Altering Ligand Microenvironment of Atomically Dispersed CrN4 by Axial Ligand Sulfur for Enhanced Oxygen Reduction Reaction in Alkaline and Acidic Medium.

Because of the instability and Fenton reactivity of non-precious metal nitrogen-carbon based catalyst when processing the oxygen reduction reaction (ORR), seeking for electrocatalysts with highly efficient performance becomes very highly desired to speed up the commercialization of fuel cell. Herein, chromium (Cr)-N4  electrocatalyst containing extraterrestrial S formed axial S1 -Cr1 N4  bonds (S1 Cr1 N4 C) is achieved via an assembly polymerization and confined pyrolysis strategy. Benefiting from the adjusting  coordination configuration and electronic structure of the metal center through axial coordination, S1 Cr1 N4 C exhibits enhanced the intrinsic activity (half-wave potential (E1/2 ) is 0.90 V versus reversable hydrogen electrode, RHE) compared with that of CrN4 C and Pt/C catalysts. More notably, the catalyst is almost inert in catalyzing the Fenton reaction, and thus shows the high stability. Density functional theory (DFT) results further reveal that the existence of axial S atoms in S1 Cr1 N4 C moiety has the better ORR activity than Cr1 N4 C moieties. The axial S ligand in S1 Cr1 N4 C moiety can break the electron localization around the planar Cr1 N4  active center, which facilitated the rate-limiting reductive release of OH* and accelerated overall ORR process. The present work opens up a new avenue to modulate the axial ligand type of the single-atoms (SAs) active center to enhance intrinsic SAs performances.

A Dirac nodal surface semi-metallic carbon-based structure as a universal anode material for metal-ion batteries with high performance.

The rapid development of electronic devices requires high power storage batteries. However, reported 3D carbon-based materials are semiconductors or metals and are used in Li- or Na-ion batteries with low capacities. Thus, it is of interest to discover whether there is a universal semi-metallic material for use in high performance Li-, Na-, and K-ion batteries. Inspired by the recent synthesis of 3D carbon-based materials, in the research reported here, a 3D regular porous structure (bct-C56) is designed using graphene sheets. The porous carbon-based material has mechanical, dynamic, thermal, and mechanical stabilities. Interestingly, bct-C56 exhibits semi-metallic features with two Dirac nodal surfaces with mirror symmetry, as well as high Fermi velocities, indicating high electron-transport abilities. More excitingly, its theoretical capacities are 743.8, 478.2, and 425.0 mA h g-1, with diffusion barriers of 0.05-0.12, 0.07-0.12, and 0.03-0.05 eV, average OCVs of 0.31, 0.45, and 0.59 V, and volume expansion levels of 1.2%, 0.02%, and 3.1%, in Li-, Na-, and K-ion batteries, respectively. All these excellent characteristics suggest that semi-metallic bct-C56 is a universal anode material for use in metal-ion batteries with a fast charge-discharge rate. In this research, not only was a new material with a Dirac nodal surface feature designed, but it also offers an approach for the creation of high performance and universal metal-ion battery anodes with 3D porous carbon materials.

Photodriven Disproportionation of Nitrogen and Its Change to Reductive Nitrogen Photofixation.

Nitrogen fixation is an essential process for sustaining life. Tremendous efforts have been made on the photodriven fixation of nitrogen into ammonia. However, the disproportionation of dinitrogen to ammonia and nitrate under ambient conditions has remained a grand challenge. In this work, the photodriven disproportionation of nitrogen is realized in water under visible light and ambient conditions using Fe-doped TiO2 microspheres. The oxygen vacancies associated with the Fe dopants activate chemisorbed N2 molecules, which can then be fixed into NH3 with H2 O2 as the oxidation product. The generated H2 O2 thereafter oxidizes NH3 into nitrate. This disproportionation reaction can be turned to the reductive one by loading plasmonic Au nanoparticles in the doped TiO2 microspheres. The generated H2 O2 can be effectively decomposed by the Au nanoparticles, resulting in the transformation of the disproportionation reaction to the completely reductive nitrogen photofixation.

