Boosting Hydrogen Production of a MOF-based Multicomponent Photocatalyst with Clean Interface via Facile One-pot Electrosynthesis.

Hydrogen production from photocatalysis via the usage of multicomponent photocatalysts represents a promising pathway for carbon peaking and carbon neutrality, owing to their structural advantages in dealing with the three crucial processes in photocatalysis, namely, light harvesting, charge transfer, and surface redox reactions. We demonstrate the fabrication of a MOF-based multicomponent photocatalyst, denoted as semiconductor/MOF/cocatalyst, by a one-pot electrochemical synthetic route. The as-fabricated multicomponent photocatalyst has a clean interface among the components, leading to close connections that contribute to high-quality heterojunction and facilitate photogenerated charge transfer and separation, thereby the efficient hydrogen evolution. The hydrogen production rate of the resultant ZrO2 /Zr-MOF/Pt is 1327 µmol ⋅ g-1 ⋅ h-1 , which is much higher than that of ZrO2 /Zr-MOF (15 µmol ⋅ g-1 ⋅ h-1 ) and pure Zr-MOF (10.1 µmol ⋅ g-1 ⋅ h-1 ), as well as the photodeposited-Pt products ZrO2 /Zr-MOF/PtPD (287 µmol ⋅ g-1 ⋅ h-1 ) and Zr-MOF/PtPD (192 µmol ⋅ g-1 ⋅ h-1 ) obtained by the step-wise synthetic approach. The work gives a good inspiration for the rational design and construction of MOF-based multicomponent photocatalysts through the one-pot electrosynthesis.

Chitosan-polyvinyl alcohol-diatomite hydrogel removes methylene blue from water.

Dye pollution in the aquatic environment can harm ecosystems and human health. Here, we developed a new green adsorbent by applying an improved drying process. Diatomite was embedded in a network structure formed between chitosan and polyvinyl alcohol without using any crosslinking agent to prepare chitosan-polyvinyl alcohol-diatomite hydrogel beads through alkali solidification. The beads were tested for removing a cationic dye (methylene blue (MB)) from water. The structure of the adsorbent beads was analysed using scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy. The adsorption capacity was investigated, and the results indicated excellent MB adsorption properties. The adsorbents had a rough surface and high swelling capacity of 66.9 g/g. The maximum MB adsorption capacity was 414.70 mg/g, and the adsorption followed the Freundlich isothermal and quasi-second-order kinetic models. The adsorption was an endothermic spontaneous process governed by both intra-particle and external diffusion processes. The proposed adsorption mechanisms involved hydrogen bonding and electrostatic interactions. These adsorbent beads have considerable application potentials owing to their high adsorption capacity, green composition, and non-polluting nature.

Epitaxial growth of Si thin films with hexagonal close-packed structures on metal substrates.

We have studied the epitaxial growth of Si thin films on the Cd(0001) surface using low-temperature scanning tunneling microscopy. When deposited at low temperatures (100 K), Si atoms form dendritic islands with triangular shapes, indicating the existence of anisotropic edge diffusion in the process of Si film growth. After annealing to elevated temperatures, the triangular dendritic Si islands become hexagonal compact islands. Moreover, the 2D Si islands located on two different substrate terraces exhibit different heights due to the influence of quantum-well states in Cd(0001) films. Based on high-resolution scanning tunneling microscopy images, it is observed that the first, second, and third Si layers show the pseudomorphic 1 × 1 structure. In particular, the first and second layer islands reveal the opposite triangles, indicating the hexagonal close-packed stacking of Si atoms. These results provide important information for the growth of pristine Si films on metal substrates and the understanding of Si-metal interaction.

Boosting Oxygen Evolution Performance of Nickel-Iron Layered Double Hydroxides by Controlling Oxygen Vacancies and Structural Disorder via n-Butyllithium Treatment.

