stability toward oxygen reduction reaction (ORR) are extremely desirable, but its development still remains a great challenge. Here, a novel magnetically separable hybrid of multimetal oxide, cobalt ferrite (CoFe2O4), anchored on nitrogen-doped reduced graphene oxide (CoFe2O4/NG) is prepared via a facile solvothermal method followed by calcination at 500 °C. The structure of CoFe2O4/NG and the interaction of both components are analyzed by several techniques. The possible formation of Co/Fe-N interaction in the CoFe2O4/NG catalyst is found. As a result, the well-combination of CoFe2O4 nanoparticles with NG and its improved crystallinity lead to a synergistic and efficient catalyst with high performance to ORR through a four-electron-transfer process in alkaline medium. The CoFe2O4/NG exhibits particularly comparable catalytic activity as commercial Pt/C catalyst, and superior stability against methanol oxidation and CO poisoning. Meanwhile, it has been proved that both nitrogen doping and the spinel structure of CoFe2O4 can have a significant contribution to the catalytic activity by contrast experiments. Multimetal oxide hybrid demonstrates better catalysis to ORR than a single metal oxide hybrid. All results make the low-cost and magnetically separable CoFe2O4/NG a promising alternative for costly platinum-based ORR catalyst in fuel cells and metal-air batteries.

NH2-MIL-125-Derived N-Doped TiO2@C Visible Light Catalyst for Wastewater Treatment.

The utilization of titanium dioxide (TiO2) as a photocatalyst for the treatment of wastewater has attracted significant attention in the environmental field. Herein, we prepared an NH2-MIL-125-derived N-doped TiO2@C Visible Light Catalyst through an in situ calcination method. The nitrogen element in the organic connector was released through calcination, simultaneously doping into the sample, thereby enhancing its spectral response to cover the visible region. The as-prepared N-doped TiO2@C catalyst exhibited a preserved cage structure even after calcination, thereby alleviating the optical shielding effect and further augmenting its photocatalytic performance by increasing the reaction sites between the catalyst and pollutants. The calcination time of the N-doped TiO2@C-450 °C catalyst was optimized to achieve a balance between the TiO2 content and nitrogen doping level, ensuring efficient degradation rates for basic fuchsin (99.7%), Rhodamine B (89.9%) and tetracycline hydrochloride (93%) within 90 min. Thus, this study presents a feasible strategy for the efficient degradation of pollutants under visible light.

Cellular Advanced Glycation End Products Aggravate the Immune Response in Mononuclear Cells from Patients with Type 1 Diabetes.

BACKGROUND: Type 1 diabetes mellitus (T1DM) is an autoimmune disease characterized by immune response mediated islet beta cells destruction. However, the mechanisms that cause immune response in TIDM are still under investigation. Therefore, the goal of this study was to investigate the role of advanced glycation end products (AGEs) in the regulation of the immune response in peripheral blood mononuclear cells (PBMCs) from patients with T1DM. METHODS: PBMCs isolated from T1DM patients and control subjects were used in the current study. Cytokines, AGEs related to glyoxalase 1 (GLO1), methylglyoxal (MG)-derived AGEs were assessed longitudinally. RESULTS: The results of published T1DM PBMC microarray datasets using random-effects meta-analysis models revealed immune responses in the PBMCs of patients with T1DM compared with control subjects. Moreover, the activity of GLO1, which is the key MG-metabolizing enzyme, was significantly reduced in PBMCs from T1DM patients. We confirmed that, compared to the control subjects, GLO1 expression and activity were markedly decreased and MG-derived AGEs were significantly accumulated in the PBMCs from T1DM patients. In addition, phytohemagglutinin stimulated the secretion of tumor necrosis factor alpha (TNF-α), and interferon gamma (IFN-γ) was positively correlated with the accumulation of cellular AGEs. Therefore, the exposure of PBMCs from control subjects to MG and a GLO1 inhibitor enhanced the accumulation of cellular MG-derived AGEs and the secretion of TNF-α and IFN-γ. CONCLUSIONS: The results of this study showed that the accumulation of cellular AGEs causes a decline in the immune response of patients with T1DM.

