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In this study, we aim to synthesize self-assembled amphiphilic diblock poly(PEGA-b-HEA-PCL) copolymers through RAFT living polymerization, targeting the delivery of hydrophobic anticancer drugs. The synthesized self-assembled diblock copolymers polymeric micelles (PMs) comprising poly(ethylene glycol) methyl ether acrylate (PEGA), as a hydrophilic segment and 2-hydroxyethyl acrylate-polyhexanoate monomer (HEA-PCL) with different block lengths, as a hydrophobic segment. The chemical structures, compositions, and self-assembled behavior were identified through 1H NMR spectroscopy. The thermal stability was assessed through TGA and DSC. Furthermore, DOX was encapsulated into all PMs. The drug-loaded PMs exhibited enhanced drug release profiles in acidic medium. Particle diameter was measured through DLS and TEM techniques. The cell viability of diblock polymers and selected DOX-loaded PMs were evaluated against non-cancerous (L929) and cancerous cells (SK-N-AS), respectively, through well-known MTT assay. Micellar aggregates with mean diameters of approximately 127.2–145.3 nm formed in aqueous solution. The diameters of PMs increased to 141.5–173.1 nm upon the incorporation of DOX. The drug loading content and encapsulation efficiency of PMs were approximately 8.09–18.84% and 30.43–54.07%, respectively. The MTT assay results indicated that all synthesized materials had minimal effects on the viability of L929 cells, while DOX-loaded materials inhibited the viability of neuroblastoma cells by 68.7%. The highest drug release was 89.20% at pH 7.4, while 83.45% at pH 5.0 for 40 h. These findings suggest that the synthesized amphiphilic PMs are promising candidates for drug delivery systems. [ABSTRACT FROM AUTHOR]

The composites (SiO2/HATP) were prepared by condensation reflux and high-temperature calcination using natural attapulgite and silica particles, and it was utilized for the adsorption of toluene. The physicochemical properties of the composite adsorbents were characterized using XRD, FT-IR, SEM, and BET techniques. The SiO2/HATP composite material was successfully prepared, with silica particles uniformly loaded onto the surface of ATP. The adsorption performance of the composite materials for toluene was investigated using different feed ratios. The results showed that the composite materials with the mass ratio SiO2/ATP equal to 4 exhibited the highest static adsorption capacity for toluene, reaching 236 mg/g. Additionally, dynamic adsorption performance of toluene was evaluated under conditions of 0 and 80% relative humidity, with corresponding breakthrough times of 90 and 36 min, respectively. The adsorption capacity of the composite materials for toluene was 6–8 times higher than that of pure attapulgite clay. Furthermore, the adsorption mechanisms of the composite materials were investigated through adsorption kinetics, adsorption isotherms, and adsorption thermodynamics. The results indicated that the adsorption of toluene by the composite materials followed a pseudo-first-order kinetic model and Langmuir adsorption isotherm, suggesting a spontaneous exothermic physical adsorption process at a monolayer level. Moreover, regeneration experiments were conducted, and after 5 cycles of adsorption-desorption tests, the composite materials maintained a penetration time of 85 and 30 min for toluene under conditions of 0 and 80% relative humidity, respectively, demonstrating good recyclability. [ABSTRACT FROM AUTHOR]

Photothermal catalytic oxidation emerges as a promising method for the removal of volatile organic compounds (VOCs). Herein, via sol-gel impregnation method, spinel CuMn2O4 was coated on attapulgite honeycombs with integrating biochar (BC) film as the second carrier, using chestnut shell as complexation agent. Various mass ratios of CuMn2O4 to chestnut shell was modulated to investigate the catalytic toluene degradation performance. Results indicated that the monolithic CuMn2O4/BC/honeycomb catalyst demonstrated superior photothermal catalytic toluene degradation with a low T90 (temperature at 90% degradation) of 263 °C when the mass ratio of CuMn2O4 to biomass was 1:4. The addition of BC film substantially increased the honeycomb's specific surface area and improved the photothermal conversion of spinel, leading to enhanced photothermal catalytic activity. This study presents a cost-effective strategy for eliminating industrial VOCs using clay-biomass based monolithic catalyst. [ABSTRACT FROM AUTHOR]

Tumor-infiltrating lymphocyte (TIL) deficiency is the most conspicuous obstacle to limit the cancer immunotherapy. Immune checkpoint inhibitors (ICIs), such as anti-PD-1 antibody, have achieved great success in clinical practice. However, due to the limitation of response rates of ICIs, some patients fail to benefit from monotherapy. Thus, novel combination therapy that could improve the response rates emerges as new strategies for cancer treatment. Here, we reported that the natural product rocaglamide (RocA) increased tumor-infiltrating T cells and promoted Th17 differentiation of CD4+ TILs. Despite RocA monotherapy upregulated PD-1 expression of TILs, which was considered as the consequence of T cell activation, combining RocA with anti-PD-1 antibody significantly downregulated the expression of PD-1 and promoted proliferation of TILs. Taken together, these findings demonstrated that RocA could fuel the T cell anti-tumor immunity and revealed the remarkable potential of RocA as a therapeutic candidate when combining with the ICIs. [ABSTRACT FROM AUTHOR]