Nickel-iron-based layered double hydroxides (NiFe-LDHs) are promising catalysts for the oxygen evolution reaction (OER) because of their high activity, availability, and low cost. Defect engineering, particularly the formation of oxygen vacancies, can improve the catalytic activity of NiFe-LDHs. However, the controllable introduction of uniform oxygen vacancies remains challenging. Herein, an n-butyllithium treatment method is developed to tune oxygen vacancy defects and change the degree of amorphization in NiFe-LDHs via deep reduction, followed by partial oxidization at low temperatures. Interestingly, the Ni in the NiFe-LDHs is selectively reduced to the alloy state by n-butyllithium, whereas Fe is not. The different structural transformations of Ni and Fe during the treatment successfully produce an oxygen-defect-rich amorphous/crystalline electrocatalyst. Under optimal conditions, the treated NiFe-LDHs exhibit high OER activity with an overpotential of 223 mV at 10 mA cm-2 (68 mV lower than that of a commercial IrO2 electrocatalyst) and long-term stability. Notably, the n-butyllithium treatment can be applied to other electrocatalysts, such as CoFe-LDHs and IrO2 (treated IrO2 with an overpotential of 197 mV at 10 mA cm-2). This n-butyllithium reduction/partial oxidization treatment constitutes a novel top-down strategy for the controllable modification of metal oxide structures, with various energy-related applications.

Vaccination with mycobacterial lipid loaded nanoparticle leads to lipid antigen persistence and memory differentiation of antigen-specific T cells.

Mycobacterium tuberculosis (Mtb) infection elicits both protein and lipid antigen-specific T cell responses. However, the incorporation of lipid antigens into subunit vaccine strategies and formulations has been underexplored, and the characteristics of vaccine-induced Mtb lipid-specific memory T cells have remained elusive. Mycolic acid (MA), a major lipid component of the Mtb cell wall, is presented by human CD1b molecules to unconventional T cell subsets. These MA-specific CD1b-restricted T cells have been detected in the blood and disease sites of Mtb-infected individuals, suggesting that MA is a promising lipid antigen for incorporation into multicomponent subunit vaccines. In this study, we utilized the enhanced stability of bicontinuous nanospheres (BCN) to efficiently encapsulate MA for in vivo delivery to MA-specific T cells, both alone and in combination with an immunodominant Mtb protein antigen (Ag85B). Pulmonary administration of MA-loaded BCN (MA-BCN) elicited MA-specific T cell responses in humanized CD1 transgenic mice. Simultaneous delivery of MA and Ag85B within BCN activated both MA- and Ag85B-specific T cells. Notably, pulmonary vaccination with MA-Ag85B-BCN resulted in the persistence of MA, but not Ag85B, within alveolar macrophages in the lung. Vaccination of MA-BCN through intravenous or subcutaneous route, or with attenuated Mtb likewise reproduced MA persistence. Moreover, MA-specific T cells in MA-BCN-vaccinated mice differentiated into a T follicular helper-like phenotype. Overall, the BCN platform allows for the dual encapsulation and in vivo activation of lipid and protein antigen-specific T cells and leads to persistent lipid depots that could offer long-lasting immune responses.

Phase Interface Regulating on Amorphous/Crystalline Bismuth Catalyst for Boosted Electrocatalytic CO2 Reduction to Formate.

Electroreduction of carbon dioxide into readily collectable and high-value carbon-based fuels is greatly significant to overcome the energy and environmental crises yet challenging in the development of robust and highly efficient electrocatalysts. Herein, a bismuth (Bi) heterophase electrode with enriched amorphous/crystalline interfaces was fabricated via cathodically in situ transformation of Bi-based metal-phenolic complexes (Bi-tannic acid, Bi-TA). Compared with amorphous or crystalline Bi catalyst, the amorphous/crystalline structure Bi leads to significantly enhanced performance for CO2 electroreduction. In a liquid-phase H-type cell, the Faraday efficiency (FE) of formate formation is over 90% in a wide potential range from -0.8 to -1.3 V, demonstrating a high selectivity toward formate. Moreover, in a flow cell, a large current density reaching 600 mA cm-2 can further be rendered for formate production. Theoretical calculations indicate that the amorphous/crystalline Bi heterophase interface exhibits a favorable adsorption of CO2 and lower energy barriers for the rate-determining step compared with the crystalline Bi counterparts, thus accelerating the reaction process. This work paves the way for the rational design of advanced heterointerface catalysts for CO2 reduction.

