First-principles studies on the electronic and photocatalytic water splitting properties of surface functionalized Y2C-based MXenes.

Recently, MXenes, an emerging family of two-dimensional (2D) materials, have attracted increasing interest for photocatalytic water splitting due to their various excellent physical and chemical properties, such as large specific surface area, good hydrophilicity, and remarkable light absorption ability. However, the photocatalysts of MXenes with symmetric structures are limited by rapid recombination of photo-generated carriers and the prerequisite of a large band gap no less than 1.23 eV. Differently, Janus MXenes with different surface functional groups facilitate the separation of photo-generated electrons and holes with the help of the intrinsic electric field. And, at the same time, there is no prerequisite for the band gap of Janus MXene photocatalysts as long as they possess appropriate band edge positions. Here, we explored the structural, electronic and photocatalytic water splitting properties of symmetric Y2CT2 and Janus Y2CTT' MXenes (T, T' = H, F, Cl, OH) using the density functional theory (DFT) method. Our calculations show that all the investigated Y2CT2 are not suitable photocatalysts for photocatalytic water splitting at all pH values (pH = 0, 7, and 14). In contrast, all the investigated Janus Y2CTT' MXenes are good water splitting photocatalysts with high optical absorption coefficients and remarkable solar-to-hydrogen (STH) efficiencies larger than 18% at pH = 14. Moreover, the STH efficiencies are larger than 18% even at all investigated pH values for Y2CHCl (18.5-22.6%), Y2 CFCl (∼18.7%), and Y2 C(OH)Cl (∼19.4%). Based on the first-principles calculations, we here for the first time propose an easy strategy to design Janus MXene photocatalyst candidates with possible high STH efficiency according to the electronic properties of their symmetric counterparts. Our study is helpful for the future design of Janus MXenes and more generally Janus 2D photocatalysts for water splitting with high STH efficiency.

Coordination coupling enhanced two-photon absorption of a ZnS-based microhybrid for two-photon microscopy imaging in HepG2.

Coordination coupling induced self-assembly of ZnS microparticles was performed with the help of a π-conjugated sulphur-terminal Zn(ii) complex ZnS2L (L = N-hexyl-3-{2-[4-2,2':6',2''-terpyridin-4'-yl-phenyl]ethenyl}-carbazole). The interactions between ZnS and ZnS2L components at the interface, which were analyzed by far-IR and XPS, resulted in a tunable single-photon excited fluorescence and an enhanced nonlinear optical response, including a two-photon absorption cross section and a two-photon excited fluorescence. Such an enhancement in nonlinear optical properties was triggered by the coordination coupling effect between terminal S atoms of ZnS2L and naked Zn2+ ions at the surface of ZnS particles. Thus, the novel hybrid system displayed a unique two-photon excited fluorescence to facilitate promising two-photon microscopy imaging of HepG2 cells upon NIR light illumination at 840 nm. The hybrid shows a stronger ability to enter the cells than free ZnS2L.

Highly Sensitive Electrochemical Dopamine Sensor from Poly(diallyldimethylammonium chloride)-Functionalized Graphene Nanoribbon/Gold Nanoparticle Nanocomposite.

A novel graphene oxide nanoribbon/poly(diallyldimethylammonium chloride)/gold nanoparticle (GONR/PDDA/AuNP) nanocomposite was synthesized successfully and used for the sensitive detection of dopamine. The GONR/PDDA/AuNP nanocomposite was characterized by transmission and scanning electron microscopy. The electrochemical sensor based on GONR/PDDA/AuNP nanocomposite. was studied by cyclic voltammetry and electrochemical impedance spectroscopy. Experimental parameters such as GONR/PDDA concentration, volume ratio of GONR/PDDA to AuNP, scan rates, and pH were studied to investigate their effect on peak currents. Under optimal conditions, the GONR/PDDA/AuNP-based sensor exhibited excellent electrocatalytic activity for the detection of dopamine with a wide linear range from 9.99 x 10(-8) to 8.69 x 10(-4) M and a low detection limit of 3.33 x 10(-8) M. Moreover, the proposed sensor exhibits high sensitivity, good reproducibility, and stability, and could therefore potentially be applied in other bioanalytical systems.