Human umbilical cord mesenchymal stem cell-derived exosomes act via the miR-1263/Mob1/Hippo signaling pathway to prevent apoptosis in disuse osteoporosis.

Disuse osteoporosis (DOP) is a common complication resulting from the lack of or disuse of mechanical loading and has been unsatisfactorily treated. We hypothesized that exosomes derived from human umbilical cord mesenchymal stem cells (HUCMSCs) could reduce bone marrow mesenchymal stem cell (BMSC) apoptosis in rat DOP via the miR-1263/Mob1/Hippo signaling pathway. To evaluate the function of exosomes derived from HUCMSCs (HUCMSC-Exos) in DOP, hind limb unloading (HLU)-induced DOP rat models were prepared. In vitro, the proliferation of BMSCs were evaluated using CCK-8 assays. Further, the apoptosis of BMSCs were evaluated using annexin V-FITC assay and Western blots. In vivo, the protective effects of HUCMSC-Exos were evaluated using HE staining and microCT analysis. The underlying molecular mechanism of exosome action on BMSC apoptosis through the miR-1263/Mob1/Hippo pathway was also investigated by high-throughput RNA sequencing, luciferase reporter assays, RNA-pull down assays and Western blots. The RNA-seq and q-PCR results showed that the level of miR-1263 was most abundant among differentially expressed microRNAs. Exosomal miR-1263 could bind to the 3'untranslated region (3' UTR) of Mob1 and exert its function by directly targeting Mob1 in recipient cells. The inhibition of Mob1 could activate YAP expression. Hippo inhibition reversed the in vitro HLU-induced apoptotic effect on BMSCs. The microCT and HE staining results indicated that HUCMSC-Exos ameliorated DOP in vivo. Exosomes derived from HUCMSCs are effective at inhibiting BMSC apoptosis and preventing rat DOP. This mechanism is mediated by the miR-1263/Mob1/Hippo signaling pathway.

Structure-based engineering of heparinase I with improved specific activity for degrading heparin.

BACKGROUND: Heparinase I from Pedobacter heparinus (Ph-HepI), which specifically cleaves heparin and heparan sulfate, is one of the most extensively studied glycosaminoglycan lyases. Enzymatic degradation of heparin by heparin lyases not only largely facilitates heparin structural analysis but also showed great potential to produce low-molecular-weight heparin (LMWH) in an environmentally friendly way. However, industrial applications of Ph-HepI have been limited by their poor yield and enzyme activity. In this work, we improve the specific enzyme activity of Ph-HepI based on homology modeling, multiple sequence alignment, molecular docking and site-directed mutagenesis. RESULTS: Three mutations (S169D, A259D, S169D/A259D) exhibited a 50.18, 40.43, and 122.05% increase in the specific enzyme activity and a 91.67, 108.33, and 75% increase in the yield, respectively. The catalytic efficiencies (kcat/Km) of the mutanted enzymes S169D, A259D, and S169D/A259D were higher than those of the wild-type enzyme by 275, 164, and 406%, respectively. Mass spectrometry and activity detection showed the enzyme degradation products were in line with the standards of the European Pharmacopoeia. Protein structure analysis showed that hydrogen bonds and ionic bonds were important factors for improving specific enzyme activity and yield. CONCLUSIONS: We found that the mutant S169D/A259D had more industrial application value than the wild-type enzyme due to molecular modifications. Our results provide a new strategy to increase the catalytic efficiency of other heparinases.

Stabilization of two-dimensional penta-silicene for flexible lithium-ion battery anodes via surface chemistry reconfiguration.