The specific surface area of attapulgite was significantly enhanced (from 128 to 212 m2/g) by its purification with sodium hexametaphosphate and nitric acid. Subsequently, an acid modification method was employed to prepare a coated attapulgite cordierite honeycomb with a specific surface area approximately 39 times larger than that of the bare cordierite honeycomb. SEM images showed that the surface of the cordierite was rough and uneven, with the attapulgite filling the large pores on its surface, forming a "nail-like" interaction between the coating and the carrier. After loading the catalyst, no significant mass loss was observed after 1 h of ultrasonic testing, indicating good adhesion stability of the coating. Furthermore, under test conditions of GHSV (Gas Hourly Space Velocity) = 10 000 h–1 and a toluene concentration of 1500 ppm, the prepared integrated catalyst exhibited excellent activity for the catalytic oxidation of toluene, with T50 and T90 values of 261 and 290°C, respectively, suggesting broad application prospects. [ABSTRACT FROM AUTHOR]

Simultaneous conversion of CO2 and biomass into value-added chemicals through solar-driven catalysis holds tremendous importance for fostering a sustainable circular economy. Herein, plasmonic Bi quantum dots were immobilized on phosphoric acid modified attapulgite (P-ATP) nanorod using an in-situ reduction–deposition method, and were employed for photocatalytic reduction of CO2 coupled with oxidation of biomass-derived benzyl alcohol. Results revealed that Bi atoms successfully integrated into the basal structure of P-ATP, forming chemically coordinated Bi–O–Si bonds that served as efficient transportation channels for electrons. The incorporation of high-density monodispersed Bi quantum dots induced a surface plasmon resonance (SPR) effect, expanding the light absorption range into the near-infrared region. As a consequence, the photo-thermal transformation was significantly accelerated, leading to enhanced reaction kinetics. Notably, 50% Bi/P-ATP nanocomposite exhibited the highest plasmon-mediated photocatalytic CH4 generation (115.7 µmol·g−1·h−1) and CO generation (44.9 µmol·g−1·h−1), along with remarkable benzaldehyde generation rate of 79.5 µmol·g−1·h−1 in the photo-redox coupling system under solar light irradiation. The hydrogen protons released from the oxidation of benzyl alcohol facilitated the incorporation of more hydrogen protons into CO2 to form key CH3O− intermediates. This work demonstrates the synergistic solar-driven valorization of CO2 and biomass using natural mineral based catalyst. [ABSTRACT FROM AUTHOR]

Micro-cracks inevitably form in cement concrete structures, presenting substantial risks to safety, service life, and eco-efficiency. Developing high-intrinsic self-healing concrete offers a promising approach to promptly alleviate issues caused by microcracks. These issues include rapid matrix degradation and frequent maintenance requirements. This paper reviews recent advancements in autogenous self-healing concrete technologies. It discusses their classification, efficiency, and mechanisms based on concrete component categorisation, normalisation methods, and statistical analyses. Results indicate that intrinsic self-healing relies heavily on the physical and chemical properties of the concrete, external water, and crack dimensions. Several methods for adjusting concrete component parameters, types, and proportions enhance self-healing capability. In addition, minimising crack width proves beneficial. Enhancement mechanisms of each technology demonstrate significant diversity and complexity due to the intricate self-healing process. They primarily fall into three categories: mechanical mechanisms (microparticle accumulation, fibre bridging), physical mechanisms (swelling, ion adsorption, matrix porosity, roughness, crack width), and chemical mechanisms (improved hydration reaction, expansion product generation, precipitation reaction mechanisms, complexation-precipitation and chelation reactions). [ABSTRACT FROM AUTHOR]

Hyaluronic acid (HA) is one of the main components of the extracellular matrix, and functions as a stabilizing molecule for cell-niche interactions. Although the mechanism of HA in supporting cell attachment is debatable, HA-based scaffolds are increasingly being applied in tissue engineering owing to their excellent mechanical properties and biocompatibility. HA reportedly enhances the intestinal growth in postnatal mice. In the present study, we aimed to investigate the effects of HA on intestinal stem cells (ISCs) using an in vitro enteroid culture system. A high-concentration of HA (0.5 mg/mL) significantly lowered the proliferative activity of ISCs with decreased enteroid-forming efficiency compared to the control ISCs. In contrast, a low-concentration of HA (0.1 mg/mL) did not affect the enteroid-forming efficiency of ISCs, but up regulated markers of enterocytic differentiation, villin, and HA receptor, CD44 and TLR4, in the enteroid cells. When enteroid fragments were seeded on an intestinal submucosa bioscaffold, HA treatment enhanced the growth and differentiation of enteroid cells on the material with a high villin expression level in the cell grafts. These results suggest that HA treatment is effective in promoting enterocytic differentiation of ISCs and enteroid grafting on scaffolds. [ABSTRACT FROM AUTHOR]

Most of the gas exchange in the human body is carried out by the lungs, and the physiological activities of the lungs are uninterrupted. Due to the deterioration of the external environment, pulmonary cell lesions are common clinical lung diseases. Mechanical cyclic stretching is one kind of bionic technology to observe lung cancer cells. The A549 cell line is the human lung adenocarcinoma cell line derived from a primary lung tumor. This study investigated the effects of mechanical cyclic stretching on A549 cell activity and gene expression profile. Whereas mechanical cyclic stretching had no significant difference in colony formation and cell migration of A549 cells, the cell invasion increased significantly in A549 cells after stretching. In addition, the microarray data showed that mechanical cyclic stretching altered gene expression, induced inflammation of cells, and activation of Wnt/β-catenin and tumor necrosis factor pathways. More importantly, mechanical cyclic stretching activated the expression of tumor necrosis factor-alpha (TNF-α) protein. Therefore, the increase of cell invasion induced by mechanical cyclic stretching might be associated with the activation of TNF-α in human lung adenocarcinoma cells. [ABSTRACT FROM AUTHOR]