Porf-2 Inhibits Neural Stem Cell Proliferation Through Wnt/ß-Catenin Pathway by Its GAP Domain.

Neural stem cell (NSC) proliferation and differentiation play a pivotal role in the development of brain, the plasticity of the brain network, and the repair for brain function in CNS diseases. The mechanisms regulating NSC behavior are not well elucidated. Previous studies showed porf-2 functions as a modulator in central nerve system development. We here show that porf-2, a conserved family of RhoGAPs, is highly and specifically expressed in NSCs. We also demonstrate that porf-2 inhibits the proliferation of NSCs in vivo and in vitro, but has no effect on NSC differentiation. We investigated which domain is required for the role of porf-2 on NSC proliferation. By using neurosphere formation and Edu assay we confirmed the GAP domain is necessary for its function. In addition, we surveyed a few classical pathways on NSC proliferation and found that porf-2 inhibits NSC proliferation by suppressing the ß-catenin nuclear translocation. Taken together, we show for the first time that porf-2 inhibits NSC proliferation through Wnt/ß-catenin pathway by its GAP domain.

Synthesis of TiO2-loaded Co0.85Se thin films with heterostructure and their enhanced catalytic activity for p-nitrophenol reduction and hydrazine hydrate decomposition.

P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO2-loaded Co0.85Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co0.85Se nanofilms, and the NH3 · H2O plays an important role in the generation and crystallization of TiO2 nanoparticles. Brunauer-Emmett-Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m(2) g(-1)) than that of Co0.85Se nanofilms (55.17 m(2) g(-1)) and TiO2 nanoparticles (19.49 m(2) g(-1)). The catalytic tests indicate Co0.85Se-TiO2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co0.85Se nanofilms and TiO2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction.

Electrochemical biosensor for Ni(2+) detection based on a DNAzyme-CdSe nanocomposite.

The detection and speciation analysis of metal-ion is very important for environmental monitoring. A novel electrochemical biosensor for Nickel(II) detection based on a DNAzyme-CdSe nanocomposite was developed. We firstly hybridized with capture probe (DNA1) and sequentially with DNA (DNA2) on the gold electrode. Then CdSe QDs were incorporated the specific recognition of DNA2 by covalent assembling. Upon addition of nickel ion into the above system, the substrate strand of the immobilized DNAzyme was catalytically cleaved by target Ni(2+), resulting in disassociation of the shorter DNA fragments containing CdSe QDs. The remaining CdSe QDs on the electrode surface detected by differential pulse anodic stripping voltammetry (DPASV). Under optimal conditions, the as-prepared sensor exhibited high sensitivity and fast response to Ni(2+) with the linear range from 20 nM to 0.2mM and a low detection limit of 6.67 nM. The prepared biosensor also shows good stability and good reproducibility and high selectivity toward target Ni(2+) against other metal ions because of highly specific Ni(2+)-dependent DNAzyme. Thus, our strategy has a good potential in the environment surveys.

Optimal target range for blood glucose in hyperglycaemic patients in a neurocritical care unit.

