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The effect of the atmosphere in a reactor prior to hydride vapour phase epitaxy on the surface stoichiometry of both the GaN template and layer growth was studied. The surface stoichiometry of metallic Ga layers was clarified by X-ray photoelectron spectroscopy using templates without NH3 protection. The metallic Ga layer acted as a mask and exerted a significant effect on the subsequent epitaxial layer growth mode. GaN grown on the template without protection followed island growth in the initial growth stage. In contrast, GaN epitaxy on the template with NH3 protection quickly converts to pseudo-2D growth. The images of CL illustrate that the GaN epilayer on the template without protection has a lower dislocation density than the GaN epilayer grown on the template with NH3 protection. Reasons behind this effect have been discussed. [ABSTRACT FROM AUTHOR]

Human calcitonin (hCT) is an endogenous polypeptide commonly employed in treating bone resorption-related illnesses, but its clinical application is limited due to its high aggregation tendency. Metalloporphyrins are effective in suppressing amyloid fibrillation, positioning them as potential drug candidates for amyloidogenic disorders like Alzheimer's and type 2 diabetes. In this work, we investigated the effects of Fe(III) meso -tetra(4-sulfonatophenyl)porphine chloride (FeTPPS), a highly efficient ONOO - decomposition catalyst, on hCT aggregation. Our findings reveal that FeTPPS effectively precludes hCT fibrillation by stabilizing the monomers and delaying the structural transition from α-helix bundles to β-sheet-rich aggregates. The macrocyclic ring of FeTPPS plays a significant role in disrupting hCT self-associations. Among various porphyrin analogs, those with an iron center and negatively charged peripheral substituents exhibit a stronger inhibitory effect on hCT aggregation. Spectroscopic analyses and computational simulations indicate that FeTPPS binds to hCT's core aggregation region via complexation with His20 in a 1 : 1 molar ratio. Hydrophobic interaction, hydrogen bonding, and π-π stacking with the residues involving Tyr12, Phe19, and Ala26 also contribute to the interactions. Collectively, our study provides a promising approach for developing novel hCT drug formulations and offers theoretical guidance for designing metalloporphyrin-based inhibitors for various amyloidosis conditions.

Substituting oxygen evolution with alcohol oxidation is crucial for enhancing the cathodic hydrogen evolution reaction (HER) at low voltages. However, the development of high-performance bifunctional catalysts remains a challenge. In this study, an ultrathin and porous PdMoPt trimetallene is developed using a wet-chemical strategy. The synergetic effect between alloying metals regulates the adsorption energy of reaction intermediates, resulting in exceptional activity and stability for the electrooxidation of various alcohols. Specifically, the mass activity of PdMoPt trimetallene toward the electrooxidation of methanol, ethylene glycol, and glycerol reaches 6.13, 5.5, and 4.37 A mg Pd+Pt -1 , respectively. Moreover, the catalyst demonstrates outstanding HER activity, requiring only a 39 mV overpotential to achieve 10 mA cm -2 . By employing PdMoPt trimetallene as both the anode and cathode catalyst, we established an alcohol-water hybrid electrolysis system, significantly reducing the voltage requirements for hydrogen production. This work presents a promising avenue for the development of bifunctional catalysts for energy-efficient hydrogen production., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We propose a three-dimensional computational framework to simulate the flow-induced cell membrane damage and the resulting enhanced intracellular mass transport in a cross-slot microchannel. We model the cell as a liquid droplet enclosed by a viscoelastic membrane and solve the cell deformation using a well-tested immersed-boundary lattice-Boltzmann method. The cell membrane damage, which is directly related to the membrane permeability, is considered using continuum damage mechanics. The transport of the diffusive solute into the cell is solved by a lattice-Boltzmann model. After validating the computational framework against several benchmark cases, we consider a cell flowing through a cross-slot microchannel, focusing on the effects of the flow strength, channel fluid viscosity and cell membrane viscosity on the membrane damage and enhanced intracellular transport. Interestingly, we find that under a comparable pressure drop across the device, for cells with low membrane viscosity, the inertial flow regime, which can be achieved by driving a low-viscosity liquid at a high speed, often leads to much larger membrane damage, compared with the high-viscosity low-speed viscous flow regime. However, the enhancement can be significantly reduced or even reversed by an increase of the cell membrane viscosity, which limits cell deformation, particularly in the inertial flow regime. Our computational framework and simulation results may guide the design and optimisation of microfluidic devices, which use cross-slot geometry to disrupt cell membranes to enhance intracellular delivery of solutes.