Silicon-based two-dimensional (2D) materials have unique properties and extraordinary engineering applications. However, penta-silicene is unstable. Herein, by employing first-principles calculations, we provide a facile surface chemistry method, i.e. functionalization, to acquire and reconfigure stable penta-silicene for use in flexible lithium-ion batteries. Our results of density functional theory calculations showed that the reconfigured penta-silicene nanosheets possess a broad range of properties, including semiconductors with an indirect bandgap, semiconductors with a direct bandgap, semimetals and metals. For fluorinated penta-silicene, a fluorine-concentration-induced transition from a semiconductor to a metal is found. For fully fluorinated penta-silicene, a mechanically induced transition from a semiconductor with an indirect bandgap to a semiconductor with a direct bandgap is obtained. Our calculation results showed the reconfigured penta-silicene is a high-performance anode for use in flexible lithium (Li)-ion batteries. A transition from a semiconductor to a metal with adsorption of Li atoms indicates a high electrical conductivity. It possesses low Li diffusion barriers (0.08-0.28 eV), demonstrating a high mobility of Li ions. The metallic feature and low Li diffusion barriers reveal that it has an ultrafast charge/discharge rate. This work suggests that surface chemistry reconfiguration provides new stable materials with excellent mechanical properties and tunable electronic properties for their promising applications in flexible metal-ion batteries and solar batteries as well as nanoelectronics devices.

Understanding the roles of plasmonic Au nanocrystal size, shape, aspect ratio and loading amount in Au/g-C3N4 hybrid nanostructures for photocatalytic hydrogen generation.

Hybrid photocatalysts containing plasmonic metal and semiconductor building blocks can alleviate charge carrier recombination and broaden the range of light absorption of the semiconductor. In this work, plasmonic Au nanocrystals of different sizes and shapes (spheres and rods) are attached on graphitic carbon nitride (g-C3N4) nanosheets through electrostatic attraction. The effects of the morphology and loading amount of the Au nanocrystals are carefully studied for understanding and optimizing the hybrid photocatalysts. The optimized 18 nm-sized Au nanospheres/g-C3N4 photocatalyst exhibits a superior activity for H2 evolution at a rate of 540 µmol g-1 h-1 under visible light (λ > 420 nm), exceeding those produced over larger-sized Au nanospheres/g-C3N4, Au nanorods/g-C3N4 and photodeposited Au nanoparticles/g-C3N4 photocatalysts. The excellent activity for H2 evolution is attributed to the electron sink and plasmonic effects of the Au nanocrystals in different spectral regions, as evidenced by photocurrent measurements. The introduced plasmonic Au nanocrystals not only enhance the photocatalytic activity, but they also endow the hybrid photocatalysts with an extended light absorption range. Our results and understanding will be useful for the design of efficient plasmonic photocatalysts for solar to fuel energy conversion as well as for other plasmon-driven chemical reactions.

Highly negative Poisson's ratio in a flexible two-dimensional tungsten carbide monolayer.

Auxetic materials have numerous promising engineering applications such as fracture resistance and energy storage due to their negative Poisson's ratios (NPRs). However, compared to materials possessing positive Poisson's ratios (PPRs), auxetic materials are rare. In this paper, by employing first principles calculations, we found a high NPR two-dimensional (2D) material, tungsten carbide (W2C), in the transition metal carbides (MXenes). Our results of the relatively moderate Young's modulus and fracture strength as well as the critical strain showed that the 2D monolayer W2C is an extraordinary flexible material. Our DFT results also demonstrated that W2C possesses high NPRs while Hf2C and Ta2C have PPRs. Furthermore, the mechanically induced deformation mechanism and the NPR formation mechanism of W2C have been proposed. Such an intrinsic NPR in W2C is attributed to the strong coupling between the C-p and W-d orbitals in the pyramid structural unit. The mechanically induced deformation mechanism and the PPR formation mechanism of Hf2C have also been determined. The intrinsic NPR for W2C transforms to PPR upon the surface functionalization induced. The behavior occurs due to the W-C interaction weakening. The excellent NPR in the 2D MXene material combined with other outstanding properties such as the metallic state would bring about its promising engineering prospects, ranging from the metal-ion battery, to automobiles and aircraft.

Photophysical/Chemistry Properties of Distyryl-BODIPY Derivatives: An Experimental and Density Functional Theoretical Study.