Biomass Derived, Hierarchically Porous, Activated Starbons® as Adsorbents for Volatile Organic Compounds.

The use of potassium hydroxide activated Starbons® derived from starch and alginic acid as adsorbents for 29 volatile organic compounds (VOCs) was investigated. In every case, the alginic acid derived Starbon (A800K2) was found to be the optimal adsorbent, significantly outperforming both commercial activated carbon and starch derived, activated Starbon (S800K2). The saturated adsorption capacity of A800K2 depends on both the size of the VOC and the functional groups it contains. The highest saturated adsorption capacities were obtained with small VOCs. For VOC's of similar size, the presence of polarizable electrons in lone pairs or π-bonds within non-polar VOCs was beneficial. Analysis of porosimetry data suggests that the VOC's are being adsorbed within the pore structure of A800K2 rather than just on its surface. The adsorption was completely reversible by thermal treatment of the saturated Starbon under vacuum.

Constructing a Hierarchical Hydrophilic Crosslink Network on the Surface of a Polyvinylidene Fluoride Membrane for Efficient Oil/Water Emulsion Separation.

Oil/water mixtures from industrial and domestic wastewater adversely affect the environment and human beings. In this context, the development of a facile and improved separation method is crucial. Herein, dopamine was used as a bioadhesive to bind tea polyphenol (TP) onto the surface of a polyvinylidene fluoride (PVDF) membrane to form the first hydrophilic polymer network. Sodium periodate (NaIO4) is considered an oxidising agent for triggering self-polymerisation and can be used to introduce hydrophilic groups via surface manipulation to form the second hydrophilic network. In contrast to the individual polydopamine (PDA) and TP/NaIO4 composite coatings for a hydrophobic PVDF microfiltration membrane, a combination of PDA, TP, and NaIO4 has achieved the most facile treatment process for transforming the hydrophobic membrane into the hydrophilic state. The hierarchical superhydrophilic network structure with a simultaneous underwater superoleophobic membrane exhibited excellent performance in separating various oil-in-water emulsions, with a high water flux (1530 L.m-2 h-1.bar) and improved rejection (98%). The water contact angle of the modified membrane was 0° in 1 s. Moreover, the steady polyphenol coating was applied onto the surface, which endowed the membrane with an adequate antifouling and recovery capability and a robust durability against immersion in an acid, alkali, or salt solution. This facile scale-up method depends on in situ plant-inspired chemistry and has remarkable potential for practical applications.

Vaccination with mycobacterial lipid loaded nanoparticle leads to lipid antigen persistence and memory differentiation of antigen-specific T cells.

Mycobacterium tuberculosis (Mtb) infection elicits both protein and lipid antigen-specific T cell responses. However, the incorporation of lipid antigens into subunit vaccine strategies and formulations has been underexplored, and the characteristics of vaccine-induced Mtb lipid-specific memory T cells have remained elusive. Mycolic acid (MA), a major lipid component of the Mtb cell wall, is presented by human CD1b molecules to unconventional T cell subsets. These MA-specific CD1b-restricted T cells have been detected in the blood and disease sites of Mtb-infected individuals, suggesting that MA is a promising lipid antigen for incorporation into multicomponent subunit vaccines. In this study, we utilized the enhanced stability of bicontinuous nanospheres (BCN) to efficiently encapsulate MA for in vivo delivery to MA-specific T cells, both alone and in combination with an immunodominant Mtb protein antigen (Ag85B). Pulmonary administration of MA-loaded BCN (MA-BCN) elicited MA-specific T cell responses in humanized CD1 transgenic mice. Simultaneous delivery of MA and Ag85B within BCN activated both MA- and Ag85B-specific T cells. Notably, pulmonary vaccination with MA-Ag85B-BCN resulted in the persistence of MA, but not Ag85B, within alveolar macrophages in the lung. Vaccination of MA-BCN through intravenous or subcutaneous route, or with attenuated Mtb likewise reproduced MA persistence. Moreover, MA-specific T cells in MA-BCN-vaccinated mice differentiated into a T follicular helper-like phenotype. Overall, the BCN platform allows for the dual encapsulation and in vivo activation of lipid and protein antigen-specific T cells and leads to persistent lipid depots that could offer long-lasting immune responses.