Decellularized human umbilical arteries (dHUA) is an off-the-shelf graft that can potentially serve as vascular scaffolds in tissue engineering of small-diameter vascular grafts. This research aimed to investigate that dHUA could exhibit adequate endothelialization for a long term in xenogenic transplantation. 13 dHUAs were implanted in rat abdominal aortas up to 90 days. Rats were divided into three groups in terms of survival period: Group 1, one to seven days (n = 6); Group 2, 14 to 30 days (n = 4) and Group 3, 90 days (n = 3). The explants were analyzed by histological, immunohistochemistry and magnetic resonance angiography (MRA) examination. Allograft implantation of 12 decellularized rat abdominal aortas' were processed the same way as the rat in order to make a comparison for survival rates (Group 1, n = 5; Group 2, n = 4; Group 3, n = 3). The results demonstrated that the survival rates of xenograft and allograft implantation were estimated to be 59.2% vs. 58.3% in Group 1, 50.7% vs. 58.3% in Group 2 and 3. Grafts harvested from Group 2 were showed CD31, endothelial nitric oxide synthase expression at intima, and α-smooth muscle actin, CD45, CD68 and CD168 expression at the tunica externa. A layer structure with obvious endothelialization and fiber regeneration/orientation could be inspected from the explants of Group 3. MRA demonstrated the patency of dHUA on day 30 and 90. In conclusion, more than 50% dHUA maintained patency in the xenogenic model till 90 days after surgery. A mature vessel-like functional structure with intact endothelial layer was observed then. This warrants further study in the reinforcement of decellularized vascular scaffolds. [ABSTRACT FROM AUTHOR]

Repair and regeneration of vascular tissue is a crucial current research focus in the fields of biomedical engineering and regenerative medicine. Numerous studies revealed that cells are required to grow on an appropriate extracellular matrix to maintain or enhance functionality. In the present study, various surface modification methods were evaluated to fix fibronectin on the surface of a bio-based and aligned poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) film for vascular tissue engineering. After chemical modification, the properties of the fibronectin-fixed PHBV films were examined and compared with the original films, including -NH2 group expression, contact angle, mechanical properties, and fibronectin binding amount. Then, cytotoxicity and biocompatibility were measured by culture with L929 cells and endothelial progenitor cells (EPCs) of the fibronectin-fixed PHBV films. In addition, cell morphology, cell growth kinetics, acetylated low-density lipoprotein uptake ability, lectin binding ability and specific gene expressions of cultured EPCs on fibronectin-fixed PHBV films were also analyzed. Taken together, our data demonstrated that the surface of the aligned PHBV films could be successfully modified to immobilize fibronectin. Importantly, EPCs cultured on the fibronectin-fixed PHBV films showed excellent cell biocompatibility, a rapid proliferation rate, an aligned growth direction and correct cell functions. We believed that fibronectin-fixed PHBV films can serve as a potential scaffold for vascular tissue engineering. [ABSTRACT FROM AUTHOR]

Complex pollutants are discharging and accumulating in rivers and oceans, requiring a coupled strategy to resolve pollutants efficiently. A novel method is proposed to treat multiple pollutants with C,N co-doped TiO2 hollow nanofibers coated stainless steel meshes which can realize efficient oil/water separation and visible light-drove dyes photodegradation. The poly(divinylbenzene-co-vinylbenzene chloride), P(DVB-co-VBC), nanofibers are generated by precipitate cationic polymerization on the mesh framework, following with quaternization by triethylamine for N doping. Then, TiO2 is coated on the polymeric nanofibers via in-situ sol–gel process of tetrabutyl titanate. The functional mesh coated with C,N co-doped TiO2 hollow nanofibers is obtained after calcination under nitrogen atmosphere. The resultant mesh demonstrates superhydrophilic/underwater superoleophobic property which is promising in oil/water separation. More importantly, the C,N co-doped TiO2 hollow nanofibers endow the mesh with high photodegradation ability to dyes under visible light. This work draws an affordable but high-performance multifunctional mesh for potential applications in wastewater treatment. [ABSTRACT FROM AUTHOR]

Pyrolysis or dissolution of waste PET plastics (WPP) by specific solvents, which is inevitable in the resource's secondary utilization, will lead to chemical bond fracture thus resulting in loss of mechanical strength. This greatly restricts the secondary utilization of WPP. We proposed a simple and economical new chemical method to transform WPP into a high–value monolithic material, which not only solves the problem of environmental pollution, but also provides a new idea for the disposal of WPP. The new high temperature resistant chemical structure Al–O–P–O–Al was successfully generated through the reaction of high temperature resistant adhesive Al(H2PO4)3 (AHP) with the monomer or polymer from dissolved WPP. New chemical bonds such as –OH, C = O, C–Cl, P = O were also formed in the transformed monolithic material structure, and they were the principal reason for the increase in mechanical strength of monolithic material. The original hydrophilic group on the surface of the monolithic material was replaced by the hydrophobic group –CH3 after the treatment by triethoxyoctylsilane (TS). Ultimately, the resulting monolithic material exhibited good comprehensive properties of high flame retardancy, flame retardancy (~ 1300 °C), mechanical strength (maximum compressive strength of 29.1 MPa), and hydrophobicity (water contact angle: 110°). This work has important implications for solving the serious problem of a sharp decline in mechanical strength and inflammability in the reuse of WPP. [ABSTRACT FROM AUTHOR]