Singlet oxygen is the key element for photodynamic therapy. In this paper, six novel distyryl-BODIPY compounds were synthesized and investigated in detail to fully evaluate their photophysical/chemistry characteristics. Specially, the singlet oxygen (1O2) quantum yield of compounds 2 and 4 each bearing two bromine atoms in their skeleton revealed the position effect of heavy atom for 1O2 production. The 1O2 quantum yield of 4, which was brominated at 2/6 position of BODIPY skeleton, was much higher than that of compound 2, brominated at styryl group with a long distance toward BODIPY core. Importantly, theoretical calculations were carried out to elaborate the essential reason for the difference of 2 and 4 by investigating intersystem crossing rate.

Modulation of the electronic and mechanical properties of phagraphene via hydrogenation and fluorination.

Recently, a new carbon sheet, phagraphene, was proposed by theoretical calculations [Nano Lett. 2015, 15, 6182]. In this paper, hydrogenated and fluorinated phagraphene (denoted as H-PHA and F-PHA) sheets have been systematically studied using first-principles calculations. The results of formation energy, ab initio molecular dynamics, phonon dispersion and elastic constants confirm that the modified phagraphene sheets are thermodynamically and dynamically as well as mechanically stable. We find that hydrogenation or fluorination is an effective way to modulate the bandgap, and we also find that adsorption-induced semimetal-semiconductor transition and adsorption-induced semimetal-insulator transition occur. Configuration-dependent bandgaps for partially H-PHA and configuration-independent bandgaps for fully H-PHA are determined. Adsorption-ratio-dependent bandgaps of H-PHA and F-PHA are also identified. Bandgaps calculated from HSE06 and PBE functionals of fully H-PHA are larger than those of F-PHA, and they are comparable to hydrogenated/fluorinated penta-graphene while they are larger than their corresponding graphene. Dependence of bandgaps of fully H-PHA and F-PHA on the tensile strain is investigated, and our calculations show that an insulator-semiconductor transition occurs upon increasing the tensile strain. Our results also show that the mechanical properties can be controlled using hydrogenation and fluorination. The calculations of Young's modulus and Poisson's ratio reveal that functionalized phagraphene sheets possess suitable stiffness and resistance to volume deformation, and both are smaller than those of the pristine phagraphene.

Plasmon Modes Induced by Anisotropic Gap Opening in Au@Cu2 O Nanorods.

Integration of semiconductors with noble metals to form heteronanostructures can give rise to many interesting plasmonic and electronic properties. A number of such heteronanostructures have been demonstrated comprising noble metals and n-type semiconductors, such as TiO2 , ZnO, SnO2 , Fe3 O4 , and CuO. In contrast, reports on heteronanostructures made of noble metals and p-type semiconductors are scarce. Cu2 O is an unintentional p-type semiconductor with unique properties. Here, the uniform coating of Cu2 O on two types of Au nanorods and systematic studies of the plasmonic properties of the resultant core-shell heteronanostructures are reported. One type of Au nanorods is prepared by seed-mediated growth, and the other is obtained by oxidation of the as-prepared Au nanorods. The (Au nanorod)@Cu2 O nanostructures produced from the as-prepared nanorods exhibit two transverse plasmon peaks, whereas those derived from the oxidized nanorods display only one transverse plasmon peak. Through electrodynamic simulations the additional transverse plasmon peak is found to originate from a discontinuous gap formed at the side of the as-prepared nanorods. The existence of the gap is verified and its formation mechanism is unraveled with additional experiments. The results will be useful for designing metal-semiconductor heteronanostructures with desired plasmonic properties and therefore also for exploring plasmon-enhanced applications in photocatalysis, solar-energy harvesting, and biotechnologies.

Ultrafast growth of carbon nanotubes on graphene for capacitive energy storage.