Volatile organic compounds (VOCs) originating from diverse sources with complex compositions pose threats to both environmental safety and human health. Photocatalytic treatment of VOCs has garnered attention due to its high efficacy at room temperature. However, the intricate photochemical reaction generates ozone (O 3 ), causing secondary pollution. Herein, our work developed a novel "synergistic effect" system for photocatalytic co-treatment of VOCs and O 3 secondary pollution. Under the optimized reactor conditions simulated with computational fluid dynamics (CFD), MgO-loaded g-C 3 N 4 composites (MgO/g-C 3 N 4 ) were synthesized as efficient catalysts for the photocatalytic synergistic treatment process. Density functional theory (DFT) calculations, characterization, and electron paramagnetic resonance (EPR) tests revealed that the addition of MgO reduced the band gap of g-C 3 N 4 , and increased O 3 molecule adsorption in the composites, efficiently harnessing the synergistic effect of O 3 to generate a significant quantity of reactive oxygen radicals, thereby facilitating the removal of VOCs and O 3 . This study provides new insights for simultaneous elimination of VOCs and O 3 secondary pollution by a photocatalytic process., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn 3 O 4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn 2+ cations inserted in the first discharge and trapped in the Mn 3 O 4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl - redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g. , [Cl 3 ] - and [Cl 5 ] - , inside the Zn 2+ -trapped Mn 3 O 4 , and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Layered double hydroxides (LDHs) have been intensively investigated as promising cathodes for the new concept chloride ion battery (CIB) with multiple advantages of high theoretical energy density, abundant raw materials and unique dendrite-free characteristics. However, driven by the great compositional diversity, a complete understanding of interactions between metal cations, as well as a synergetic effect between metal cations and lattice oxygen on LDH host layers in terms of the reversible Cl-storage capability, is still a crucial but elusive issue. In this work, we synthesized a series of chloride-inserted trinary Mo x -doped NiCo 2 -Cl LDH ( x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) with gradient oxygen vacancies as enhanced cathodes toward CIBs. The combination of advanced spectroscopic techniques and theoretical calculations reveals that the Mo dopant facilitates oxygen vacancy formation and varies the valence states of coordinated transition metals, which can not only tune the electronic structure effectively and promote Cl-ion diffusion, but improve the redox activity of LDHs. The optimized Mo 0.3 NiCo 2 -Cl LDH delivers a reversible discharge capacity of 159.7 mA h g -1 after 300 cycles at 150 mA g -1 , which is almost a triple enhancement compared to that of NiCo 2 Cl LDH. The superior Cl-storage of trinary Mo 0.3 NiCo 2 Cl LDH is attributed to the reversible intercalation/deintercalation of chloride ions in the LDH gallery along with the oxidation state changes in Ni 0 /Ni 2+ /Ni 3+ , Co 0 /Co 2+ /Co 3+ and Mo 4+ /Mo 6+ couples. This simple vacancy engineering strategy provides critical insights into the significance of the chemical interaction of various components on LDH laminates and aims to effectively design more LDH-based cathodes for CIBs, which can even be extended to other halide-ion batteries like fluoride ion batteries and bromide ion batteries.

Considering the molar mass between entanglements to be an intrinsic property of ultra-high molecular weight polyethylene (UHMWPE), the number of entanglements per chain increases with increasing molar mass, correspondingly making the UHMWPE intractable. Herein, we dispersed TiO 2 nanoparticles with different characteristics into UHMWPE solutions to disentangle the molecular chains. Compared with the UHMWPE pure solution, the viscosity of the mixture solution declines by 91.22%, and the critical overlap concentration increases from 1 wt% to 1.4 wt%. A rapid precipitation method was utilized to obtain UHMWPE and UHMWPE/TiO 2 composites from the solutions. The melting index of UHMWPE/TiO 2 is 68.85 mg, which is in sharp contrast to that of UHMWPE which is 0 mg. We characterized the microstructures of UHMWPE/TiO 2 nanocomposites using TEM, SAXS, DMA, and DSC. Accordingly, this significant improvement in processability contributed to the reduction of entanglements and a schematic model was proposed to explain the mechanism by which nanoparticles disentangle molecular chains. Simultaneously, the composite demonstrated better mechanical properties than UHMWPE. In summary, we provide a strategy to promote the processability of UHMWPE without sacrificing its outstanding mechanical properties.

Chloride ion batteries (CIBs) have drawn growing attention as attractive candidates for large-scale energy storage technology because of their high theoretical energy densities (2500 W h L -1 ), dendrite-free characteristics and abundance of chloride-containing materials available worldwide. However, the further development of CIBs is greatly limited by sluggish Cl - diffusion and distinct structural variation of cathode materials, resulting in severe decayed capacity and inferior rate performance. Metal-organic framework (MOF) materials possess regular pores/channels and flexible structural designability to accommodate charge carrier ions, but the application of MOFs in anion-type batteries has not been reported. Here, we demonstrate the first example of Ni(dpip) with two different opening sizes of tubular channels serving as the cathode for high performance CIBs. The Ni-based MOF exhibited a stable reversible capacity of 155 mA h g -1 with an admirable low capacity decay of 0.026% per cycle over 500 cycles and superior kinetics with a 10 -10 cm 2 s -1 average diffusion coefficient for chloride ions as well. The high performance of the Ni(dpip) cathode results from the synergetic redox couples of Ni metal nodes and N-ligands, the unique double-channel structure for reversible Cl-storage, and the low chloride diffusion energy barrier. This work switches on the new application of MOF-based materials as cathodes for CIBs., Competing Interests: The authors have declared no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Exploring two-dimensional (2D) van der Waals materials with out-of-plane polarization and electromagnetic coupling is essential for the development of next-generation nano-memory devices. A novel class of 2D monolayer materials with predicted spin-polarized semi-conductivity, partially compensated antiferromagnetic (AFM) order, fairly high Curie temperature, and out-of-plane polarization is analyzed in this work for the first time. Based on density functional theory calculations, we systematically studied these properties in asymmetrically functionalized MXenes (Janus Mo 2 C)-Mo 2 CXX' (X, X' = F, O, and OH). Using ab initio molecular dynamics (AIMD) and phonon spectrum calculations, the thermal and dynamic stabilities of six functionalized Mo 2 CXX' were identified. Our DFT+ U calculation results also provided a switching path for out-of-plane polarizations, where the reverse of electric polarization is driven by terminal-layer atom flipping. More importantly, strong coupling between magnetization and electric polarization originating from spin-charge interactions was observed in this system. Our results confirm that Mo 2 C-FO would be a novel monolayer electromagnetic material, and its magnetization can be modulated by electric polarization.