The humoral and cellular immune evasion of SARS-CoV-2 Omicron and sub-lineages.

The recently discovered SARS-CoV-2 variant Omicron (B.1.1.529) has rapidly become a global public health issue. The substantial mutations in the spike protein in this new variant have raised concerns about its ability to escape from pre-existing immunity established by natural infection or vaccination. In this review, we give a summary of current knowledge concerning the antibody evasion properties of Omicron and its subvariants (BA.2, BA.2.12.1, BA.4/5, and BA.2.75) from therapeutic monoclonal antibodies and the sera of SARS-CoV-2 vaccine recipients or convalescent patients. We also summarize whether vaccine-induced cellular immunity (memory B cell and T cell response) can recognize Omicron specifically. In brief, the Omicron variants demonstrated remarkable antibody evasion, with even more striking antibody escape seen in the Omicron BA.4 and BA.5 sub-lineages. Luckily, the third booster vaccine dose significantly increased the neutralizing antibodies titers, and the vaccine-induced cellular response remains conserved and provides second-line defense against the Omicron.

Immune escape mechanisms of severe fever with thrombocytopenia syndrome virus.

Severe fever with thrombocytopenia syndrome (SFTS), which is caused by SFTS virus (SFTSV), poses a serious threat to global public health, with high fatalities and an increasing prevalence. As effective therapies and prevention strategies are limited, there is an urgent need to elucidate the pathogenesis of SFTS. SFTSV has evolved several mechanisms to escape from host immunity. In this review, we summarize the mechanisms through which SFTSV escapes host immune responses, including the inhibition of innate immunity and evasion of adaptive immunity. Understanding the pathogenesis of SFTS will aid in the development of new strategies for the treatment of this disease.

Robust humoral and cellular immune responses in long-term convalescent COVID-19 individuals following one-dose SARS-CoV-2 inactivated vaccination.

COVID-19, caused by SARS-CoV-2, has resulted in hundreds of millions of infections and millions of deaths worldwide. Preliminary results exhibited excellent efficacy of SARS-CoV-2 vaccine in preventing hospitalization and severe disease. However, data on inactivated vaccine-induced immune responses of naturally infected patients are limited. Here, we characterized SARS-CoV-2 RBD-specific IgG (anti-S-RBD IgG) and neutralizing antibodies (NAbs) against SARS-CoV-2 wild type and variants of concerns (VOCs), as well as RBD-specific IgG-secreting B cells and antigen-specific T cells respectively in 51 SARS-CoV-2 recovered subjects and 63 healthy individuals. In SARS-CoV-2 recovered patients, a single dose vaccine is sufficient to reactivate robust anti-S-RBD IgG and NAbs. The neutralizing capacity against VOCs increased significantly post-vaccination no matter healthy individuals or SARS-CoV-2 recovered patients. In addition, RBD-specific IgG-secreting B cells in SARS-CoV-2 recovered patients were significantly higher than that in healthy vaccine recipients. After the vaccine booster, the frequencies of specific IFN-γ+ CD4+ T cell, IL-2+ CD4+ T cell, and TNF-α+ CD4+ T cell responses were significantly increased in SARS-CoV-2 recovered patients. Our data highlighted the safety and utility of SARS-CoV-2 inactivated vaccine and demonstrated that robust humoral and cellular immune response can be reactivated by one-dose inactivated vaccine in SARS-CoV-2 recovered patients.