Biomimetic design of platelet-rich plasma controlled release bacterial cellulose/hydroxyapatite composite hydrogel for bone tissue engineering.

Bacterial cellulose (BC) hydrogel is renowned in the field of tissue engineering for its high biocompatibility, excellent mechanical strength, and eco-friendliness. Herein, we present a biomimetic mineralization method for preparing BC/hydroxyapatite (HAP) composite hydrogel scaffolds with different mineralization time and ion concentration of the mineralized solution. Spherical HAP reinforcement enhanced bone mineralization, thereby imparting increased bioactivity to BC matrix materials. Subsequently, platelet-rich plasma (PRP) was introduced into the scaffold. The PRP-loaded hydrogel enhanced the release of growth factors, which promoted cell adhesion, growth, and bone healing. After 3 weeks of MC3T3-E1 cell-induced osteogenesis, PRP positively affected cell differentiation in BC/HAP@PRP scaffolds. Overall, these scaffolds exhibited excellent biocompatibility, mineralized nodule formation, and controlled release in vitro, demonstrating great potential for application in bone tissue repair.

Metal-organic framework derived transition metal sulfides grown on carbon nanofibers as self-supported catalysts for hydrogen evolution reaction.

Metal-organic framework (MOF) derived transition metal-based electrocatalysts have received great attention as substitutes for noble metal-based hydrogen evolution catalysts. However, the low conductivity and easy detachments from electrodes of raw MOF have seriously hindered their applications in hydrogen evolution reaction. Herein, we report the facile preparation of Co-NSC@CBC84, a porous carbon-based and self-supported catalyst containing Co9S8 active species, by pyrolysis and sulfidation of in-situ grown ZIF-67 on polydopamine-modified biomass bacterial cellulose (PDA/BC). As a binder-free and self-supported electrocatalyst, Co-NSC@CBC84 exhibits superior electrocatalytic properties to other reported cobalt-based sulfide catalytic materials and has good stability in 0.5 M H2SO4 electrolyte. At the current density of 10 mA cm-2, only an overpotential of 138 mV was required, corresponding to a Tafel slope of 123 mV dec-1, owing to the strong synergy effect between Co-NSC nanoparticles and CBC substrate. This work therefore provides a feasible approach to prepare self-supported transition metal sulfides as HER catalysts, which is helpful for the development of noble metal-free catalysts and biomass carbon materials.

Oriented bacterial cellulose microfibers with tunable mechanical performance fabricated via green reassembly avenue.

Bacterial cellulose has garnered remarkable interest from researchers, particularly those working in the biomedical field. In this work, BC microfibers were fabricated via green dissolution (ZnCl2) and regeneration (ethanol). The orientation of cellulose chains was investigated during extrusion and simple post-processing via polarized optical microscopy and small-angle X-ray scattering. The results implied that the mechanical properties of BC microfibers can be tuned by rational pre-stretching. The BC microfibers can be programmable, and be used to suture hard or soft tissues. The as-designed paralleled BC microfibers have good biocompatibility and can regulate the directional growth of cells on their surface. The as-obtained BC microfiber with a high tensile strength of up to ∼115 MPa is suitable for surgical sutures. The tunable BC microfibers may be utilized as an adequate fiber-derived biomedical material product.

Quaternized chitosan/oxidized bacterial cellulose cryogels with shape recovery for noncompressible hemorrhage and wound healing.

Management of noncompressible torso hemorrhage is an urgent clinical requirement, desiring biomaterials with rapid hemostasis, anti-infection and excellent resilient properties. In this research, we have prepared a highly resilient cryogel with both hemostatic and antibacterial effects by chemical crosslinking and electrostatic interaction. The network structure crosslinked by quaternized chitosan and genipin was interspersed with oxidized bacterial cellulose after lyophilization. The as-prepared cryogel can quickly return to the original volume when soaking in water or blood. The appropriately sized pores in the cryogel help to absorb blood cells and further activate coagulation, while the quaternary ammonium salt groups on quaternized chitosan inhibit bacterial infections. Both cell and animal experiments showed that the cryogel was hypotoxic and could promote the regeneration of wound tissue. This research provides a new pathway for the preparation of double crosslinking cryogels and offers effective and safe biomaterials for the emergent bleeding management of incompressible wounds.