High performance electrochemical energy storage device is an important means to solve the energy problem. As one of the next generation energy storage components, supercapacitor has received more and more attention in recent years. In this work, we synthesized a self-supporting MnCo2O4@Co(OH)2 core–shell heterostructure (CSHs), this can not only enhance the strength of the material, but also generate abundant electron transport pathways. In addition, we also added flaky carbon nitride (g-C3N4) after treatment with nitric acid (HNO3) to improve the cycle stability and specific capacitance of the material. By adjusting the chemical bath (CBD) time, the loading amount of Co(OH)2 nanosheets can be controlled, giving full play to the synergy between the materials, so that the prepared composite has greater specific capacitance, higher rate performance and better cycle stability. When the current density is 0.5 A·g−1, the specific capacitance of the composite is about 1932 F·g−1. In the two electrode system, the energy density is 23.2 Wh·kg−1 at a power density of 600 W·kg−1. At a high current density of 10 A·g−1, after 10,000 cycles, the initial capacitance of the composite material maintained 83.3%. [ABSTRACT FROM AUTHOR]

Nickel aluminum hydrotalcite/clay/activated carbon (LDH/BE/AC) composites were prepared by urea hydrolysis from spent bleaching earth (SBE) to adsorb and remove Chlorotetracycline (CTC), Tetracycline (TC) and Ciprofloxacin (CIP) in aqueous solution. The adsorption method has the advantages of low cost, high efficiency, no secondary pollution and simple and easy operation. A series of performance tests were carried out on the composites. The results show that when the dosage of clay/activated carbon (BE/AC) is 0.2 g, the distribution of LDH/BE/AC on BE/AC is relatively uniform, which is conducive to the adsorption of pollutants. Compared with BE/AC, because the synthesis of LDH/BE/AC occupies the pores on the surface and inside of BE/AC, the specific surface area and pore volume of LDH/BE/AC composites are reduced. But at the same time, the adsorption sites of BE/AC are increased and the adsorption capacity is enhanced. The optimum adsorption capacities of the composites for CTC, TC and CIP are 160.4 mg/g, 122.3 mg/g and 91.3 mg/g respectively, and have good cycle stability. This paper provides an idea for industrial sewage treatment, that is treating waste with waste. [ABSTRACT FROM AUTHOR]

A series of SmFeAsO1-xFx (Sm1111) tapes were fabricated by the ex situ powder-in-tube (PIT) method. A powder-impregnated post-rolling sintering (PRS) process was applied to the Sm1111 tapes to suppress the loss of F element in the tapes during PRS. By this method, the Sm1111 tapes can endure long-time sintering at 850 ℃ without Tc degradation. A series of Sm1111 tapes with high transition temperature (> 50 K) were obtained. EPMA analysis reveals that the superconducting cores in tapes after this PRS process have the similar F concentration with the Sm1111 precursor bulk. [ABSTRACT FROM AUTHOR]

Ultra-high performance fiber reinforced concrete (UHPFRC) is well known for its superior workability, strength, ductility as well as durability, but its intrinsic self-healing ability is rarely valued and developed. This review focuses on the inherent potential or superiority, characterization, and mechanism of autogenous healing UHPFRC, aiming to obtain fundamental data for its mixture innovation, design, and application. High potentialities of autogenous self-healing UHPFRC depend on its excellent component requirements (fiber; abundant binding particles), mix design (high cementitious materials content, low water-binder ratio, moderate fiber content), rehydration capacity, and shrinkage or loading-initiated cracking features. Meantime, the generation of cracks makes the internal substances include active ingredients exposed to the external environment such as air, water, and temperature, which induces physical, chemical, and mechanical interaction between them at cracks. Intrinsic partial or entire sealing of the multiple cracks in UHPFRC has been proven to improve the safety and durability of UHPFRC infrastructures. A higher healing rate exists in cracks with a width of 75–175 μm, which is connected with crack healing kinetics, and the width of total healing cracks can reach up to 162 μm, which is mainly filled with calcium carbonate. Continuous accumulation of healing products at cracks can effectively improve the mechanical properties and suppress the decay of transport performance and steel fiber corrosion. Furthermore, mild fiber corrosion contributes to the partial restoration of flexural strength during the self-healing process. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Central South University is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

A high-efficiency carbon-based metal catalyst was prepared using inexpensive raw materials and a simple synthetic method to replace the commercial platinum-based catalyst in oxygen reduction reaction (ORR). In this article, clay was used as the template, and residual organic matter after oil adsorption was used as the carbon source and the nitrogen source, respectively. Through ion adsorption, nitrogen-doped porous carbon catalyst (Fe3C/NC) modified by iron carbide was synthesized by high-temperature pyrolysis and etching of clay mineral template. Fe3C/NC was characterized by Fourier-transform infrared spectroscopy (FT-IR), High-resolution transmission electron microscopy (TEM) and X-ray diffractometer. Further experiment showed that this catalyst had good electrochemical activity for ORR. In this paper, we use the organic matter in the waste clay as the carbon source and nitrogen source and use the characteristics of clay in the waste clay to introduce iron ions into the reaction. After high-temperature calcination, we get Fe3C/NC composite. Fe-N co-doping can expose more graphite defects and more active sites, which can also improve the electrocatalytic performance of ORR. [ABSTRACT FROM AUTHOR]