We have demonstrated a novel three-dimensional (3D) architecture of a graphene/carbon nanotube (G-CNT) hybrid synthesized at large scale within just 5 s via a simple microwave-heating method without the usage of any other conducting or expanding agent for the first time. The carbon composites obtained consist of evenly grown CNTs with an average diameter of about 15 nm on the surface of graphene nanosheets. The G-CNT hybrid exhibits enhanced electrochemical performance for both aqueous and organic supercapacitor devices. Particularly, the G-CNT electrodes demonstrate an enhanced specific capacitance of 361 F g(-1) at a current density of 1.1 A g(-1) in an aqueous electrolyte and a volumetric capacitance of 254 F cm(-3) in an organic electrolyte. They also display excellent cycle stability with nearly 91.2% of the initial capacitance retained after 10 000 charging-discharging cycles at a current density of 15 A g(-1). This demonstrates that the developed composites have potential applications in supercapacitors and other energy storage devices.

Prevalence of hepatitis B surface antigen (HBsAg) in a blood donor population born prior to and after implementation of universal HBV vaccination in Shenzhen, China.

BACKGROUND: Neonatal hepatitis B vaccination program at birth has been implemented nationwide since 1992 in China. However, current HBV prevalence status in blood donors has not been entirely examined, which may impact HBV safety in blood donations as the vaccinees over 18 years old progressively become the majority population of blood donors. METHODS: In this study, 569,145 blood donors were screened for HBsAg by rapid tests and enzyme immunoassays, among them 475,538 blood samples with negative HBsAg were further screened for HBV DNA by nucleic acid testing between 2005 and 2014 at Shenzhen blood center. RESULTS: An overall 2.3 % HBsAg prevalence was found in the blood donor population during the past 10 years (2.86 % in 2005, 1.76 % in 2010, and 2.79 % in 2014, respectively). HBsAg seroconversion occurred in 0.37 % of repeat-donors. When stratified by age, the prevalence of HBsAg was found significantly higher in younger donors age 18-25 years (2.73 %) than in those 26-35 years (2.13 %), 36-45 years (2.03 %) and 46-58 years (1.71 %) (P < 0.001), unexpectedly suggesting that younger donors remained at risk of chronic HBV infection. Assuming that donors aged 18-22 born before or after 1992 were non-vaccinated and vaccinated, respectively, HBsAg prevalence was higher in first-time donors born ≥1992 (3.9 %) than prior to 1992 (3.5 %, P = 0.005). The incidence of HBV infection in the 5-year period examined was significantly lower in repeat-donors born ≥1992 (0.27 %) than prior to 1992 (0.6 %, P = 0.008). The yield of HBV DNA+/HBsAg- donors was 1:3,302, including 1:4,486 occult infections and 1:43,231 window period infections. CONCLUSION: Young blood donors born after implementation of universal HBV vaccination in China presented higher prevalence of HBsAg but lower incidence of HBsAg seroconversion than older, presumed unvaccinated, donors. HBV vaccine boosting for adolescents at 15-17 years old prior to reaching blood donor age might help improve blood safety.

Tunable thermal transport and mechanical properties of graphyne heterojunctions.

By employing molecular dynamics simulations, a family of graphyne heterojunctions (GYHJs) made by two different graphynes (GYs) have been designed and prepared. The dependence of tunable properties of GYHJs, such as thermal conductivity, mechanical properties, interfacial thermal resistance and rectification, on the composition and type of GYHJs is determined. Upon changing the composition of a GYHJ, one can keep a constant value of its fracture strength (and/or Young's modulus), while tuning its thermal conductivity. The thermal conductivities of GYHJs in the zigzag direction are larger than those in the armchair direction, indicating GYHJs are anisotropic. By decreasing the percentage of γ-GY, the thermal conductivities of GYHJs γ-GY/6,6,12-GY/γ-GY and γ-GY/14-GY/γ-GY decrease linearly in the armchair direction, whereas they undergo three stages (first decrease, then keep a constant value, and finally increase) in the zigzag direction. Regarding the mechanical response, by increasing the percentage of the graphyne in the GYHJ which possesses smaller Young's modulus, the Young's modulus of the GYHJ decreases. These findings would provide significant insights into the potential applications of graphyne-family materials in nanodevices.

