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Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C--H functionalization of arylphosphine oxides. Involving C--H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework. [ABSTRACT FROM AUTHOR]

A new ionic current rectification device responsive to a broad range of pH stimuli has been fabricated using porous anodic alumina membrane with tailor-made branching nanochannel array. The asymmetric geometry Is achieved by changing oxidation voltage using a simple two-step anodization process. Due to the protonation/deprotonation of the intrinsic hydroxyl groups upon solution pH variation, the nanochannels array-based device is able to regulate ionic current rectification properties. The ion rectification ratio of the device is mainly determined by the branching size and surface charges, which is also confirmed by theoretical simulations. In addition, theoretical simulations show that the slight difference in ion rectification ratio for the nanochannel devices with different branching numbers is due to the propagation of concentration polarization. Three dimensional simulations clearly show the nonuniform concentration profiles in stem nanochannel near the junction interface due to the presence of branching nanochannels. The present ionic device is promising for biosensing, molecular transport and separation, and drug delivery in confined environments. [ABSTRACT FROM AUTHOR]

An unprecedented attempt was conducted on suitably functionahzed integration of three-dimensional hyperbranched titania architectures for efficient multistack photoanode, constructed via layer-bylayer assembly of hyperbranched hierarchical tree-like titania nanowires (underlayer), branched hierarchical rambutan-like titania hollow submicrometer- sized spheres (intermediate layer), and hyperbranched hierarchical urchin-like titania micrometer-sized spheres (top layer). Owing to favorable charge-collection, superior light harvesting efficiency and extended electron lifetime, the multilayered TiO2-based devices showed greater Jsc and Voc than those of a conventional TiO2 nanoparticle (TNP), and an overall power conversion efficiency of 11.01% (Jsc = 18.53 mA cm-2; Voc = 827 mV and FF = 0.72) was attained, which remarkably outperformed that of a TNP-based reference cell (n = 7.62%) with a sirriilar film thickness. Meanwhile, the facile and operable film-fabricating technique (hydrothermal and drop-casting) provides a promising scheme and great simplicity for high performance/cost ratio photovoltaic device processability in a sustainable way. [ABSTRACT FROM AUTHOR]

In biological metabolism, a given metabolic process usually occurs via a group of enzymes working together in sequential pathways. To explore the metabolism mechanism requires the understanding of the multienzyme coupled catalysis systems. In this paper, an approach has been proposed to study the kinetics of a two-enzyme coupled reaction using SECM combining numerical simulations. Acetylcholine esterase and choline oxidase are immobilized on cysteamine self-assembled monolayers on tip and substrate gold electrodes of SECM via electrostatic interactions, respectively. The reaction kinetics of this two-enzyme coupled system upon various separation distance precisely regulated by SECM are measured. An overall apparent Michaelis–Menten constant of this enzyme cascade is thus measured as 2.97 mM at an optimal tip–substrate gap distance of 18 μm. Then, a kinetic model of this enzyme cascade is established for evaluating the kinetic parameters of individual enzyme by using the finite element method. The simulated results demonstrate the choline oxidase catalytic reaction is the rate determining step of this enzyme cascade. The Michaelis–Menten constant of acetylcholine esterase is evaluated as 1.8 mM. This study offers a promising approach to exploring mechanism of other two-enzyme coupled reactions in biological system and would promote the development of biosensors and enzyme-based logic systems. [ABSTRACT FROM AUTHOR]

Continuous plasma separation will be greatly helpful for dynamic metabolite monitoring in kinetics research and drug development. In this work, we proposed a continuous on-chip plasma separation method based on the natural aggregating and sedimentation behavior of red blood cells at low shear rate. In this approach, a glass capillary was first used to realize quick and obvious delamination of blood cells from plasma. A novel "dual-elbow" connector was designed to change the direction of delamination. The blood was finally separated by laminar flow and bifurcation on the microchip. Results demonstrated that the present device can efficiently and stably separate plasma from blood in a continuous means, e.g., in a 4 h separation we did not observe clogging or a trend of clogging. In addition, the present approach can avoid the damage to cells which usually occurs in separation with high shear rate in a microchannel and possible contaminants to plasma. The proposed microchip device is robust, simple, and inexpensive for long time plasma separation with high plasma recovery and less sample consumption. The present work provides an effective tool for metabolite monitoring in pharmacokinetics research and drug development. [ABSTRACT FROM AUTHOR]