BACKGROUND: Hyperglycaemia is common among patients with critical neurological injury, even if they have no history of diabetes. The optimal target range for normalizing their blood glucose is unknown. METHODS: Retrospective data were extracted from 890 hyperglycaemic individuals (glucose > 200 mg/dL) admitted to neuroscience critical care unit (NCCU) and these patients were divided into two groups: intensive glucose control group with target glucose of < 140 mg/dL achieved and moderate control with glucose levels 140-180 mg/dL. The groups were also stratified according to the hyperglycaemia type (pre-existing diabetes or stress-related). We defined the primary endpoint as death from any cause during NCCU admission. RESULTS: In NCCU, tighter control of blood glucose at ≤ 140 mg/dL was associated with increased, mortality of individuals with pre-existing diabetes compared with moderate control [29 of 310 patients (9.4%) vs 15 of 304 patients (4.9%), p = 0.034]. Patient age [adjusted odds ratio (OR) = 1.12; 95% confidence interval (CI) = 1.05-1.19; p < 0.001], level of glycated haemoglobin (adjusted OR = 1.24; 95% CI = 1.04-1.48; p = 0.017) and hypoglycaemia (adjusted OR = 10.3; 95% CI = 2.92-36.6; p < 0.001) were positively associated with higher mortality. Death rate was lower among stress-related hyperglycaemic patients with tighter glucose controlled at ≤ 140 mg/dL [6 of 140 patients (4.3%) vs 15 of 136 patients (11.0%), p = 0.035]. CONCLUSION: A differential association is evident between glucose levels and mortality in diabetes and stress-related hyperglycaemia patients. However, given the observational nature of our work, no clinical recommendations can be given and prospective studies are required to further investigate these findings.

Fabrication of GO/PANi/CdSe nanocomposites for sensitive electrochemiluminescence biosensor.

A novel graphene oxide sheets/polyaniline/CdSe quantum dots (GO/PANi/CdSe) nanocomposites were successfully synthesized and used for the sensitive electrochemiluminescence (ECL) biosensing. The GO/PANi/CdSe nanocomposites were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Finally, the nanocomposites were employed to construct the biosensor via layer-by-layer assembly for the ECL detection of Cytochrome C (Cyt C). The whole process was characterized by cyclic voltammogram (CV) and electrochemical impedance spectroscopy (EIS). Experimental parameters such as the ratio of GO/PANi, the K(2)S(4)O(8) concentration and the pH value of electrolyte solution were studied to investigate the effect on the ECL intensity. Under the optimized conditions, the ECL intensity decreased linearly with the Cyt C concentrations in the range from 5.0×10(-8) to 1.0×10(-4) M with detection limit of 2.0×10(-8) M. Besides, the as-proposed biosensor exhibits high specificity, good reproducibility, and stability, and may be applied in more bioanalytical systems.

Direct electrochemistry and electrocatalytic behavior of hemoglobin entrapped in Ag@C nanocables/gold nanoparticles nanocomposites film.

Direct electrochemistry of hemoglobin (Hb) was successfully fabricated by immobilizing Hb on the nanocomposites containing of Ag@C nanocables and Au nanoparticles (AuNPs) modified glassy carbon electrode (GCE). The immobilized Hb retained its biological activity and shown high catalytic activities to the reduction of H2O2 by circular dicroism (CD) spectrum, fourier transform infrared (FT-IR) spectrum and cyclic voltammetry (CV). Experimental conditions such as scan rate and pH Value were studied and optimized. The results indicated that the resulting biosensor are linear to the concentrations of H2O2 in the ranges of 6.67 x 10(-7)-2.40 x 10(5) M, and the detection limit is 2.02 x 10(-7) M. The electrochemical biosensor has also high stability and good reproducibility.

A novel enzymatic hydrogen peroxide biosensor based on Ag/C nanocables.

A novel enzymatic hydrogen peroxide sensor was successfully fabricated based on the nanocomposites containing of Ag/C nanocables and gold nanoparticles (AuNPs). Ag/C nanocables have been synthesized by a hydrothermal method and then AuNPs were assembled on the surface of Ag/C nanocables. The nanocomposites were confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDS). The above nanocomposites have satisfactory chemical stability and excellent biocompatibility. Cyclic voltammetry (CV) was used to evaluate the electrochemical performance of the Ag/C/Au nanocomposites at glassy carbon electrode (GCE). The results indicated that the Ag/C/Au nanocomposites exhibited excellent electrocatalytic activity to the reduction of H(2)O(2). It offered a linear range of 6.7×10(-9) to 8.0×10(-6) M, with a detection limit of 2.2×10(-9) M. The apparent Michaelis-Menten constant of the biosensor was 51.7×10(-6) M. These results indicated that Ag/C/Au nanocomposites have potential for constructing of a variety of electrochemical biosensors.