Spent bleaching earth (SBE) as an industrious solid rubbish seriously causes the environmental pollution problem. The resourceful utilization of SBE has become increasingly important. In this work, silicon and carbon ingredients derived from SBE were coincidently employed to synthesize a 4A zeolite/carbon composite molecular sieve (4A/CMS). Therein, the graphite carbon components in the form of porous lamellar scattering among the interlayer, surface, and periphery of 4A zeolite promote the rate of mass transfer for the lipophilic gas, which can effectively improve the adsorption property for the volatile organic compounds. The obtained 4A/CMS has large specific surface area, hierarchical pore structure, satisfactory adsorption capacity, and regeneration performance, and its equilibrium adsorption capacity of p-xylene can achieve 209.57 mg·g−1. The pseudo-first-order rate equation is appropriate for the adsorption kinetics. In the end, the formation mechanism of 4A/CMS was illuminated in detail. □ Spent bleaching earth (SBE) as an industrious solid rubbish were utilized resourcefully. Silicon and carbon ingredients from SBE were coincidently employed to synthesize 4A/CMS. Graphitic carbon with hierarchical pore promoted the rate of mass transfer of organic gas. 4A/CMS exhibited excellent adsorption capacity and regeneration performance of p-xylene. [ABSTRACT FROM AUTHOR]

Despite strong evidence that human genetic variants affect the expression of many key transcription factors involved in autoimmune diseases, establishing biological links between non-coding risk variants and the gene targets they regulate remains a considerable challenge. Here, we combine genetic, epigenomic, and CRISPR activation approaches to screen for functional variants that regulate IRF8 expression. We demonstrate that the locus containing rs2280381 is a cell-type-specific enhancer for IRF8 that spatially interacts with the IRF8 promoter. Further, rs2280381 mediates IRF8 expression through enhancer RNA AC092723.1, which recruits TET1 to the IRF8 promoter regulating IRF8 expression by affecting methylation levels. The alleles of rs2280381 modulate PU.1 binding and chromatin state to regulate AC092723.1 and IRF8 expression differentially. Our work illustrates an integrative strategy to define functional genetic variants that regulate the expression of critical genes in autoimmune diseases and decipher the mechanisms underlying the dysregulation of IRF8 expression mediated by lupus risk variants. The functional effects of genetic loci associated with autoimmune disease are not well understood. By dissecting an autoimmune disease genetic locus, the authors define an immune cell-type-specific enhancer and the molecular mechanisms underlying the dysregulation of IRF8 expression by lupus risk variants. [ABSTRACT FROM AUTHOR]

High-performance electrochemical energy storage device is an important means to solve the energy problem. As one of the next-generation energy storage components, supercapacitor has received more and more attention in recent years. In this study, MoS2/N-CNTs nanocomposites were synthesized using MoO3 as the template. The ultra-thin MoS2 nanosheets were modified on nitrogen-doped carbon nanotubes. The nanocomposites showed rapid electron transfer efficiency, increased charge storage, and good cycle stability. When the current density is 1 A g−1, the specific capacitance of the composite is about 225 F g−1. In the two-electrode system, the energy density is 9.89 Wh kg−1 at a power density of 699.3 W·kg−1. At a high current density of 10 A g−1, the initial capacitance of the composite material maintained 87% even after 10,000 cycles. [ABSTRACT FROM AUTHOR]

Copyright of Rare Metals is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Based on the three-dimensional ordered macroporous titanium dioxide (3DOM-TiO2), a series of gold-embedded 3DOM-TiO2 (nAu@3DOM-TiO2) with controlled Au loading amount (n = 0.24, 1.2, 2.4, 4.8, 12, and 24 wt%) was successfully fabricated via in-situ pyrolysis for the first time. Compared with the surface-modified Au/3DOM-TiO2 by traditional impregnation–reduction route, this body-doped Au@3DOM-TiO2 structure exhibited smaller particle size and better dispersive property which are important for photocatalysis. Therefore, the photocatalytic activities of nAu@3DOM-TiO2 have been tested and the optimized photocatalyst of 4.8Au@3DOM-TiO2 was identified. A possible mechanism of Au@3DOM-TiO2 for the enhanced photoactivity was well discussed. The present work demonstrated a unique "gold-embedded" interface with potential advantages of highly dispersed, anti-aggregation, easy recovery, and enhanced catalytic performance, and that this approach could provide an ideal platform for the further design of noble metal-doped semiconductors. [ABSTRACT FROM AUTHOR]