Indium borate has been prepared by a sol-gel method. The structure, morphology, and photophysics of the resultant photocatalysts have been studied via the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and diffuse reflectance UV-visible light spectroscopy. These photocatalysts have been used to photodegrade 4-chlorophenol. The photocatalytic activity depends on the annealing temperature during preparation. It is found that borates can exhibit a high photodegradation activity under UV-light irradiation, for which the efficiency can be higher than that of as-prepared TiO2. This is explained according to the results of fluorescence spectra and valence band X-ray photoelectron spectroscopy (XPS). It is confirmed by the results of time-resolved photoluminescence decay spectra; i.e., the lifetime of electrons and holes involved in the radiative process can be longer for the borates than that for TiO2. This implies that indium borate can be a promising photocatalyst for future applications in treatment of environment contaminants. [ABSTRACT FROM AUTHOR]

The structures and energies of Asn (n = 2-8) neutrals, anions, and cations have been systematically investigated by means of the G3 schemes. The electron affinities, ionization potentials, binding energies, and several dissociation energies have been calculated and compared with limited experimental values. The results revealed that the potential surfaces of neutral Asn clusters are very shallow, and two types of structural patterns compete with each other for the ground-state structure of Asn with n ≥ 6. One type is derived from the benzvalene form of As6, and another is derived from the trigonal prism of As6. The previous photoelectron spectrum (taken from J. Chem. Phys. 1998, 109, 10727) for As3 has been reassigned in light of the G3 results. The experimental electron affinities of As3 were measured to be 1.81 eV, not 1.45 eV. We inferred from the conclusion of G3 and density functional theory that the experimental electron affinities of 1.7 and 3.51 eV for As5 are unreliable. The reliable electron affinities were predicted to be 0.83 eV for As2, 1.80 eV for As3, 0.54 eV for As4, 3.01 eV for As5, 2.08 eV for As6, 2.93 eV for As7, and 2.02 eV for As8. The G3 ionization potentials were calculated to be 9.87 eV for As2, 7.33 eV for As3, 8.65 eV for As4, 6.68 eV for As5, 7.97 eV for As6, 6.58 eV for As7, and 7.65 eV for As8. The binding energies per atom were evaluated to be 1.99 eV for As2, 2.01 eV for As3, 2.61 eV for As4, 2.39 eV for As5, 2.51 eV for As6, 2.55 eV for As7, and 2.67 eV for As8. These theoretical values of As2, As3, and As4 are in excellent agreement with those of experimental results. Several dissociation energies were carried out to examine relative stabilities. This characterized the even-numbered clusters as more stable than the odd-numbered species. [ABSTRACT FROM AUTHOR]

Wheat HMGa protein is a typical member of the plant HMGA family. It has four AT hooks and a histone H1-like region. A panel of deletion mutants of HMGa was generated to study the role of different regions of HMGa in its binding to 4H (a synthetic DNA that mimics the in duo structure of intermediates of homologous recombination and DNA repair) and linear DNAs. Although the histone HI-like region of HMGa does not bind to 4H or linear DNAs, it does enhance the binding. Mutants with any two adjacent AT hooks show specific binding to both 4H and linear P268 (and P31) with different binding affinities, which is partly due to the flanking regions between AT hooks. Conformational studies indicate that the α-helical content of HMGa increases significantly when it binds to 4H compared to that after binding to P31, linear DNA. In contrast, linear DNA, but not 4H, undergoes substantial conformational change when it binds to HMGa, indicating that linear DNA is relatively more flexible than 4H. A more significant difference in the affinities of binding of the mutants of HMGa to 4H was observed compared to their affinities of binding to linear DNA, P31. These differences could be due to the rigidity of the DNA and the characters of the AT hook regions in the mutants. [ABSTRACT FROM AUTHOR]

Describes the biochemistry and physiology of bacteria. Characterization of organisms; Effectiveness of resonance raman spectroscopy with ultraviolet excitation; Use of continuous-wave lasers and charge-coupled device detectors.

Reports on the synthesis and characterization of faceted hexagonal aluminum nitride nanotubes. Nitride application in aluminum powder impregnated within cobalt sulfate; Contrasting features of the nanotubes; Implications for the construction of nanoheterostructures in nanoelectronics.