Neutrophil extracellular traps aggravate intestinal epithelial necroptosis in ischaemia-reperfusion by regulating TLR4/RIPK3/FUNDC1-required mitophagy.

Neutrophil extracellular trap (NET) has been confirmed to be related to gut barrier injury during intestinal ischaemia-reperfusion (II/R). However, the specific molecular regulatory mechanism of NETs in II/R-induced intestinal barrier damage has yet to be fully elucidated. Here, we reported increased NETs infiltration accompanied by elevated inflammatory cytokines, cellular necroptosis and tight junction disruption in the intestine of human II/R patients. Meanwhile, NETs aggravated Caco-2 intestinal epithelial cell necroptosis, impairing the monolayer barrier in vitro. Moreover, Pad4-deficient mice were used further to validate the role of NETs in II/R-induced intestinal injury. In contrast, NET inhibition via Pad4 deficiency alleviated intestinal inflammation, attenuated cellular necroptosis, improved intestinal permeability, and enhanced tight junction protein expression. Notably, NETs prevented FUN14 domain-containing 1 (FUNDC1)-required mitophagy activation in intestinal epithelial cells, and stimulating mitophagy attenuated NET-associated mitochondrial dysfunction, cellular necroptosis, and intestinal damage. Mechanistically, silencing Toll-like receptor 4 (TLR4) or receptor-interacting protein kinase 3 (RIPK3) via shRNA relieved mitophagy limitation, restored mitochondrial function and reduced NET-induced necroptosis in Caco-2 cells, whereas this protective effect was reversed by TLR4 or RIPK3 overexpression. The regulation of TLR4/RIPK3/FUNDC1-required mitophagy by NETs can potentially induce intestinal epithelium necroptosis.

Diabetes mellitus is a risk factor for incident chronic kidney disease: A nationwide cohort study.

Objective: Diabetes mellitus and chronic kidney disease are multifactorial conditions with multiple etiologies that share similar pathophysiologies. This nationwide cohort study examined the impact of diabetes mellitus on the follow-up development of chronic kidney disease. Methods: By retrieving the Longitudinal Health Insurance Database 2005, 5121 patients with diabetes mellitus were included in this study and 5121 patients without diabetes mellitus, who were matched according to sex, age, and Charlson comorbidity index made up the control group. The adjusted hazard ratios for chronic kidney disease were calculated using Cox proportional hazards regression analysis. Kaplan-Meier analysis was used to estimate the cumulative incidence of chronic kidney disease rate in the diabetes mellitus and control groups. Results: After adjusting for sex, age, and Charlson comorbidity index score, the diabetes mellitus group had a 1.380 times higher (95% CI: 1.277-1.492) risk of developing chronic kidney disease than the control group. Further stratified analysis showed that patients with diabetes mellitus had a significantly higher risk of developing chronic kidney disease regardless of their sex, age, and Charlson comorbidity index score, compared to those without diabetes mellitus. Conclusions: There is a possibility that diabetes mellitus serves as an independent risk factor for chronic kidney disease development. Early screening and monitoring of diabetes mellitus appear to be of great importance in the prevention of chronic kidney disease.

Rational Design of Dynamic Interface Water Evolution on Turing Electrocatalyst toward the Industrial Hydrogen Production.

Manipulating the structural and kinetic dissociation processes of water at the catalyst-electrolyte interface is vital for alkaline hydrogen evolution reactions (HER) at industrial current density. This is seldom actualized due to the intricacies of the electrochemical reaction interface. Herein, this work introduces a rapid, nonequilibrium cooling technique for synthesizing ternary Turing catalysts with short-range ordered structures (denoted as FeNiRu/C). These advanced structures empower the FeNiRu/C to exhibit excellent HER performance in 1 m KOH with an ultralow overpotential of 6.5 and 166.2 mV at 10 and 1000 mA cm-2, respectively, and a specific activity 7.3 times higher than that of Pt/C. Comprehensive mechanistic analyses reveal that abundant atomic species form asymmetric atomic electric fields on the catalyst surface inducing a directed evolution and the dissociation process of interfacial H2O molecules. In addition, the locally topologized structure effectively mitigates the high hydrogen coverage of the active site induced by the high current density. The establishment of the relationship between free water population and HER activity provides a new paradigm for the design of industrially relevant high performance alkaline HER catalysts.

