The possibility of using C20 fullerene and graphene as semiconductor segments for detection,and destruction of cyanogen-chloride chemical agent

Detection of hazardous chemical species by changing the electrical conductivity of a semiconductor matter is a proposed and applied way for decreasing their subsequent unpleasant effects. Recently, many examples of using inorganic or organic materials, polymeric, and also nano-sized species as sensors were reported in which, in some cases, those matters were strongly affective and suitable.In this project, we have made an assessment on whether the graphene segment or C₂₀ fullerene, able to sense the existence of cyanogen chloride NCCl? In order to gain trustable results, the possible reaction pathways along with the adsorption kinetics were investigated. Moreover, the electronic density of states DOS showed that C₂₀ fullerene senses the existence of cyanogen chloride agent with a clearer signal (ΔE_g = 0.0110 eV) compared to the graphene segment (ΔE_g = 0.0001 eV). Also the adsorption energy calculations showed that cyanogen chloride could be adsorbed by the fullerene in a multi-step process (E_ads1 = −0.852 kcal mol⁻¹; E_ads2 = −0.446 kcal mol⁻¹; E_ads3 = −2.330 kcal mol⁻¹).     

Reaction mechanism and free energy profile for acylation of Candida Antarctica lipase B with methylcaprylate and acetylcholine: Density functional theory calculations

Candida Antarctica lipase B (CALB), a specific enzyme to catalyze the hydrolysis of esters, can be a good candidate for acetylcholine (ACh) hydrolysis instead of acetylcholinesterase. The catalytic mechanism of the CALB acylation, as the first stage in the hydrolysis reaction, with ACh and methylcaprylate (MEC) has been examined by using density functional theory technique. The significant emphasis of this article is on the free energy barriers for the acylation step of hydrolysis reactions. Computed free energy barriers of the first step are 9.2 and 15.9 kcal mol⁻¹, but for the second step are 7.9 and 11.6 kcal mol⁻¹ for MEC and ACh respectively. Activation free energies are in the comparable and acceptable range and imply both of two reactions are theoretically possible. The stability role of the adjacent amino acids was examined by using two applied tools. It is exposed that the oxyanion hole residues decrease energy barriers by stabilizing the transition state structures.     

Perchlorate-selective polymeric membrane electrode based on a cobaloxime as a suitable carrier

A cobaloxime ([chlorobis(dimethylglyoximeato)(triphenylphosphine)] cobalt (III), [Co(dmgH)₂pph₃Cl]) incorporated in a plasticized poly(vinyl chloride) membrane was used to develop a perchlorate-selective electrode. The influence of membrane composition on the electrode response was studied. The electrode exhibits a Nernstian response over the perchlorate concentration range 1.0 × 10⁻⁶ to 1 × 10⁻¹ mol l⁻¹ with a slope of −56.8 ± 0.7 mV per decade of concentration, a detection limit of 8.3 × 10⁻⁷, a wide working pH range (3–10) and a fast response time (<15 s). The electrode shows excellent selectivity towards perchlorate with respect to many common anions. The electrode was used to determine perchlorate in water and human urine.     

Simultaneous determination of epinephrine and ascorbic acid at the electrochemical sensor of triazole SAM modified gold electrode