A novel cascade Cp*Rh(III)-catalyzed C-H alkylation/Cu(II)-promoted α-oxygenation which enabled a three-component carboxygenation of activated alkene is reported. Mild reaction conditions, broad substrate scope, and good functional group tolerance were observed. The synthetic utility of the protocol was showcased by the facile transformations of the product to a variety of structurally diverse molecules. Preliminary mechanistic studies were conducted. [ABSTRACT FROM AUTHOR]

The sensitive identification of single nucleotide polymorphisms becomes increasingly important for disease diagnosis, prevention, and practical applicability of pharmacogenomics. Herein, we propose a simple, highly selective, label-free single nucleotide polymorphisms (SNPs) sensing device by electrochemically monitoring the diffusion flux of ferricyanide probe across probe DNA/morpholino duplex functionalized nanochannels of porous anodic alumina. When perfectly matched or mismatched target DNA flows through the nanochannels modified with probe DNA/morpholino duplex, it competes for the probe DNA from morpholino, resulting in a change of the surface charges. Thus, the diffusion flux of negatively charged electroactive probe ferricyanide is modulated since it is sensitive to the surface charge due to the electrostatic interactions in electric double layer-merged nanochannels. Monitoring of the change in diffusion flux of probe enables us to detect not only a single base or two base mismatched sequence but also the specific location of the mismatched base. As is demonstrated, SNPs in the PML/RARα fusion gene, known as a biomarker of acute promyelocytic leukemia (APL), have been successfully detected. [ABSTRACT FROM AUTHOR]

Previously, our group has utilized the luminol electrochemiluminescence to analyze the active cholesterol at the plasma membrane in single cells by the exposure of one cell to a photomultiplier tube (PMT) through a pinhole. In this paper, fast analysis of active cholesterol at the plasma membrane in single cells was achieved by a multimicroelectrode array without the pinhole. Single cells were directly located on the microelectrodes using cell-sized microwell traps. A cycle of voltage was applied on the microelectrodes sequentially to induce a peak of luminescence from each microelectrode for the serial measurement of active membrane cholesterol. A minimal time of 1.60 s was determined for the analysis of one cell. The simulation and the experimental data exhibited a semisteady-state distribution of hydrogen peroxide on the microelectrode after the reaction of cholesterol oxidase with the membrane cholesterol, which supported the relative accuracy of the serial analysis. An eight-microelectrode array was demonstrated to analyze eight single cells in 22 s serially, including the channel switching time. The results from 64 single cells either activated by low ion strength buffer or the inhibition of intracellular acyl-coA/cholesterol acyltransferase (ACAT) revealed that most of the cells analyzed had the similar active membrane cholesterol, while few cells had more active cholesterol resulting in the cellular heterogeneity. The fast single-cell analysis platform developed will be potentially useful for the analysis of more molecules in single cells using proper oxidases. [ABSTRACT FROM AUTHOR]

A novel indium (III)-catalyzed cydotrimerization of alkynes in the presence of 2-iodophenol gave 1,3,5-substituted benzenes in excellent yields with complete regioselectivity. The reaction condition is tolerant to air, and atom economical, in accordance with the concept of modem green chemistry. This method provides a rapid and efficient access to 1,3,5-substituted benzenes. [ABSTRACT FROM AUTHOR]

The vapor-liquid-solid (VLS) growth model has been widely used to direct the growth of one- dimensional (1D) nanomaterials, but the origin of the proposed process has not been experimentally confirmed. Here we report the experimental evidence of the origin of VLS growth. Al69Ni31 alloyed particles are used as "catalysts" for growing AIN nanowires by nitridation reaction in N2-NH3 at different temperatures. The nanowire growth occurs following the emergence of the catalyst droplets as revealed by in situ X-ray diffraction and thermal analysis. The physicochemical process involved has been elucidated by quantitative analysis on the evolution of the lattice parameters and relative contents of the nitridation products. These direct experimental results reveal that VLS growth of AIN nanowires is dominated by the phase equilibrium of the Al-Ni alloy catalyst. The in-depth insight into the VLS mechanism indicates the general validity of this growth model and may facilitate the rational design and controllable growth of 1 D nanomaterials according to the corresponding phase diagrams. [ABSTRACT FROM AUTHOR]