Biomimetic Design of Double-Sided Functionalized Silver Nanoparticle/Bacterial Cellulose/Hydroxyapatite Hydrogel Mesh for Temporary Cranioplasty.

A structurally stable and antibacterial biomaterial used for temporary cranioplasty with guided bone regeneration (GBR) effects is an urgent clinical requirement. Herein, we reported the design of a biomimetic Ag/bacterial cellulose/hydroxyapatite (Ag/BC@HAp) hydrogel mesh with a double-sided functionalized structure, in which one layer was dense and covered with Ag nanoparticles and the other layer was porous and anchored with hydroxyapatite (HAp) via mineralization for different durations. Such a double-sided functionalized design endowed the hydrogel with distinguished antibacterial activities for inhibiting potential infections and GBR effects that could prevent endothelial cells and fibroblasts from migrating to a defected area and meanwhile show biocompatibility to MC3T3-E1 preosteoblasts. Furthermore, it was found from in vivo experimental results that the Ag/BC@HAp hydrogel with 7-day mineralization achieved optimal GBR effects by improving barrier functions toward these undesired cells. Moreover, this BC-based hydrogel mesh showed an extremely low swelling ratio and strong mechanical strength, which facilitated the protection of soft brain tissues without gaining the risk of intracranial pressure increase. In a word, this study offers a new approach to double-sided functionalized hydrogels and provides effective and safe biomaterials used for temporary cranioplasty with antibacterial abilities and GBR effects.

Sustainable bacterial cellulose derived composites for high-efficiency hydrogen evolution reaction.

Incorporating heteroatoms into carbon structure has been demonstrated to be efficient for hydrogen evolution reaction (HER). However, the preparation complexity and poor durability are insufficient for the future hydrogen economy. In this work, the preparation of ZIF-67/BC precursor with BC as the template was done for the in-situ growth of MOFs (ZIF-67) crystals, followed by the carbonization and phosphating of ZIF-67/BC to prepare the CoP-NC/CBC N-doped composite carbon material with CoP as the primary active material. The results show that as an HER catalyst, CoP-NC/CBC can provide a current density of 10 mA cm-2 at an overpotential of 182 mV in the acidic electrolyte of 0.5 M H2SO4 or the same current density at an overpotential of 151 mV in the alkaline electrolyte of 1.0 M KOH. The work validates a design idea for advanced non-precious metal-based HER catalysts with high activity and stability.

Sulfur-doped carbonized bacterial cellulose as a flexible binder-free 3D anode for improved sodium ion storage.

Carbon-based materials have received wide attention as electrodes for energy storage and conversion owing to their rapid mass transfer processes, outstanding electronic conductivities, and high stabilities. Here, sulfur-doped carbonized bacterial cellulose (S-CBC) was prepared as a high-performance anode for sodium-ion batteries (SIBs) by simultaneous carbonization and sulfidation using the bacterial cellulose membrane produced by microbial fermentation as the precursor. Doping sublimed sulfur powder into CBC results in a greater degree of disorder and defects, buffering the volume expansion during the cycle. Significantly, the three-dimensional (3D) network structure of bacterial cellulose endows S-CBC with flexible self-support. As an anode for sodium ion batteries, S-CBC exhibits a high specific capacity of 302.9 mA h g-1 at 100 mA g-1 after 50 cycles and 177.6 mA h g-1 at 2 A g-1 after 1000 cycles. Compared with the CBC electrode, the S-CBC electrode also exhibits enhanced rate performance in sodium storage. Moreover, theoretical simulations reveal that Na+ has good adsorption stability and a faster diffusion rate in S-CBC. The doping of the S element introduces defects that enlarge the interlayer distance, and the synergies of adsorption and bonding are the main reasons for its high performance. These results indicate the potential application prospects of S-CBC as a flexible binder-free electrode for high-performance SIBs.