Structural transition and interconversion between the 2D self-assembled structures of pentacene.

The 2D self-assemblies and structural transitions of pentacene on a Cd(0001) surface have been investigated with low temperature scanning tunneling microscopy (STM). With increasing coverage, pentacene molecules show a structural evolution from the initial disordered gas-like phase through the porous network phase to the herringbone phase, and finally to the brickwall phase at the full monolayer. In particular, orientational frustration and cooperative rotation of pentacene molecules take place in the herringbone phase. Furthermore, successive STM scanning leads to structural interconversions between the porous network phase, herringbone phase, and brickwall phase, indicating the metastability of the 2D assembled structures of pentacene on Cd(0001). These structural transitions and interconversion can be attributed to the interplay between the repulsive electrostatic forces resulting from the charge transfer from the substrate to pentacene and the attractive effects originating from dipole-dipole interactions and intermolecular van der Waals forces.

Fecal Microbiota Transplantation Alters the Outcome of Hepatitis B Virus Infection in Mice.

The susceptibility of mice to hepatitis B virus (HBV) infection depends on their genetic background. The gut microbiota modulates the antiviral immune response in the liver and plays a protective role against HBV infection. However, whether HBV infection outcomes depend on the gut microbiota remains unclear. In this study, we assessed the gut microbiota composition in naïve BALB/c and C57BL/6 mice using 16S rRNA gene sequencing. The gut microbiota in BALB/c mice was depleted using broad-spectrum antibiotics (ABX) and then reconstituted with fecal microbiota from naïve BALB/c or C57BL/6 mice to evaluate the effect of fecal microbiota transplantation (FMT) on the outcomes of and immune response to HBV infection. We found that HBV infection outcomes and the gut microbiota composition differed between BALB/c and C57BL/6 mice. Commensal bacteria from the fecal microbiota selectively colonized the guts of ABX-treated BALB/c mice. Mice receiving fecal microbiota from BALB/c or C57BL/6 mice displayed different HBV infection outcomes. The fecal microbiota from C57BL/6 mice induced immune tolerance in the liver and prolonged HBV infection. In conclusion, HBV infection outcomes in mice are determined by the host genetic background and gut microbiota composition. Reconstitution of the gut microbiota by FMT can alter the susceptibility to HBV infection in mice.

Spontaneous chiral resolution of pentahelicene molecules on Cd(0001).

Chiral resolution is of fundamental importance to conglomerate or racemate crystallization. Here we demonstrate that the spontaneous chiral resolution of pentahelicene racemates occurred in the monolayer domains. When deposited on a Cd(0001) surface, pentahelicene molecules crystallize into a commensurate (6 × 6)R0° structure built mainly from homochiral trimers. Spontaneous chirality separation takes place in the form of opposite mirror domains, where 2D enantiomorphism is not expressed by the oblique adlattice, but by the supramolecular chirality of the pentahelicene trimers. Furthermore, annealing the sample or extreme close-packing lead to the presence of lattice handedness through the formation of a porous network structure or an edge-on phase. These results provide valuable insight for 2D conglomerate crystallization and stereochemical recognition.

Freestanding Surface Disordered NiCu Solid Solution as Ultrastable High Current Density Hydrogen Evolution Reaction Electrode.

The poor performance of conventional powdery catalysts under large current density and the slow kinetics of the Volmer step limit the large-scale application of alkaline hydrogen generation. Here, we report the preparation of freestanding surface disordered NiCu solid solution as an ultrastable hydrogen evolution reaction electrode. The introduction of ammonium ion could tailor the reduction/nucleation rate of metal ions during the hydrothermal process, thus contributing to its unique intertwined 3D microstructure. The catalyst exhibits superior HER activity with an overpotential of 322 mV at 1000 mA cm-2, and limited degradation after 110 h continuous operation at 1000 mA cm-2. Density functional theory calculations confirm that the substitution of Cu could accelerate the hydroxyl desorption process (OHads + e- → OH-) and thereby enhance the overall kinetics of the Volmer step. Our work demonstrates the strong efficacy of optimizing catalysts' structures and facilitating intermediate desorption for boosting industrial-scale alkaline HER performance.