The electrochemical sensor of triazole (TA) self-assembled monolayer (SAM) modified gold electrode (TA SAM/Au) was fabricated. The electrochemical behaviors of epinephrine (EP) at TA SAM/Au have been studied. The TA SAM/Au shows an excellent electrocatalytic activity for the oxidation of EP and accelerates electron transfer rate. The diffusion coefficient is 1.135 × 10⁻⁶ cm² s⁻¹. Under the optimum experiment conditions (i.e. 0.1 mol L⁻¹, pH 4.4, sodium borate buffer, accumulation time: 180 s, accumulation potential: 0.6 V, scan rate: 0.1 Vs⁻¹), the cathodic peak current of EP versus its concentration has a good linear relation in the ranges of 1.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol L⁻¹ and 1.0 × 10⁻⁵ to 6.0 × 10⁻⁴ mol L⁻¹ by square wave adsorptive stripping voltammetry (SWASV), with the correlation coefficient of 0.9985 and 0.9996, respectively. Detection limit is down to 1.0 × 10⁻⁸ mol L⁻¹. The TA SAM/Au can be used for the determination of EP in practical injection. Meantime, the oxidative peak potentials of EP and ascorbic acid (AA) are well separated about 200 ± 10 mV at TA SAM/Au, the oxidation peak current increases approximately linearly with increasing concentration of both EP and AA in the concentration range of 2.0 × 10⁻⁵ to 1.6 × 10⁻⁴ mol L⁻¹. It can be used for simultaneous determination of EP and AA.     

A DFT study on the central-ring doped HBC nanographenes

Nanographenes (NGs) are a segment of graphene whose dangling bonds are saturated with hydrogen atoms, introducing different properties and promising applications. Here we investigate the electronic, thermodynamic, optical, and structural properties of four C₃₆X₃Y₃H₁₈ NGs (X = B, and Al; and Y = N, and P) based on the density functional theory calculations. It was mainly found that 1) BN-NG is planar molecule and the others are buckybowl-shaped ones, 2) The bowl-to-bowl inversion Gibbs free energies (ΔG^#) of buckybowl shaped NGs are very huge and the rate constant is very small, hindering the inversion, 3) The relative energetic stability order based on the standard enthalpy of formation (ΔH_f^°) is as BN > AlN > BP > AlP, which the BN, and AlN doped NGs are stable at room temperature but the BP and AlP doped ones are instable, 4) The electrical conductivity order of magnitude is inverse of that of stability, 5) An exciton binding energy is predicted in the range of 0.57–0.75 eV for the NGs which corresponds to Frenkel exciton type, 6) the NGs are not soluble in organic solvent in agreement with the experimental results and is partially soluble in water solvent with Gibbs free energy of solvation (ΔG_solv) in the range of −6.1 to −10.1 kcal/mol.     

Flow-injection determination of iron(III) in soil by biamperometry using two independent redox couples

A flow-injection biamperometric method for the determination of iron(III) has been described. The detector consists of two chambers separated by a salt bridge, and one platinum wire working electrode is embedded in each chamber, respectively. When iron(III) solution and hydrogen peroxide solution simultaneously flow through two chambers, the reduction of iron(III) at one platinum electrode is associated with the oxidation of hydrogen peroxide at the other platinum electrode, forming such a system as similar to a reversible couple one. The biamperometric system can perform the determination of iron(III) without any external potential difference. The linear relationship is obtained from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol l⁻¹ with a detection limit of 6.0 × 10⁻⁷ mol l⁻¹. The proposed method exhibits the satisfactory reproducibility with a relative standard derivation (R.S.D.) of 1.4% for 17 successive determinations of 2.0 × 10⁻⁵ mol l⁻¹ iron(III) and is applied to the determination of iron(III) in soil.     

Cationic P⋯N interaction in XH3P+⋯NCY complexes (X = H,F, CN,NH2, OH; Y = H,Li, F,Cl) and its cooperativity with hydrogen/lithium/halogen bond

The geometries, interaction energies and bonding properties of cationic pnicogen bond (CPB) interactions are studied in binary XH₃P⁺⋯NCY (X = H, F, CN, NH₂, OH; Y = H, Li, F, Cl) complexes by means of MP2/aug-cc-pVTZ calculations. Interaction energies of these binary complexes span a large range, from −16.36 kcal/mol in (NH₂)H₃P⁺⋯NCF to −71.36 kcal/mol in FH₃P⁺⋯NCLi complex. The spin–spin coupling constant across P⋯N interaction depends considerably on the nature of X and Y substituents. The characteristic of CPB interactions is analyzed in terms of parameters derived from quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. The charge transfer from the nitrogen base to the cationic acid stabilizes these pnicogen–bonded complexes. For a given XH₃P⁺, the net charge transfer value increases as the interaction energy of the complex becomes more negative, i.e., NCLi > NCCl > NCH > NCF. Moreover, mutual influence between the CPB and hydrogen/halogen/lithium bond is studied in the ternary XH₃P⁺⋯NCY⋯NCH complexes. The results indicate that the formation of a Y⋯N interaction tends to strengthen CPB in the ternary systems.     