Synthesis, crystal structure, electrochemistry and in situ FTIR spectroelectrochemistry of a bisferrocene pyrazole derivative.

One novel bisferrocene pyrazole derivative, bis [2-(5-trifluoromethyl-3-ferrocenyl) pyrazolyl] methane (abbreviated as (3)), was synthesized and fully characterized. A single crystal of (3) was obtained and solved by X-ray diffraction analysis. The bisferrocene derivative exhibits MLCT (metal to ligand charge transfer) and π→π* transitions in the UV-visible range, which have been verified by density functional theory (DFT) calculations. Its electrochemical properties were studied with the aid of cyclic voltammetry (CV), differential pulse voltammetry (DPV) and rapid scan time-resolved Fourier transform infrared spectroscopy (RS-TRS FT-IR) analysis. Furthermore, the electrochemical mechanism was elucidated based on the results from the cyclic voltabsorptometry (CVA) determination technique. (3) apparently shows a single wave in the cyclic voltammetric experiments which indicates there is no intermediate, however, the intermediate of (3) was observed by employing the RS-TRS FT-IR spectroelectrochemistry technique. The detailed investigation brought us safely to the conclusion that the methylene can also act as a linker, leading to electronic communication in either D-π-D and A-π-A systems.

Functionalized ferrocenes and ferroceniums: synthesis, crystal structures and electrochemical properties based on carbazole/phenothiazine-ferrocene conjugated molecules.

Four new D-pi-D (or D-pi-D-pi-D) complexes 9-ethyl-3-E-((1-ferrocenyl)vinyl)-carbazole (1), 9-ethyl-3,6-E,E-((1,1-diferrocenyl)vinyl)- carbazole(2), 10-ethyl-3-E-((1-ferrocenyl)vinyl)-phenothiazine (3), 10-ethyl- 3,7-E,E- ((1,1-diferrocenyl)vinyl)-phenothiazine (4), have been obtained by solid-phase Wittig reactions and fully characterized. The four complexes were treated with iodine leading to four corresponding [D-pi-A](+) I(3)(-) ferrocenium triiodides (+)I(3)(-) (5), (+)I(3)(-) (6), (+)I(3)(-) (7) and 4(+)I(3)(-) (8), respectively. The results of single crystal X-ray diffraction analysis show that and display better coplanarity between the Fc and carbazole subunits than that between the phenothiazine and ferrocene moieties, which leads to a better pi-electron delocalization. Both the poor pi-electron in [D-pi-A](+) ferroceniums and the heavy iodine atom have a negative effect on the electrochemical properties. The complexes 1-8 undergo multi-step redox processes and show lower oxidation potentials compared with those of ferrocene. Density functional theory (DFT) calculations are performed and the experimental redox properties of the complexes are studied. The eight complexes show MLCT and pi-pi transitions in the UV-visible range in solution, which have been verified by TD-DFT theoretical calculations. In all cases the highest-lying occupied molecular orbitals of the eight complexes are mainly localized on the Fe d orbitals and show a greater Fe proportion than that of alkyl in the complexes, whereas the LUMOs and LUMO+1 are mainly from the pi orbitals of the conjugated vinyl carbazole or phenothiazine unit.

IR spectroelectrochemical cyclic voltabsorptometry and derivative cyclic voltabsorptometry.