High prevalence of anti-hepatitis B core antigen in hepatitis B virus-vaccinated Chinese blood donors suggests insufficient protection but little threat to the blood supply.

BACKGROUND: In East Asia, individuals systematically vaccinated at birth to hepatitis B virus (HBV) are an increasing part of the blood donor population. Their environment presents a high risk of contact with HBV. HBV vaccine efficacy and potential safety risk carried by vaccinated donors were examined. STUDY DESIGN AND METHODS: A total of 2028 vaccinated blood donors were recruited in 2012 and 2013 and tested for serologic (hepatitis B surface antigen [HBsAg], antibody to hepatitis B surface antigen [anti-HBs], and antibody to hepatitis B core antigen [anti-HBc]) and molecular (HBV DNA) markers of HBV. HBsAg, anti-HBs, and viral load were quantified. RESULTS: Donors 18 to 21 years systematically vaccinated at birth and 22 to 25 years and older donors had both 30.0% negative serology and 1.8% anti-HBc only but the latter group carried significantly higher prevalence of anti-HBc (p < 0.0001). Anti-HBc, mostly associated with anti-HBs, increased from 10.7% at age 18 to 31.5% at age 25. The level of anti-HBs was significantly higher in anti-HBc-positive donors than in anti-HBs-only donors (p < 0.0001). Samples from 24 donors contained low viral load (25 ± 22 IU/mL), half of them undetected by standard nucleic acid testing (NAT), and were classified as four recent infections, 17 occult HBV infections (OBI), and three primary OBIs. Eighteen of 24 carried anti-HBs; 14 of 15 strains were wild-type Genotype B and one was Genotype C. CONCLUSIONS: In an environment of frequent high Genotype B or C viremia, blood donors vaccinated at birth are frequently but mildly infected: asymptomatic and normal alanine aminotransferase level, identified by anti-HBc seroconversion and boosting of anti-HBs. Low viral load and frequent anti-HBs limit transfusion risk.

Two decades of voluntary nonremunerated blood donation in Shenzhen, China.

BACKGROUND: As an emerging metropolis with population expansion from 2 million to 10 million from 1993 to 2012, the clinical demand for blood in Shenzhen has increased 20 times. To deal with this big challenge, Shenzhen utilized voluntary nonremunerated blood donation (VNRBD) in 1993 for the first time in China. After two decades of efforts, Shenzhen has achieved self-sufficiency in its blood supply and guaranteed its blood security by nonpaid blood donation. STUDY DESIGN AND METHODS: We summarized the strategies to achieve self-sufficiency and security in the blood supply in Shenzhen during two decades, including the legal construction of VNRBDs and the continuously improving strategies to recruit and retain nonpaid donors. The collection data of whole blood (WB) and apheresis platelet (PLT) donations were retrieved, and donor demographic and donation characteristics were analyzed. RESULTS: From 1993 to 1998, paid and nonpaid blood donations coexisted in Shenzhen. From the year 1999, all WB for clinical use came from VNRBDs. From 1999 to 2012, the donors who chose to donate 400 mL each time and repeat and regular donors increased sharply to meet the fast growth of clinical demand. From the year 2005, the clinical demand for PLTs was entirely satisfied by nonpaid donations. CONCLUSIONS: After two decades of practice, we believe that the legal regime of VNRBD is fundamental guarantee for long-term self-sufficiency and security in the blood supply. In addition, strengthening the publicity to improve the public's awareness and improving donation services and measures to recruit more nonpaid donors and retain repeat and regular donors are very important.

Freestanding polyaniline nanorods grown on graphene for highly capacitive energy storage.