Since most variants that impact polygenic disease phenotypes localize to non-coding genomic regions, understanding the consequences of regulatory element variants will advance understanding of human disease mechanisms. Here, we report that the systemic lupus erythematosus (SLE) risk variant rs2431697 as likely causal for SLE through disruption of a regulatory element, modulating miR-146a expression. Using epigenomic analysis, genome-editing and 3D chromatin structure analysis, we show that rs2431697 tags a cell-type dependent distal enhancer specific for miR-146a that physically interacts with the miR-146a promoter. NF-kB binds the disease protective allele in a sequence-specific manner, increasing expression of this immunoregulatory microRNA. Finally, CRISPR activation-based modulation of this enhancer in the PBMCs of SLE patients attenuates type I interferon pathway activation by increasing miR-146a expression. Our work provides a strategy to define non-coding RNA functional regulatory elements using disease-associated variants and provides mechanistic links between autoimmune disease risk genetic variation and disease etiology. Enhancers shape gene expression patterns and are involved in disease pathogenesis. Here the authors demonstrate a strategy to screen functional regulatory elements for non-coding RNAs ― illustrated with miR-146a ― and link autoimmune disease risk genetic variants to autoimmune disease etiology. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) synthesis is a critical chemical process to develop nitrogen-containing commodities which remains a significant challenge in chemistry and industry. Photocatalysis reduction has been deemed as one of the most promising strategies for N2 fixation under mild conditions. Herein, a series of Pr doped LiNbO3 (Pr3+:LiNbO3) were synthesized by a facile sol–gel method. Results showed that the Pr3+:LiNbO3 upconverted visible light into ultraviolet light and had the highest up-conversion efficiency when the molar ratio of Pr3+ was 2.5 mol%. In addition, the oxygen vacancies generated by the incorporation of Pr3+ into the LiNbO3 crystal lattice acted as active sites boosting the adsorption and activation of N2. The NH4+ production rate reached the highest of 30.72 μmol/L, attributed to the synergistic effects combining spontaneous polarization of the nonlinear optical (NLO) material LiNbO3 and up-conversion luminescence of Pr3+, which not only broaden the adsorption range of solar light but also enhance the charge separation. The up-conversion NLO material Pr3+:LiNbO3 in this study provides a novel alternative for guiding the design of ammonia synthesis photocatalyst. [ABSTRACT FROM AUTHOR]

BE/C-A750-1/1 is prepared by carbonizing SBE and then activating with KOH. BE/C-A750-1/1 has good adsorption capacity for Pb(II), and the adsorption capacity for Pb(II) is 206.65 mg/g. The harmful effects of coexisting cations are listed in ascending order: K+ < Na+ < Mg2+. Adsorption and desorption studies show that the adsorption capacity of BE/C-A750-1/1 for Pb(II) after adsorption and desorption 3 times is 183.62 mg/g. The adsorption mechanism mainly includes electrostatic attraction, ion exchange, physical adsorption, and chemical complexation. This suggests that activated BE/C may be a promising candidate for removing Pb(II) from industrial wastewater. [ABSTRACT FROM AUTHOR]

In this paper, rutile phase titanium oxide/Sb-SnO2/anatase phase titanium oxide (TiO2 (R)/C-TiO2 (A)) heterostructured nanocomposites were prepared by a sol–gel method and a hydrothermal method. By optimizing the mass ratio between TiO2 (R) and C-TiO2 (A), the rod-ball heterostructures of TiO2 (R)/C-TiO2 (A) were formed and exhibited enhanced simulated sunlight-driven photocatalytic desulfurization performance. According to the results, the desulfurization rate of TiO2 (R)/C-TiO2 (A) was 93.98% after 60 min, which is higher than C-TiO2 (A) and TiO2 (R)/TiO2 (A). In addition, the photocatalytic recyclability test indicated that after three times the reuse of TiO2 (R)/C-TiO2 (A) could still reach 85.98%. The enhanced photocatalytic performance could be attributed to the double Z-scheme heterojunction in the TiO2 (R)/C-TiO2 (A) and the uniformly structure of rod array, which resulted in the higher separation efficiency of electrons and holes. Furthermore, the results of photocatalytic active radical species trapping experiments showed that the main substances in the photocatalytic reaction are ∙O2− and h+. This paper also established the double Z-scheme heterojunction reaction mechanism. [ABSTRACT FROM AUTHOR]

Developing photocatalysts with wide spectrum absorption and strong nitrogen activation is critical for nitrogen fixation under mild conditions. Herein, one-dimensional natural clay attapulgite (ATP) supported YF3:Sm3+ were successfully synthesized via microwave hydrothermal method, and the composites were employed as the catalyst for photocatalytic nitrogen fixation under visible-light irradiation. Results indicated that the production of ammonia reached as high as 41.2 mg·L−1 within 3 h when the molar ratio of Sm3+ and the mass fraction of YF3:Sm3+ were optimized. The enhanced fixation performance is mainly due to that the modified ATP fibber with abundant active sites and the doped fluoride with defective vacancy facilitate the adsorption and activation of N2. Furthermore, the upconversion property of YF3:Sm3+ increases the harvesting of visible-light energy, meanwhile the Z-scheme heterostructure built between YF3:Sm3+ and modified ATP inhibits the recombination of charge carriers and retains high redox potentials for N2 reduction. [ABSTRACT FROM AUTHOR]

A series of morphology-controlled BiOBr nano/macrostructures was successfully synthesized via a novel biomass-route derived from bacterial cellulose (BC). In the BiOBr/BC system compared with pure BiOBr, the three-dimensional BC scaffolds not only effectively prevented the aggregation of BiOBr units by pore confinement, but also strengthened the controllability of BiOBr size with the help of abundant anchoring sites provided by cross-linked BC fibers. By associating the results of characterizations and the photodegradation of RhB dye, the relationship between morphology and photocatalytic activity of BiOBr/BC was investigated. In addition, a possible mechanism for the enhanced photocatalytic activity of the optimized BiOBr/BC has been discussed. This biomass-derived route provides a platform for further design of bismuth-based composite photocatalysts with potential advantages of being anti-aggregation, highly-dispersed, easily recovered and having enhanced catalytic performance. [ABSTRACT FROM AUTHOR]