Ti 3 C 2 T x -MXenes have extremely promising applications in electrochemistry, but the development of Ti 3 C 2 T x is limited due to severe self-stacking problem. Here, we introduced oxygen vacancy-enriched molybdenum trioxide (MoO 3- x ) with pseudocapacitive properties as the intercalator of Ti 3 C 2 T x and PEDOT with high electronic conductivity as the co-intercalator and conductive binder of Ti 3 C 2 T x to synthesize Ti 3 C 2 T x /MoO 3- x /PEDOT:PSS (TMP) free-standing films by vacuum-assisted filtration and H 2 SO 4 soaking. The tightly intercalated free-standing film structure can effectively improve the self-stacking phenomenon of Ti 3 C 2 T x , expose more active sites and facilitate electron/ion transport, thus making TMP show excellent electrochemical performance. The volumetric and gravimetric capacitance of optimized TMP-2 can reach 1898.5 F cm -3 and 523.0 F g -1 at 1 A g -1 with a rate performance of 90.5% at the current density from 1 A g -1 to 20 A g -1 , which is significantly better than those of MXene-based composites reported in the literature. The directly-assembled TMP-2//TMP-2 flexible solid-state supercapacitor displays high energy/power output performances (25.1 W h L -1 at 6383.1 W L -1 , 6.9 W h kg -1 at 1758.4 W kg -1 ) and there is no obvious change after 100 cycles at a bending angle of 180°. As a result, the tightly intercalated TMP-2 free-standing film with high volumetric/gravimetric capacitances is a promising material for flexible energy storage devices.

In this work, waterborne epoxy resin and graphene/ZnO (Gr/ZnO) were employed as the matrix and nanofiller to construct composite coatings with enhanced anticorrosive performance. The corrosion protection properties of the coatings were significantly improved by the dispersed Gr sheets, as well as the parallelly assembled ZnO nanoparticles. The most remarkable improvement was achieved by adding 0.04 wt% of Gr and 0.4 wt% of ZnO in the Waterborne Epoxy (WEP) coatings, where the highest impedance was 200 530 Ω cm 2 on Gr 0.04 -ZnO 0.4 , far more than pure epoxy with 6186 Ω cm 2 after 7 days of immersion in electrolytes. Furthermore, the Gr 0.04 -ZnO 0.4 coatings and corresponding corrosion products immersed in a 3.5% NaCl solution for 30 days were also characterized, which could further reveal anticorrosion mechanisms of the graphene modified WEP coatings and the passivated effect of ZnO. Through the mechanism analysis, we also found that ZnO could be employed as the barrier reinforcement to improve the dispersibility of graphene in WEP coatings, and the parallel assembly of graphene occurs spontaneously, leading to remarkable improvement of anticorrosion properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Animal studies and clinical trials have shown that dietary polyphenols and polyphenol-rich foods can reduce the risk of type 2 diabetes (T2D) and its complications, but how diabetes regulates the metabolism of polyphenol has not been fully elucidated. This study investigated the effects of diabetes on litchi pericarp oligomeric procyanidin (LPOPC) dynamic metabolism and its major static metabolites in urine. First, a high-fat and streptozotocin (STZ)-induced diabetic Sprague Dawley (SD) rat model was established. In the diabetic rat model, elevated fasting blood glucose, severely impaired glucose tolerance test, and increased reactive oxygen species (ROS) levels in serum and the liver were observed. Subsequently, 200 mg per kg body weight of LPOPC was administrated to control and diabetic SD rats, and the gastrointestinal tract was collected at 0.5 h, 1 h, 3 h, and 6 h. The results showed that the retention time of LPOPC was not changed in our diabetic rat model. However, the gut microbiota were significantly altered, with elevated Proteobacteria and Verrucomicrobia abundance in diabetic rats and decreased short chain fatty acid (SCFA)-producing bacteria. Interestingly, after one dose of 300 mg per kg body weight LPOPC, the total antioxidant capacity of urine in diabetic rats significantly decreased. We then tested the static metabolites of LPOPC, demonstrating that epicatechin had not changed in urine in diabetic rats, but that shikimic acid was significantly reduced in urine in diabetic rats. The changes in shikimic acid may be due to the alteration of gut microbiota and elevated ROS levels in serum.