Homochiral to heterochiral transition in a pentahelicene monolayer on Bi(111).

We report the nucleation and two dimensional (2D) crystallization of the helical aromatic hydrocarbon pentahelicene ([5]H) on the semimetallic Bi(111) surface studied via low-temperature scanning tunneling microscopy. Individual homochiral dimers and heterochiral trimers appear on the substrate at a low coverage. With an increase in the coverage, a chiral phase transition takes place from the 2D conglomerate of [5]H dimers to the 2D racemate of [5]H trimers. The heterochiral [5]H trimers reveal a wavy arrangement due to the swing of 5[H] trimer rows after every second or third trimers. The swing mechanism of the trimer rows can be attributed to the steric repulsion between the adjacent trimers with same handedness.

Polymer dependent acoustic mode coupling and Hooke's law spring constants in stacked gold nanoplates.

Metal nanoparticles are excellent acoustic resonators and their vibrational spectroscopy has been widely investigated. However, the coupling between vibrational modes of different nanoparticles is less explored. For example, how the intervening medium affects the coupling strength is not known. Here, we investigate how different polymers affect coupling in Au nanoplate-polymer-Au nanoplate sandwich structures. The coupling between the breathing modes of the Au nanoplates was measured using single-particle pump-probe spectroscopy, and the polymer dependent coupling strength was determined experimentally. Analysis of the acoustic mode coupling gives the effective spring constant for the polymers. A relative motion mode was also observed for the stacked Au nanoplates. The frequency of this mode is strongly correlated with the coupling constant for the breathing modes. The breathing mode coupling and relative motion mode were analyzed using a coupled oscillator model. This model shows that both these effects can be described using the same spring constant for the polymer. Finally, we present a new type of mass balance using the strongly coupled resonators. We show that the resonators have a mass detection limit of a few femtograms. We envision that further understanding of the vibrational coupling in acoustic resonators will improve the coupling strength and expand their potential applications.

Strain-Relief Patterns and Kagome Lattice in Self-Assembled C60 Thin Films Grown on Cd(0001).

We report an ultra-high vacuum low-temperature scanning tunneling microscopy (STM) study of the C60 monolayer grown on Cd(0001). Individual C60 molecules adsorbed on Cd(0001) may exhibit a bright or dim contrast in STM images. When deposited at low temperatures close to 100 K, C60 thin films present a curved structure to release strain due to dominant molecule-substrate interactions. Moreover, edge dislocation appears when two different wavy structures encounter each other, which has seldomly been observed in molecular self-assembly. When growth temperature rose, we found two forms of symmetric kagome lattice superstructures, 2 × 2 and 4 × 4, at room temperature (RT) and 310 K, respectively. The results provide new insight into the growth behavior of C60 films.

Depletion of Gut Microbiota Impairs Gut Barrier Function and Antiviral Immune Defense in the Liver.

Commensal gut microbiota protects the immune defense of extra-intestinal organs. Gut microbiota depletion by antibiotics can impair host antiviral immune responses and alter hepatitis B virus (HBV) infection outcomes. However, how gut microbiota modulates antiviral immune response in the liver remains unclear. Here, mice were treated with broad-spectrum antibiotics to deplete gut microbiota. Gut integrity was evaluated, and translocation of live commensal gut bacteria and their components into the liver was investigated. An HBV infection model was established to evaluate impairment of antiviral immune response in the liver after gut microbiota depletion. We found that gut microbiota depletion was associated with impairment of colon epithelial integrity, and live commensal gut microbiota could translocate to the liver. Further, T cell antiviral function in the liver was impaired, partially relying on enhanced PD-1 expression, and HBV immune clearance was hampered. In conclusion, gut microbiota depletion by antibiotics can impair gut barrier function and suppress T cell antiviral immune response in the liver.