Freestanding polyaniline (PANI) nanorods grown in situ on microwave-expanded graphene oxide (MEGO) sheets were prepared through a facile solution method. The morphological characterization indicates that large quantity of free-standing PANI nanorods with average diameter of 50 nm were uniformly deposited onto the double sides of the MEGO nanosheets to form a sandwich structure. The hybrid of PANI/MEGO (GPANI) exhibit high specific surface area and high electrical conductivity, compared with pristine PANI nanorods. When evaluated as electrodes for supercapacitors, the GPANI demonstrate high specific capacitance of 628 F g(-1) at a current density of 1.1 A g(-1), high-rate performance, and excellent cycle stability compared to individual component. Such excellent electrochemical performance should be attributed to the combined double-layer capacitance and pseudo -capacitance mechanisms from the MEGO sheets and PANI nanorods.

Mechanical properties and failure mechanisms of graphene under a central load.

By employing molecular dynamics simulations, the evolution of deformation of a monolayer graphene sheet under a central transverse loading are investigated. Dependence of mechanical responses on the symmetry (shape) of the loading domain, on the size of the graphene sheet, and on temperature, is determined. It is found that the symmetry of the loading domain plays a central role in fracture strength and strain. By increasing the size of the graphene sheet or increasing temperature, the tensile strength and fracture strain decrease. The results have demonstrated that the breaking force and breaking displacement are sensitive to both temperature and the symmetry of the loading domain. In addition, we find that the intrinsic strength of graphene under a central load is much smaller than that of graphene under a uniaxial load. By examining the deformation processes, two failure mechanisms are identified namely, brittle bond breaking and plastic relaxation. In the second mechanism, the Stone-Wales transformation occurs.

Organosilane-functionalized graphene quantum dots and their encapsulation into bi-layer hollow silica spheres for bioimaging applications.

Graphene quantum dots (GQDs) represent an important class of luminescent quantum dots owing to their low toxicity and superior biocompatibility. Chemical functionalization of GQDs and subsequent combination with other materials further provide attractive techniques for advanced bioapplications. Herein, we report the facile fabrication of fluorescent organosilane-functionalized graphene quantum dots (Si-GQDs) and their embedding into mesoporous hollow silica spheres as a biolabel for the first time. Well-proportioned Si-GQDs with bright and excitation dependent tunable emissions in the visible region were obtained via a simple and economical solvothermal route adopting graphite oxide as a carbon source and 3-(2-aminoethylamino)-propyltrimethoxysilane as a surface modifier. The as-synthesized Si-GQDs can be well dispersed and stored in organic solvents, easily manufactured into transparent film and bulk form, and particularly provide great potential to be combined with other materials. As a proof-of-principle experiment, we demonstrate the successful incorporation of Si-GQDs into hollow mesoporous silica spheres and conduct preliminary cellular imaging experiments. Interestingly, the Si-GQDs not only serve as fluorescent chromophores in the composite material, but also play a crucial role in the formation of mesoporous hollow silica spheres with a distinctive bi-layer architecture. The layer thickness and optical properties can be precisely controlled by simply adjusting the silane coupling agent addition procedure in the preparation process. Our demonstration of low-cost Si-GQDs and their encapsulation into multifunctional composites may expand the applications of carbon-based nanomaterials for future biomedical imaging and other optoelectronic applications.

Photoelectron spectroscopy of CoC2H2(-) and density functional study of Co(n)C2H2 (n = 1-3) anion and neutral clusters.

The anionic and neutral ConC2H2 (n = 1-3) clusters were investigated using anion photoelectron spectroscopy and density functional calculations. The adiabatic detachment energies and vertical detachment energies of ConC2H2(-) (n = 1-3) were determined. Our results show that the most stable geometries of anionic ConC2H2(-) (n = 1-2) and neutral ConC2H2 (n = 1-3) are composed of ConC2H clusters adsorbing a hydrogen atom on the top or bridge sites of Con, whereas Co3C2H2(-) consists of a five-member ring of Co3C2 carbide adsorbing two hydrogen atoms on two bridge sites of Co3. The reaction mechanisms show that the inserted isomer HCoC2H can convert into the vinylidene complex Co═C═CH2 via a side-on isomer M-η(2)-(C2H2).