Fe is not only the most abundant metal on the planet but is also the key component of many enzymes in organisms that are capable of catalyzing many chemical conversions. Mono-dispersed Fe atoms on carbonaceous materials are single atom catalysts (SACs) that function like enzymes. To take advantage of the outstanding catalytic performance of Fe-based SACs, we extended a CO oxidation reaction network over mono-dispersed Fe atoms on graphene (FeGR) by first-principles based calculations. FeGR-catalyzed CO oxidation is initiated with a revised Langmuir-Hinshelwood pathway through a CO-assisted scission of the O-O bond in peroxide species (OCOO). We showed that carbonate species (CO3), which were previously generally considered as a persistent species blocking reaction sites, may form from CO2 and negatively charged O species. This pathway competes with desorption of CO2 and reduction of the Fe center with gaseous CO, and it is exothermic and inevitable, especially at low temperatures and with high CO2 content. Although direct dissociation of CO3 is demanding on FeGR, further adsorption of CO on Fe in CO3 is plausible and takes place spontaneously. We then showed that adsorbed CO may react with CO3, forming a cyclic-carbonate-like species that dissociates easily to CO2. These findings highlight the reaction condition-dependent formation and evolution of CO3 as well as its contribution to CO conversion, and it may extend the understanding of the performance of SACs in low temperature CO oxidation.

Microcapsules, consisting of a liquid droplet enclosed by a viscoelastic membrane, have a wide range of biomedical and pharmaceutical applications and also serve as a popular mechanical model for biological cells. In this study, we develop a novel high throughput approach, by combining a machine learning method with a high-fidelity mechanistic capsule model, to accurately predict the membrane elasticity and viscosity of microcapsules from their dynamic deformation when flowing in a branched microchannel. The machine learning method consists of a deep convolutional neural network (DCNN) connected by a long short-term memory (LSTM) network. We demonstrate that with a superior prediction accuracy the present hybrid DCNN-LSTM network can still be faster than a conventional inverse method by five orders of magnitude, and can process thousands of capsules per second. We also show that the hybrid network has fewer restrictions compared with a simple DCNN.

Spinel LiMn 2 O 4 (LMO) with a three-dimensional structure has become one of the cathode materials that has gained the most interest due to its safety, low price and abundant resources. However, the lithium ion transmission is limited by large particle size and particle agglomeration of LMO. Thus, reducing the particle size and agglomeration of LMO can effectively improve its lithium ion transmission. Here, we synthesized a LMO cathode material with a nanoscale crystal size using the flexible expanded graphite (EG) soft template and Pichini method. EG-controlled particle size and particle agglomeration of LMO is conducive to charge transfer and diffusion of lithium ions between LMO and the electrolyte, meanwhile, there are more redox sites on the nanosized LMO particles, which makes the redox reaction of LMO more thorough during the charge and discharge process, resulting in high capacitance performance. In order to obtain the considerably required lithium-ion capacitors (LICs) with high energy density and power density, we assembled aqueous LMO//activated carbon (AC) LICs with 5 M LiNO 3 as the aqueous electrolytes, which are environmentally friendly, safe, low cost and have higher electrical conductivity than organic electrolytes. The optimal LIC has an energy density of 32.63 W h kg -1 at a power density of 500 W kg -1 and an energy density of 8.06 W h kg -1 at a power density of 10 000 W kg -1 , which is higher than most of the LMO-based LICs in previous reports. After 2000 cycles, the specific capacitance retention rate was 75.9% at a current density of 3 A g -1 . Therefore, our aqueous LMO//AC LICs synthesized by the soft template/Pichini method have wide prospects and are suitable for low-cost, high-safety and high-power applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Graphene oxide (GO) is an ideal hydrogel material because of its water solubility, non-toxicity, and excellent mechanical properties. Here, we added GO to oligo(lysine)-modified F127 to prepare a series of FLGO composite hydrogels. The FLGO hydrogel was thermally induced, stable and injectable. And the content of GO would affect the sol-gel transition, rheological properties and glass transition temperature of the FLGO hydrogel. GO was connected to the matrix through electrostatic interactions and hydrogen bonds. The cross-linking effect of GO enhanced the FLGO hydrogel. We also studied the release properties of the FLGO hydrogel loaded with anticancer drug 5-fluorouracil. Compared with F127 hydrogel, the FLGO hydrogel showed a linear, slower and stable release pattern within one week. The release rate of FLGO hydrogel could be adjusted by the pH and it was faster under acidic conditions. Therefore, the FLGO hydrogel is expected to be used as a drug release system in the field of biomedicine.

Core/shell nanocrystals (NCs) integrate collaborative functionalization that would trigger advanced properties, such as high energy conversion efficiency, nonblinking emission, and spin-orbit coupling. Such prospects are highly correlated with the crystal structure of individual constituents. However, it is challenging to achieve novel phases in core/shell NCs, generally non-existing in bulk counterparts. Here, we present a fast and clean high-pressure approach to fabricate heterostructured core/shell MnSe/MnS NCs with a new phase that does not occur in their bulk counterparts. We determine the new phase as an orthorhombic MnP structure (B31 phase), with close-packed zigzagged arrangements within unit cells. Encapsulation of the solid MnSe nanorod with an MnS shell allows us to identify two separate phase transitions with recognizable diffraction patterns under high pressure, where the heterointerface effect regulates the wurtzite → rocksalt → B31 phase transitions of the core. First-principles calculations indicate that the B31 phase is thermodynamically stable under high pressure and can survive under ambient conditions owing to the synergistic effect of subtle enthalpy differences and large surface energy in nanomaterials. The ability to retain the new phase may open up the opportunity for future manipulation of electronic and magnetic properties in heterostructured nanostructures., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A fluorescence analysis method based on gold nanocluster (AuNC) and metal-organic framework (MOF) composite materials (AuNCs@ZIF-8) was established for highly sensitive detection of bilirubin (BR). First, AuNCs@ZIF-8 was successfully obtained by co-precipitation and displayed an aggregation-induced emission enhancement by the confinement effect of the MOFs (i.e., ZIF-8). The product showed approximately 7.0 times enhancement in the quantum yield and longer fluorescence lifetime from 2.29 μs to 11.51 μs compared with AuNCs. When BR combined with the metal node Zn2+ of ZIF-8, the skeleton of the composite was destroyed, leading to a great decrease in the fluorescence intensity by the transformation of the AuNCs from the aggregated state to dispersed state. The linear range for the detection of BR was 0.1-5.0 μM, with the limit of detection (LOD) of 0.07 μM (S/N = 3). The AuNCs@ZIF-8 exhibited a selective response toward BR within 5 min and detected BR in human serum. The long-wavelength emission by AuNCs avoided the interference of the complex biomatrix background fluorescence, indicating their great application prospects for clinical diagnosis.