In this paper, we report the IR (infrared) CVA (cyclic voltabsorptometry) and DCVA (derivative cyclic voltabsorptometry) spectroelectrochemical techniques to elucidate an electrochemical mechanism. First we set potassium ferrocyanide as an example to explain the validity of this method. Then the electrochemical redox of two compounds, 1,4-benzoquinone and 1,4-bis(2-ferrocenylvinyl)benzene, was selected to be examined with this method. 1,4-Benzoquinone exhibits two single-electron waves in the cyclic voltammetric (CV) experiment, whereas two electroactive groups (Fc) are contained in p-(Fc-CH=CH)(2)BZ, but only one redox wave is observed. IR CVA results show that three IR absorption peaks in 1,4-benzoquinone, 1232 cm(-1) (the absorption of final production), 1656 cm(-1) (the absorption of original reactant), and 1510 cm(-1) (the absorption of intermediate), and two IR absorption peaks in 1,4-bis(2-ferrocenylvinyl)benzene, 1620 cm(-1) (the absorption of final oxide production) and 1589 cm(-1) (the absorption of intermediate), can be used to track the electron transfer. On the basis of the IR absorbance at the appropriate monitored wavelength (mentioned above), we can analyze simultaneously the concentration change of the corresponding redox transition during CV scans. Also the combination of the DCVA spectroelectrochemical technique with theory analysis allows reconstructing the current-potential (i-E) curve for each step of electron transfer. The reconstructed i-E curve can help us to understand the electron-transfer process. We believe IR CVA and DCVA spectroelectrochemical techniques can be applicable to the study of a wide range of complex electrochemistry processes.

Facile synthesis and systematic investigations of a series of novel bent-shaped two-photon absorption chromophores based on pyrimidine.

The synthesis, structure, and single- and two-photon spectroscopic properties of a series of pyrimidine-based (bent-shaped) molecules are reported. All these stable heterocyclic compounds are fully characterized, and exhibit intense single- and two-photon excited fluorescence (SPEF and TPEF) over a wide spectral range from blue to red, with the spectral peak position of the SPEF being basically the same as that of the TPEF. The well-conjugated pi-systems, observed from the crystal structure, indicate the charge transfer feature of the ground state. Meanwhile, the theoretical and experimental studies indicate that the charge transfer from donor to acceptor is greatly enhanced in the excited states and the different substituted donor groups on the pyrimidine have a large effect on the optical and electrochemical properties. Based on typical structure data and comprehensive spectral data, the following structure-property relationships can be determined: for such bent-shaped chromophores, the absorption and the fluorescence wavelength maximum of the SPEF and TPEF, and two-photon absorption cross sections show a similar trend with increasing electron-donating strength of the corresponding terminal group and the number of branches, while the average bond lengths of the pi-linkage and HOMO-LUMO energy levels show an inverse trend. Experimental data and theoretical calculation provide a coherent picture. With these findings, bent-shaped quadrupolar chromophores combining peak TPA cross sections (up to 2280 GM), broad TPA bands throughout the whole 700-900 nm range, and high fluorescence quantum yields could, thus, be obtained. Such compounds are of particular interest for TPEF microscopy, as well as optical data storage in the visible and NIR regions. A data recording experiment proved the potential application of these materials.

Rapid, large-scale synthesis and electrochemical behavior of faceted single-crystalline selenium nanotubes.

This article describes a rapid, solution-phase approach to the large-scale synthesis of faceted single-crystalline Se nanotubes, in the presence of cetyltrimethylammonium bromide. The products were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, laser Raman spectrography, differential scanning calorimetry analysis, and thermogravimetric analysis. The growth mechanism of the Se nanotubes was investigated by a series of experiments, and the rationality of the faceted morphology model for the Se nanotubes was demonstrated from the energetics and geometry. Furthermore, the electrochemical behavior of the Se nanotubes was studied by voltammetric techniques.

Melatonin-selenium nanoparticles inhibit oxidative stress and protect against hepatic injury induced by Bacillus Calmette-Guérin/lipopolysaccharide in mice.