Various types of hydrogen bonds, their temperature dependence and water−polymer interaction in hydrated poly(acrylic acid) (PAA) were systematically investigated using 1H CRAMPS solid-state NMR techniques in the temperature range from 25 to 110 °C. The 1H CRAMPS NMR methods are based on a recently developed continuous phase modulation technique for 1H−1H homonuclear dipolar decoupling. The 1H CRAMPS experiments revealed four types of protons in hydrated PAA which are assigned to protons from the mutually hydrogen-bonded COOH groups (1), from the free COOH groups (2), from the COOH groups bounded with water or from water bounded with COOH groups which are undergoing fast chemical exchange mutually (3), and from main chain groups (4), respectively. Furthermore, we proposed double-quantum filtered and dipolar filtered 1H CRAMPS experiments to further assign the protons according to their dipolar coupling strength. In addition, high-resolution spin echo 1H CRAMPS experiments were further employed to accurately determine the chemical shift of these protons. These NMR techniques were also used to elucidate the molecular mobility of the different groups. It was found that dehydration in PAA promotes the formation of hydrogen bonds between COOH groups. Variable-temperature 1H CRAMPS experiments demonstrated that the dissociation of the hydrogen bonds between COOH groups occurs dramatically at lower temperature in hydrated PAA and slowly over a wide range of temperature in dehydrated PAA. It was also found that the dehydration of water bounded with COOH groups in hydrated PAA occurs significantly at high temperature. The NMR results were compared with previous work using DSC and other techniques. Besides undergoing fast chemical exchange, the adsorbed water was also demonstrated in proximity with the free COOH groups and far from the hydrogen bonds between COOH groups by using two-dimensional 1H−1H spin-exchange NMR experiments. [ABSTRACT FROM AUTHOR]

Aluminum nitride nanostructures are attractive for many promising applications in semiconductor nanotechnology. Herein we report on vapor-solid growth of quasi-aligned aluminum nitride nanocones on catalyst-coated wafers via the reactions between AICI3 vapor and NH3 gas under moderate temperatures around 700 °C and the growth mechanism is briefly discussed. The as-prepared wurtzite aluminum nitride nanocones grow preferentially along the c-axis with adjustable dimensions of the sharp tips in the range of 20-60 nm. The photoluminescence spectrum reveals a broad blue emission band with a fine photon structure while the field emission study shows a notable emission current with a moderate turn-on field as expected, suggesting their potential applications in light and electron emission nanodevices. [ABSTRACT FROM AUTHOR]

Fabricating materials with excellent mechanical performance from the natural renewable and degradable biopolymers has drawn significant attention in recent decades due to the environmental concerns and energy crisis. As two of the most promising substitutes of synthetic polymers, silk fibroin (SF), and cellulose, have been widely used in the field of textile, biomedicine, biotechnology, etc. Particularly, the cellulose/SF blend film exhibits better strength and toughness than that of regenerated cellulose film. Herein, this study is aimed to understand the molecular origin of the enhanced mechanical properties for the cellulose/SF blend film, using solid-state NMR as a main tool to investigate the conformational changes, intermolecular interactions between cellulose and SF and the water organization. It is found that the content of the β-sheet structure is increased in the cellulose/SF blend film with respect to the regenerated SF film, accompanied by the reduction of the content of random coil structures. In addition, the strong hydrogen bonding interaction between the SF and cellulose is clearly elucidated by the two-dimensional (2D) 1H-13C heteronuclear correlation (HETCOR) NMR experiments, demonstrating that the SF and cellulose are miscible at the molecular level. Moreover, it is also found that the -NH groups of SF prefer to form hydrogen bonds with the hydroxyl groups bonded to carbons C2 and C3 of cellulose, while the hydroxyl groups bonded to carbon C6 and the ether oxygen are less favorable for hydrogen bonding interactions with the -NH groups of SF. Interestingly, bound water is found to be present in the air-dried cellulose/SF blend film, which is predominantly associated with the cellulose backbones as determined by 2D 1H-13C wide-line-separation (WISE) experiments with spin diffusion. This clearly reveals the presence of nanoheterogeneity in the cellulose/SF blend film, although cellulose and SF are miscible at a molecular level. Without doubt, these in-depth atomic-level structural information could help reveal the molecular origin of the enhanced mechanical properties of the blend film, and thus to establish the structure-property relationship, which could further provide guidance for the fabrication of high performance biopolymer-based materials. [ABSTRACT FROM AUTHOR]

We demonstrate a heterostructure Ni9S8/MoS2 hybrid with tight interface synthesized via an improved hydrothermal method. As compared to pure MoS2, the increased surface area and the shorten charge transport pathway in the layered hybrid significantly promote the photocatalytic efficiency for hydrogen evolution reaction (HER). In particularly, the optimized Ni9S8/MoS2 hybrid with 20 wt % Ni9S8 exhibits the highest photocatalytic activity with HER value of 406 μmolg-1h-1, which is enhanced by 70% compared to that of pure MoS2 nanosheets (285.0 μmolg-1h-1). Moreover, the value is 4 times more than the commercial MoS2 (92.0 μmolg-1h-1), indicating the high potential of the hybrid in the catalytic fields. [ABSTRACT FROM AUTHOR]