Aggregation-induced emission (AIE) probes have emerged as promising "turn-on" sensing tools for DNA and proteins, and the AIE biosensors conjugated with graphene oxide (GO) have shown improved selectivity. Collagen is an essential structural protein in the human body, and its degraded products are involved in a plethora of severe diseases. Collagen has a high content of charged amino acids, while EOG represents one of the most abundant charged triplets in Type I collagen. We, herein, for the first time report the construction of a GO-aided AIE biosensor for the detection of charged collagen peptides. We have shown that an AIE fluorophore TPE conjugated with a triple helical peptide TPE-PRG possesses strong fluorescence due to the restriction of intramolecular rotation of TPE in the trimer state. The adsorption of the probe TPE-PRG by GO leads to efficient fluorescence quenching, while the addition of target collagen peptide EOG releases the probe peptide from the GO surface and recovers its fluorescence. We have demonstrated that the TPE-PRG/GO complex provides a highly specific "turn-on" sensing platform for the target collagen peptide with a typical charged amino acid-rich sequence. The assay has shown little interference from other biomolecules, and it can also effectively distinguish the target charged collagen peptide from its single amino acid mutant type. The development of robust analytical assays for charged collagen peptides could pronouncedly extend our capability to investigate the pathology of collagen diseases, showing great potential for their molecular diagnosis.

Peptide-containing hydrogels have become a research hotspot due to their unique secondary structure and biocompatibility. Herein, we used amino-terminated F127 as a macroinitiator to initiate the ring-opening polymerization of l-lysine(z)- N CA, and the obtained oligo(lysine)-modified F127 (FL) had degrees of polymerization of lysine of 2, 5, and 8. The results showed that the FL hydrogels had reversible temperature-dependent sol-gel transitions, and the introduction of lysine increased the critical gel temperature. In the dilute solution of FL, the micelle size increased and aggregated as the pH increased; the micelle grew into a rod-like shape under alkaline conditions. Scanning electron micrographs showed that the interior of the FL hydrogel had a more complete porous structure. The FL-2 hydrogel loaded with 5-fluorouracil exhibited an approximately linear release trend within 12 h and has good biocompatibility. Therefore, FL hydrogels have potential applications in the field of biomedicine., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

The synthesis of metallaisoxazole by the [3+2] cycloaddition reaction of metallacyclopropene with nitrosonium tetra-fluoroborate has been achieved under mild conditions. Nuclear magnetic resonance spectra, X-ray crystallographic analysis, and density functional theory calculations all suggest that the metallaisoxazole exhibits an aromatic character.

Manganese dioxide (MnO 2 ) with a conversion mechanism is regarded as a promising anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity (∼1223 mA h g -1 ) and environmental benignity as well as low cost. However, it suffers from insufficient rate capability and poor cyclic stability. To circumvent this obstacle, semiconducting polypyrrole coated-δ-MnO 2 nanosheet arrays on nickel foam (denoted as MnO 2 @PPy/NF) are prepared via hydrothermal growth of MnO 2 followed by the electrodeposition of PPy on the anode in LIBs. The electrode with ∼50 nm thick PPy coating exhibits an outstanding overall electrochemical performance. Specifically, a high rate capability is obtained with ∼430 mA h g -1 of discharge capacity at a high current density of 2.67 A g -1 and more than 95% capacity is retained after over 120 cycles at a current rate of 0.86 A g -1 . These high electrochemical performances are attributed to the special structure which shortens the ion diffusion pathway, accelerates charge transfer, and alleviates volume change in the charging/discharging process, suggesting a promising route for designing a conversion-type anode material for LIBs.