Defective crystalline semiconductor plays a significant role in photocatalytic nitrogen fixation, however the rapid recombination of photoexcited electron/hole pairs largely reduces the efficiency. Spontaneous polarization of the nonlinear optical (NLO) material has emerged as a promising strategy for addressing the problem. Herein, a defects-rich NLO crystalline LiNbO3 modulated by natural nano-mineral palygorskite (LiNbO3/Pal) has been synthesized via sol–gel method. The intrinsic polarization of LiNbO3/Pal is investigated by second harmonic generation (SHG) measurements, which indicates an intensity of about 3.1 times that of typical NLO material KH2PO4 (KDP). The strong polarization can facilitate the separation of photogenerated charge carriers in the bulk phase and on the surface of LiNbO3/Pal. The existence of oxygen vacancies in LiNbO3/Pal may originate from doping of metal ions and active groups on the surface of Pal during crystallization of LiNbO3, which shortens the bandgap of LiNbO3 and facilitates the absorption and activation of N2 molecules. As a result, the polarization effect and rich oxygen vacancies make the LiNbO3/Pal an exceptional photocatalyst for N2 fixation. The 40 wt% LiNbO3/Pal composite achieves an average rate of photocatalytic NH4+ production of 52.57 μmol gcat−1 h−1 under simulated solar light, which is about sixfold higher than that of bulk LiNbO3. This work not only presents a new perspective on mineral modification of NLO material but also offers a cost-effective photocatalyst for nitrogen fixation. [ABSTRACT FROM AUTHOR]

A series of thickness-controlled SrTiO3 (commonly abbreviated ST) anchored on carbonized bacterial cellulose (CBC) was successfully prepared by a novel route of freeze-drying assisted crystallization/carbonization. For the first time, the cross-linked bacterial cellulose served as a carbon source as well as structure-directing scaffold for the construction of ST/CBC composites. Characterizations exhibited cracks and defects on the surface of CBC which provided ideal anchoring sites for the dispersion and crystallization of ST. Additionally, the relationship between morphology and photocatalytic activity of ST/CBC was carefully investigated by photocatalytic reduction of potassium dichromate (K2Cr2O7) and degradation of tetracycline in water. This unique biomass-derived carbon fibers provide an ideal platform for further design of perovskite based materials with enhanced catalytic performance. [ABSTRACT FROM AUTHOR]

To reduce phenolic pollutants in the environment, many countries have imposed firm restrictions on industrial wastewater discharge. In addition, the current industrial process of phenolic resin production uses phenol and formaldehyde as the reactants to perform a polycondensation reaction. Due to the toxicity of formaldehyde and phenolic pollutants, the main purpose of this research was to design a green process using horseradish peroxidase (HRP) enzymatic polymerization to remove phenols and to produce formaldehyde-free phenolic polymers. In this study, the optimal reaction conditions, such as reaction temperature, pH, initial phenol concentration and initial ratio of phenol, and H2O2, were examined. Then, the parameters of the enzyme kinetics were determined. To solve the restriction of enzyme inactivation, several nonionic surfactants were selected to improve the phenol removal efficiency, and the optimal operation conditions in a surfactant-containing system were also confirmed. Importantly, the molecular weight of the synthetic phenolic polymers could be controlled by adjusting the ratio of phenol and H2O2. The content of biphenols in the products was almost undetectable. Collectively, a green chemistry process was proposed in this study and would benefit the treatment of phenol-containing wastewater and the production of formaldehyde-free phenolic resin in the future. [ABSTRACT FROM AUTHOR]

Photocatalytic fixation of nitrogen has been recognized as a green and promising strategy for ammonia synthesis under ambient conditions. However, the efficient reduction of nitrogen remains a challenge due to high activation energy of nitrogen and low utilization of solar energy. Herein, lanthanum oxyfluoride with different doping content of Pr3+ (LaOF:xPr3+) upconversion nanorods were synthesized by microwave hydrothermal method. Results indicated that the doping of Pr3+ generated considerable defects on the surface of LaOF which acted as the adsorption and activation center for nitrogen. Meanwhile, the Pr3+ ion narrowed the band gap and broadened the light response range of LaOF because LaOF:Pr3+ can upconvert visible light into ultraviolet light, which excite LaOF nanorods and improve the utilization of solar light. The doping amount of Pr3+ had critical effect on the photocatalytic nitrogen fixation performance which reached as high as 180 μmol·L−1·ho1 when the molar ratio of Pr3+ to LaOF was optimized to be 2%. [ABSTRACT FROM AUTHOR]