Cp*Co(III)-catalyzed annulationsof 2-alkenylphenols with CO forthe synthesis of coumarin derivatives have been developed. The reactionfeatures mild reaction conditions, broad substrate scope, and goodfunctional group tolerance. Preliminary mechanistic studies were conducted,suggesting that C–H activation is the turnover limiting step.Furthermore, the efficiency of this reaction was demonstrated by therapid total synthesis of three natural products herniarin, xanthyletin,and seselin. [ABSTRACT FROM AUTHOR]

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction. [ABSTRACT FROM AUTHOR]

Two kinds of boron and nitrogen co-doped carbon nanotubes (CNTs) dominated by bonded or separated B and N are intentionally prepared, which present distinct oxygen reduction reaction (ORR) performances. The experimental and theoretical results indicate that the bonded case cannot, while the separated one can, turn the inert CNTs into ORR electrocatalysts. This progress demonstrates the crucial role of the doping microstructure on ORR performance, which is of significance in exploring the advanced C-based metal-free electrocatalysts. [ABSTRACT FROM AUTHOR]

By using the in situ thermal analysis-mass spectroscopic technique, combined with transmission electron microscopic characterization of the carbon nanotube (CNT) product, we have studied the chemical vapor deposition (CVD) growth of CNTs with Fe-Co/y-A1[Sub2]O[Sub3] catalyst and benzene precursor in the range of room temperature to 700 °C. The growth process has been clearly illuminated, which starts from the reduction of catalyst around 645 °C followed by the dissociation of carbon-hydrogen bonds of benzene and the sequential growth of CNTs. A surprising fact is that no possible hydrocarbon species derived from benzene was detected, indicating that the carbon-carbon bond was not broken under our experimental conditions. All of the experimental results strongly reinforce the six-membered-ring-based growth model, and a schematic elucidation is presented accordingly. This in situ study not only reveals the unique and convincing information directly related to the growth mechanism from the involved chemistry, but also provides a powerful way to clarify the mechanism of CVD synthesis of CNTs with other precursors. [ABSTRACT FROM AUTHOR]

The Fe- and Mn-containing superoxide dismutases catalize the same reaction and have almost superimposable active sites. Therefore, the details of their mechanisms have been assumed to be similar. However, we now show that the pH dependence of Escherichia coli MnSOD activity reflects a different active site proton equilibrium in (oxidized) Mn[sup 3+]SOD than the event that affects the active site pK of oxidized FeSOD. We find that the universally conserved Tyr34 that has a pK above 11.5 in Fe[sup 3+]SOD is responsible for the pK near 9.5 of Mn[sup 3+]SOD and, thus, that the oxidized state pK of Mn[sup 3+]SOD corresponds to an outer-sphere event whereas that of Fe[sup 3+]SOD corresponds to an inner sphere event [Bull, C.; Fee, J. A. J. Am. Chem. Soc. 1985, 107, 3295-3304]. We also present the first description of a reduced-state pK for MnSOD. Mn[sup 2+]SOD's pK involves deprotonation of Tyr34, as does Fe[sup 2+]SOD's pK [Sorkin, D. L.; Miller A.-F. Biochemistry 1997, 36, 4916-4924]. However, the values of the pKs, 10.5 and 8.5 respectively, are quite different and Mn[sup 2+]SOD's pK affects the coordination geometry of Mn[sup 2+], most likely via polarization of the conserved Gln146 that hydrogen bonds to axially coordinated H[sub 2]O. Our findings are consistent with the different electronic configurations of Mn[sup 2+/3+] vs Fe[sup 2+/3+], such as the stronger hydrogen bonding between Gln146 and coordinated solvent in MnSOD than that between the analogous Gln69 and coordinated solvent in FeSOD, and the existence of weakly localized H[sub 2]O near the sixth coordination site of Mn[sup 2+] in Mn[sup 2+]SOD [Borgstahl et al. J. Mol. Biol. 2000, 296, 951-959]. [ABSTRACT FROM AUTHOR]

The article cites a research study which reveals that the unusual properties and wide potential applications of carbon nanotubes, resulting from their unique tubular nanostructures, have been stimulating extensive explorations of nanotubes of various materials for over a decade. The researchers found that the acute interstitial nephritis nanotubes are different from the nanotubes of layered materials and show the faceted geometry with hexagonal cross sections. Actually, similar features also exist in the few recently reported nanotubes of other nonlayered materials using template-free approaches.