A novel functionalized graphene oxide (FGO) wrapped with Si-N-containing flame retardant (FR-fGO) was successfully synthesized via a chemical modification process and applied to enhance the thermal stability, fire resistance, and mechanical properties of epoxy resin (EP). Herein, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to explore the structure and morphology of FR-fGO to overcome the fact that the FGO cannot strongly bond with the polymer matrix. With the incorporation of FR-fGO into EP, the thermal stability improved and the total heat release decreased compared with pure EP. Meanwhile, FR-fGO composites significantly reduced the amount of flammable and toxic volatiles. A possible flame-retardant mechanism of FR-fGO was deduced from a theoretical analysis of the chemical bond energy and the experimental results of thermal decomposition: namely, well-dispersed FR-fGO nanosheets constituted a physical barrier, with an Si-N-containing synergy system forming a highly graphitized residual char with an Si-containing cross-linked network. The enhancement in mechanical properties demonstrated that the composites had remarkable compatibility. This study provides a novel modification strategy to improve the dispersion and flame retardance of graphene., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Toxicity and environmental issues have elicited research attention regarding the need to prepare a green flame retardant with high flame retardancy. Here, a supermolecular self-assembly technology was used to prepare nickel phytate as shell materials aggregated on aminated silica nanotemplates through electrostatic interactions as a green novel flame retardant (Ni@SiO 2 -PA). After incorporating the obtained core-shell structured Ni@SiO 2 -PA into epoxy resin (EP), the supermolecular shell effectively enhanced the adhesive property between the nanoparticles and the EP matrix. The thermal stability was improved, and the peak heat release rate decreased significantly after introducing the well-characterized Ni@SiO 2 -PA. The absorbance intensity of the toxic aromatic compounds also decreased. Moreover, the char yield of the EP composites was improved because of the synergetic coupled effects between the nickel phytate supermolecules and SiO 2 nanotemplates. The possible fire-retardancy mechanism was hypothesized as follows. The crosslinking structure of the silica initially enabled the formation of a polymer network to prevent further decomposition. The N-P synergistic flame-retardancy system then generated a gas barrier and P-rich intumescent char. Besides, char-residue generation was catalyzed by introducing Ni 2+ , which isolated the heat and the exchange between oxygen and the matrix. Overall, this study proposes a novel green flame retardant that may enable significant improvements in preparing environmentally friendly organic-inorganic materials with applications in the fields of flame-retardant composites., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Two new homo chiral Cu-Ln (Ln = Gd and Ho) compounds bearing a chiral Schiff base ligand (1 R ,3 S )- N ', N ''-bis[3-methoxysalicylidene]-1,3-diamino-1,2,2-trimethylcyclopentane (H 2 L) have been synthesized and characterized by elemental analysis, IR spectroscopic and single-crystal X-ray diffraction techniques. The compounds were found to exhibit 1D zig-zag skeletons with double μ-1,5 bridging dicyanamide anions. Circular dichroism (CD) spectra have been used to verify their chiroptical activities. Magnetic studies suggest that 1 and 2 hold the same magnetic behavior with the dinuclear compounds presenting ferromagnetic interaction. Furthermore, both compounds show ferroelectricity with the remnant polarization ( P r ) value of 0.23 and 0.18 μC cm -2 at room temperature, respectively., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report a novel biomimetic drug discovery platform using high expression epidermal growth factor receptor (EGFR) HEK 293 cell membrane camouflaged magnetic nanoparticles. The EGFR/magnetic cell membrane nanoparticles (MCMNs) integrated desirable magnetic features and special binding bioaffinity. Application of this drug-targeting concept is expected to pave ways to a new drug discovery strategy.

Epoxy resin (EP) composites with improved thermal resistance were fabricated. To solve the problem of low thermal resistance derived from phosphazene flame-retardant additives, we designed a system based on flame-retardant microcapsules P(H), with hexaphenoxycyclotriphosphazene as the core and polymethyl methacrylate as the shell. The core-shell structure was characterized and confirmed. The thermal resistance of the cured EP composites containing 1 wt% P(H) microcapsules was improved because of the increased glass transition temperatures. The P(2.75H)/EP composites can reach a limited oxygen index of 30.5% and V-1 rating in UL-94 tests. Heat and gas release rates were reduced during combustion tests. Residual images implied that the P(H) microcapsules may promote the formation of a flame-retardant char layer. Pyrolysis analysis demonstrated that the P(H) microcapsules can decompose in two procedures to produce flame-retardant gas components. Therefore, the flame-retardant mechanism involved the flame inhibition effect in the gas phase, and the charring effect in the condensed phase., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this paper, we studied the growth of graphene on an untreated Cu substrate and further studied the effect of carbon-based impurities on the nucleation of graphene in different growth environments. It is found that the impurities on the surface of the Cu substrate easily lead to damage of the graphene, and the impurities do not always promote nucleation as previously reported, but inhibit nucleation in a high etching environment. Finally, based on experimental results, a model of nucleation and growth of graphene around impurities is presented.