A series of Ce-doped LaMnO3 (La1-xCexMnO3) were prepared and were tested for gaseous toluene oxidation in order to investigate the effect of cerium doping in LaMnO3 on activity under photothermal conditions. It was found that the activity and CO2 yield of the catalyst can be effectively increased when x = 0.25. A group of characterization is used to characterize the morphology, composition, and physical properties of the as-prepared catalysts. Results show that the Ce-doped LaMnO3 can form coexistence of La1-xCexMnO3 and CeO2, the reaction of CeO2/La1-xCexMnO3 under photothermal conditions follows the Mars-van Krevelen redox cycle mechanism, and the prepared CeO2/La1-xCexMnO3 can form a highly efficient Z-scheme heterojunction, which can enhance the electrons transfer speed of the catalyst. Moreover, in the photothermal catalytic degradation, lattice oxygen is the most important active substance, a small amount of cerium doping can increase the lattice oxygen content of perovskite and increase the activity of the reaction. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) obtained by traditional Haber–Bosch technique under extreme conditions stimulates the exploration of sustainable approach via nitrogen photofixation process, however, efficient utilization of solar energy remains a great challenge. Herein, a novel plasmonic W18O49 supported on acid modified attapulgite (H-ATP) composite was prepared by microwave hydrothermal method. The impact of the loading fraction of W18O49 on the ammonia production rate was investigated. Results indicate that ATP possesses abundant adsorption sites after modified by phosphoric acid which facilitates the immobilization of W18O49. The 40% W18O49/H-ATP achieves the highest ammonia production rate of 138.76 μmol g−1 h−1 under solar light irradiation, even 78.76 μmol g−1 h−1 under NIR light (λ > 780 nm). The formed Z-scheme heterostructure improves the separation of charge-carriers, and the localized surface plasmon resonance (LSPR) effect of W18O49 broadens the light response range, both of which contribute to the enhanced nitrogen photofixation performance. [ABSTRACT FROM AUTHOR]

Ammonia synthesis consumes large amounts of energy in traditional industry and causes considerable air pollution to the atmosphere. Therefore, developing green strategies and novel catalysis for NH3 synthesis under ambient conditions using renewable energy is strongly desired. In this work, Er-doped lanthanum cobaltite/attapulgite composites (LaCoO3:Er3+/ATP) were prepared by a sol–gel method. The influence of the Er doping ratio and LaCoO3:Er3+ loading amount on the generation rate of ammonia under visible-light irradiation were investigated. The results show that Er3+-doped LaCoO3 can convert visible light into ultraviolet light and reach the highest conversion rate when the doping amount of the Er element is 6 mol%, which enhances the utilization of solar energy. ATP contributes to the adsorption of N2 and the Co dopant weakens the N≡N bond favoring the activation of N2. Moreover, a direct Z-scheme heterostructure is constructed between LaCoO3:Er3+ and ATP when the loading amount is 10 wt%, which facilitates the separation of charge carriers and preserves the high redox potentials, leading to the enhanced photocatalytic nitrogen fixation performance. Highlights: LaCoO3:Er3+/ATP nanocomposite prepared by sol-gel method. Er3+ doped LaCoO3 convert visible light into ultraviolet light. Co dopant weakens the N≡N bond favoring the activation of N2. Z-scheme LaCoO3:Er3+/ATP enhances the potantial for nitrogen fixation. [ABSTRACT FROM AUTHOR]

We present a novel and facile fabrication of wall-thickness controlled ZrTiO4 nanotubes (ZTNTs) using bacterial cellulose (BC) as a template. Unique porous thin-walls and interconnected channels within ZTNTs contribute a lot to the enhanced photodegradation activity. The roles of the wall-thicknesses in physicochemical properties as well as photocatalytic activities were careful investigated which might extend the synthesis of other nanotubes with higher catalytic performance. [ABSTRACT FROM AUTHOR]

The emission of nitrogen oxides has caused severe harm to the ecosystem; thus, the development of low-cost and high-efficiency denitrification catalysts and new methods are of great significance. In this work, a co-precipitation method was employed to prepare Pr-doped CeO2/attapulgite (CeO2/Pr3+/ATP) nanocomposites. X-ray diffraction (XRD), photoluminance spectroscopy (PL), ultraviolet-visible diffuse reflectance (UV-Vis), Fourier transform infrared (FT-IR), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the products. Results showed that the CeO2/Pr3+ nanoparticles were uniformly coated on the surface of ATP and demonstrated outstanding upconversion effect which converted the visible light to ultraviolet light. The upconversion luminescence of CeO2/Pr3+/ATP was strongest when the molar doping amount of Pr was 1 mol%, and the photo-SCR denitrification achieved the highest of 90% conversion and 95% selectivity when the loading amount of CeO2/Pr3+ was 40 wt%. The ATP and CeO2/Pr3+ constructed an indirect Z-type heterojunction structure mediated by oxygen vacancy which benefited the separation of charge carriers and enhanced the reduction-oxidation potentials, both are responsible for the remarkable denitrification performance. [ABSTRACT FROM AUTHOR]

CeO2/black phosphorus (BP) heterostructure nanocomposite was synthesized via a two-step assembly method. The structure and optical property of the prepared composites were characterized by X-ray diffraction, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy (UV-Vis), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Photocatalytic degradation of bisphenol A (BPA) in simulated waste water was performed by using CeO2/BP nanocomposite as catalyst. Results indicated that the degradation rate of BPA reached 82.3% within 180 min, which was remarkably improved compared with pure CeO2 and BP due to the formation of indirect Z-scheme heterostructure intermediated by oxygen vacancies originated from CeO2. The unique heterostructure facilitated the charge transfer and preserved the high redox potential leading to improve the photocatalytic degradation performance. [ABSTRACT FROM AUTHOR]