Melatonin-selenium nanoparticles (MT-Se), a novel complex, were synthesized by preparing selenium nanoparticles in melatonin medium. The present investigation was designed to determine the protective effects of MT-Se against Bacillus Calmette-Guérin (BCG)/lipopolysaccharide (LPS)-induced hepatic injury in mice. In BCG/LPS-induced hepatic injury model, MT-Se administered (i.g.) at doses of 5, 10, or 20 mg/kg to BCG/LPS-treated mice for 10 days, significantly reduced the increase in plasma aminotransferase, reduced the severe extent of hepatic cell damage and the immigration of inflammatory cells. The MT-Se particles also attenuated the increase in the content of thiobarbituric acid-reactive substances and enhanced the decrease in reduced activities of superoxide dismutase and glutathione peroxidase (GPx). However, treatment with MT-Se suppressed the increase in nitric oxide levels both in plasma and liver tissue. Furthermore, supplementation with MT-Se at the dose of 10 mg/kg (composed of 9.9 mg/kg melatonin and 0.1 mg/kg selenium) had great capability to protect against hepatocellular damage than a similar dose of melatonin (10 mg/kg) or selenium (0.1 mg/kg) alone. This effect may relate to its higher antioxidant efficacy in decreasing lipid peroxidation and increasing GPx activity. These results suggest that the mode of MT-Se hepatic protective action is, at least in part, related to its antioxidant properties.

Melatonin-selenium nanoparticles protects liver against immunological injury induced by bacillus Calmette-Guerin and lipopolysaccharide.

AIM: Melatonin-selenium nanoparticle (MT-Se), a novel complex, was synthesized by preparing selenium nanoparticles in a melatonin medium. The present investigation was designed to determine the protective effects of MT-Se against immunological liver injury in mice induced by bacillus Calmette-Guerin (BCG)/lipopolysaccharide (LPS). METHODS: The model of immunological liver injury in mice was prepared. The levels of alanine aminotransferase, aspartate amino-transferase, nitric oxide (NO) in serum, malondialdehyde content, superoxide dismutase (SOD), and glutathione peroxidase (GSH-px) activities in a liver homogenate were assayed by spectrophotometry. The content of tumor necrosis factor-alpha (TNF-alpha) and interleukin-1 (IL-1) were determined by ELISA. The splenocyte proliferation was assayed by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) dye reduction. Meanwhile, a hepatic pathological examination was observed. RESULTS: In the BCG/LPS-induced hepatic injury model, MT-Se administered at doses of 5, 10, or 20 mg/kg to the BCG/LPS-treated mice for 10 d significantly reduced the increase in serum aminotransferase, reduced the severe extent of hepatic cell damage and the immigration of inflammatory cells. It also attenuated the increase in the content of thiobarbituric acid-reactive substances and enhanced the decrease in activities of SOD and GSH-px. In contrast, the treatment with MT-Se suppressed the increase in NO level in both the serum and liver tissue. Furthermore, MT-Se significantly lowered an increase in TNF-alpha and IL-1beta levels in the liver and inhibited the production of TNF- alpha and IL-1beta by peritoneal macrophages. A downregulation effect of MT-Se on splenocyte proliferation was also observed. CONCLUSION: MT-Se showed a hepatic protective action on immunological liver injury in mice.

Application of light-absorption ratio variation approach as an optimum spectrophotometry to determination of Mn(II) in ng ml(-1) level using a competitive replacement complexation.

The light-absorption ratio variation approach (LARVA) which produces an outstandingly increasing of analytical sensitivity was applied to the quantitative detection of ultramicro amounts of Mn(II) by light-absorption spectrometry using the competitive replacement complexation among 1,5-di(2-hydroxy-5-sulfophenyl)-3-cyanoformazan (DSPCF), Zn(II) and Mn(II) in the presence of o-phenanthroline (OPTL). Not only masks OPTL foreign metal ions but also seriously sensitize the competitive complexation. All the binary and ternary complexes were characterized by the break point approach. Results have shown that the limit of detection (3delta) of Mn(II) is only 0.7 ng ml(-1). This method has been applied to analysis of water quality with satisfactory results.