This study investigates the growth promotion of vertically oriented graphene in plasma-enhanced chemical vapor deposition through Ar plasma treatment. Combined with various substrate treatments, including hydrofluoric acid etching and oxidation after Ar plasma treatment, Ar plasma pretreatment promotes vertical growth through the microcavity on the rough substrate surface and the active growth sites. The microcavity affects the strain distribution and defects of as-deposited planar films, which benefit the transition of 2D deposition to 3D vertical growth. A growth model on the effect of Ar plasma pretreatment is proposed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this work, uranium(vi) biomineralization by soluble ortho -phosphate from decomposition of the phosphate rock powder, a cheap and readily available material, was studied in detail. Penicillium funiculosum was effective in solubilizing P from the phosphate rock powder, and the highest concentration of the dissolved phosphate reached 220 mg L -1 (pH = 6). A yellow precipitate was immediately formed when solutions with different concentrations of uranium were treated with PO 4 3- -containing fermentation broth, and the precipitate was identified as chernikovite by Fourier transform infrared spectroscopy, scanning electron microscope, and X-ray powder diffraction. Our study showed that the concentrations of uranium in solutions can be decreased to the level lower than maximum contaminant limit for water (50 μg L -1 ) by the Environmental Protection Agency of China when Penicillium funiculosum was incubated for 22 days in the broth containing 5 g L -1 phosphate rock powder., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Cu 2 In x Zn 1- x SnS 4 ( x = 0.4) alloy thin films were synthesized on soda lime glass (SLG) substrate by a simple low-cost sol-gel method followed by a rapid annealing technique. The influence of sulfurization temperature and sulfurization time on the structure, morphology, optical and electrical properties of Cu 2 In x Zn 1- x SnS 4 thin films was investigated in detail. The XRD and Raman results indicated that the crystalline quality of the Cu 2 In x Zn 1- x SnS 4 alloy thin films was improved, accompanied by metal deficiency, particularly tin loss with increasing the sulfurization temperature and sulfurization time. From absorption spectra it is found that the band gaps of all Cu 2 In x Zn 1- x SnS 4 films are smaller than that (1.5 eV) of the pure CZTS film due to In doping, and the band gap of the Cu 2 In x Zn 1- x SnS 4 films can be tuned in the range of 1.38 to 1.19 eV by adjusting the sulfurization temperature and sulfurization time. Hall measurement results showed that all Cu 2 In x Zn 1- x SnS 4 alloy thin films showed p-type conductivity characteristics, the hole concentration decreased and the mobility increased with the increase of sulfurization temperature and sulfurization time, which is attributed to the improvement of the crystalline quality and the reduction of grain boundaries. Finally, the Cu 2 In x Zn 1- x SnS 4 film possessing the best p-type conductivity with a hole concentration of 9.06 × 10 16 cm -3 and a mobility of 3.35 cm 2 V -1 s -1 was obtained at optimized sulfurization condition of 580 °C for 60 min. The solar cell using Cu 2 In x Zn 1- x SnS 4 as the absorber obtained at the optimized sulfurization conditions of 580 °C for 60 min demonstrates a power conversion efficiency of 2.89%. We observed an increment in open circuit voltage by 90 mV. This work shows the promising role of In in overcoming the low V oc issue in Cu-kesterite thin film solar cells., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Several bone diseases, including arthritis, fracture and osteoporosis, have a pathophysiologically important inflammatory component. Sustained inflammation can result in delayed bone healing. Therefore, to promote bone repair, it is important to inhibit inflammatory bone erosion and suppress pro-inflammatory mediators. In this study, aspirin significantly enhanced immunomodulation and osteogenic differentiation in human mesenchymal stem cells (hMSCs). Additionally, an osteogenic BFP-1 peptide-decorated substrate (PS-PEP) enhanced osteogenic differentiation of aspirin-treated hMSCs compared to a pristine substrate. Alkaline phosphatase assay, quantitative real-time polymerase chain reaction, immunostaining and Alizarin Red S staining revealed that aspirin-treated hMSCs cultured on PS-PEP exhibited enhanced osteogenesis compared with untreated cells. Thus, we report here that the anti-inflammatory and osteogenic effects of aspirin promote the activity and osteogenesis of hMSCs. The combination of aspirin and an osteogenic BFP-1 peptide-decorated substrate suppresses the production of pro-inflammatory mediators and promotes osteogenic differentiation of hMSCs; therefore, this novel strategy has potential for application in cell therapy and bone tissue engineering.

A boron radical contact ion-pair Mes 2 B{4-(3,5-dimethylpyridinyl)}K(18-crown-6)(THF) (1K) has been isolated and characterized by electron paramagnetic resonance (EPR) spectroscopy, UV-vis absorption spectroscopy and single crystal X-ray diffraction. The geometry, bonding and spin density distribution are shown to be affected by the NK interaction. The unpaired electron resides mainly on the boron atom and falls between those of triarylboron radical anions and neutral boron radicals. The work provides a novel boron-centered radical intermediate, connecting anionic and neutral boryl radicals.

Oxygen can passivate Cu surface active sites when graphene nucleates. Thus, the nucleation density is decreased. The CuO/Cu substrate was chosen for graphene domain synthesis in our study. The results indicate that the CuO/Cu substrate is beneficial for large-scale, single-crystal graphene domain synthesis. Graphene grown on the CuO/Cu substrate exhibits fewer nucleation sites than on Cu foils, suggesting that graphene follows an oxygen-dominating growth. Hydrogen treatment via a heating process could weaken the surface oxygen's role in limiting graphene nucleation under the competition of hydrogen and oxygen and could transfer the synthesis of graphene into a hydrogen-dominating growth. However, the competition only exists during the chemical vapor deposition heating process. For non-hydrogen heated samples, oxygen-dominating growth is experienced even though the samples are annealed in hydrogen for a long time after the heating process. With the temperature increases, the role of hydrogen gradually decreases. The balance of hydrogen and oxygen is adjusted by introducing hydrogen gas at a different heating temperatures. The oxygen concentration on the substrate surface is believed to determine the reactions mechanisms based on the secondary ion mass spectrometry test results. This study provides a new method for the controllable synthesis of graphene nucleation during a heating process.

We addressed the potential catalytic role of Pt-embedded graphene in CO oxidation by first-principles-based calculations. We showed that the combination of highly reactive Pt atoms and defects over graphene makes the Pt-embedded graphene a superior mono-dispersed atomic catalyst for CO oxidation. The binding energy of a single Pt atom onto monovacancy defects is up to -7.10 eV, which not only ensures the high stability of the embedded Pt atom, but also vigorously excludes the possibility of diffusion and aggregation of embedded Pt atoms. This strong interfacial interaction also tunes the energy level of Pt-d states for the activation of O2, and promotes the formation and dissociation of the peroxide-like intermediate. The catalytic cycle of CO oxidation is initiated through the Langmuir-Hinshelwood mechanism, with the formation of a peroxide-like intermediate by the coadsorbed CO and O2, by the dissociation of which the CO2 molecule and an adsorbed O atom are formed. Then, another gaseous CO will react with the remnant O atom and make the embedded Pt atom available for the subsequent reaction. The calculated energy barriers for the formation and dissociation of the peroxide-like intermediate are as low as 0.33 and 0.15 eV, respectively, while that for the regeneration of the embedded Pt atom is 0.46 eV, indicating the potential high catalytic performance of Pt-embedded graphene for low temperature CO oxidation.

Soil pollution with herbicides is a global problem. Before phytoremediation technology is developed for the plant-based clean-up of polluted soils, investigation of potential plants that can be used to accumulate and degrade herbicides is a critical step. In this study, three selected genotypes of ryegrass were comprehensively analyzed with regard to the atrazine accumulation, degradation and toxicological response. Under the conditions of soil with 0.8 mg kg(-1) atrazine, the maximum value for atrazine accumulation was 2.70 mg kg(-1) in shoots and 0.58 mg kg(-1) in roots. The residue of atrazine in soil with ryegrass cultivation was much lower than that in soil without ryegrass cultivation. Also, the content of atrazine residues in the rhizosphere was significantly lower than that in the non-rhizosphere soil. Activities of several enzymes (urease, invertase, polyphenol oxidase, acid phosphatase and alkaline phosphatase) in soil were assayed. These enzymes were depressed by atrazine but activated by ryegrass cultivation, even in the presence of atrazine. Finally, comparative studies have been conducted on the ryegrass genotypes in response to atrazine. They showed different capacities of degradation and bioaccumulation of atrazine. One of the grass cultivars Changjiang II (CJ) had better growth and higher levels of chlorophyll, but displayed less oxidative injury than two others, Abode (AB) and Jiewei (JW), under atrazine exposure.

Two Co(II) and Mn(II) coordination polymers, which have been synthesized under hydrothermal conditions, are isomorphous with magnetic Δ-chains containing trinuclear triangular [M(3)(μ(3)-OH)] clusters. The Δ-chains are bridged by isonicotinic spacers to generate a two-dimensional scalariform layer structure. Magnetic investigations indicate that Co(II) compound exhibits not only spin canting but also metamagnetic behaviors, while only spin-canted antiferromagnetic behaviors was observed in Mn(II) compound.

Prometryne is a selective herbicide of the s-triazine chemical family. Due to its weak absorption onto soil, it readily leaches down through the soil and contaminates underground water. Application of organic manure to soil has become a widespread practice as a disposal strategy to improve soil properties. In this study, we demonstrated the effect of pig manure compost (PMC) and lake-bed sludge (SL) on the sorption/desorption, mobility and bioavailability of prometryne in soil using comprehensive analysis approaches. Downward movement of prometryne was monitored in the packed soil column. Addition of PMC or SL decreased considerably the mobility and total concentration of prometryne in the soil leachate. Bioavailability analyses with wheat plants revealed that addition of the organic matter reduced accumulation of prometryne in tissues and increased plant elongation and biomass. These results indicate that the organic amendments are effective in modifying adsorption and mobility of the pesticide in soil.

Three N,N-bidentate ligands, 5,5'-dibromo-2,2-bipyridine (L1) and two carbazole containing ligands of 5-bromo-5'-carbazolyl-2,2-bipyridine (L2), 5,5'-dicarbazolyl-2,2'-bipyridine (L3), and their corresponding rhenium Re(CO)3Cl(L) complexes (ReL1-ReL3) have been successfully synthesized and characterized by elemental analysis, 1H NMR and IR spectra. Their photophysical properties and thermal analysis, along with the X-ray crystal structure analysis of L3 and complexes ReL1 and ReL3 are also described. In CH2Cl2 solution at room temperature, all complexes display intense absorption bands at ca. 220-350 nm, which can be assigned to spin-allowed intraligand (pi-->pi*) transitions, and the low energy broad bands in the 360-480 nm region are attributed to the metal to ligand charge-transfer d(Re)-->pi* (diimine) (MLCT). The introduction of carbazole moieties improves the MLCT absorption and molar extinction coefficient of these complexes. Upon excitation at the peak maxima, all complexes show strong emissions around 620 nm, which are assigned to d(Re)-->pi* (diimine) MLCT phosphorescence. The photoluminescence lifetime decay of Re(I) complexes were measured and the quantum efficiencies of the rhenium(I) complexes were calculated by using air-equilibrated [Ru(bpy)3]2+ x 2 Cl- aqueous solution as standard (phi(std) = 0.028). The complexes with appended carbazole moieties exhibit enhanced luminescence performances relative to ReL1.