Using thermodynamic integration MD simulation to compute relative protein–ligand binding free energy of a GSK3β kinase inhibitor and its analogs

Thermodynamic integration molecular dynamics simulation was used to investigate how TI-MD simulation preforms in reproducing relative protein–ligand binding free energy of a pair of analogous GSK3β kinase inhibitors of available experimental data (see Fig. 1), and to predict the affinity for other analogs. The computation for the pair gave a ΔΔG of 1.0 kcal/mol, which was in reasonably good agreement with the experimental value of −0.1 kcal/mol. The error bar was estimated at 0.5 kcal/mol. Subsequently, we employed the same protocol to proceed with simulations to find analogous inhibitors with a stronger affinity. Four analogs with a substitution at one site inside the binding pocket were the first to be tried, but no significant enhancement in affinity was found. Subsequent simulations for another 7 analogs was focused on substitutions at the benzene ring of another site, which gave two analogs (analogs 9 and 10) with ΔΔG values of −0.6 and −0.8 kcal/mol, respectively. Both analogs had a OH group at the meta position and another OH group at the ortho position at the other side of the benzene ring, as shown in Table 3. To explore further, another 4 analogs with this characteristic were investigated. Three analogs with ΔΔG values of −2.2, −1.7 and −1.2 kcal/mol, respectively, were found. Hydrogen bond analysis suggested that the additional hydrogen bonds of the added OH groups with Gln185 and/or Asn64, which did not appear in the reference inhibitor or as an analog with one substitution only in the examined cases, were the main contributors to an enhanced affinity. A prediction for better inhibitors should interest experimentalists of enzyme and/or cell assays. Analysis of the interactions between GSK3β kinase and the investigated analogs will be useful in the design of GSK3β kinase inhibitors for compounds of this class.     

Effect of temperature on humido-sensitive conducting polymer actuators

Temperature dependence of water vapor sorption and electro-active polymer actuating behavior of free-standing films made of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) was investigated by means of sorption isotherm and electromechanical analyses. The non-porous PEDOT/PSS film, having a specific surface area of 0.13 m² g^?1, sorbed water vapor of 1080 cm³(STP) g^?1, corresponding to 87 wt%, at relative water vapor pressure of 0.95. A temperature rise from 25 °C to 40 °C lowered sorption degree, indicative of an exothermic process, where isosteric heat of sorption decreased with increasing water vapor sorption and the value reached 43.9 kJ mol^?1, being consistent with the heat of water condensation (44 kJ mol^?1). Upon application of 10 V, the film underwent contraction of 2.46% at 5 °C caused by desorption of water vapor due to Joule heating, which slightly decreased to 2.10% at 45 °C. The speed of contraction was one order of magnitude faster than that of expansion and less dependent on the temperature since water vapor sorbed in the film were forced to desorb by Joule heating. In contrast, the higher the temperature the faster the film expansion because diffusion coefficient increased as the temperature became higher.     

Calorimetric measurement of the standard enthalpy of formation of ZnSb at 298 K

After a critical review of the literature data on the standard enthalpy of formation of ZnSb, discrepancies between various experimental studies are highlighted. Moreover, experimental values disagree with values calculated by ab initio methods. As many of the experimental methods used suffer from some serious drawbacks, a new determination of the standard enthalpy of formation of ZnSb by an alternative calorimetric method, drop solution calorimetry in liquid tin, has been performed. Two different synthesis methods have been used to obtain a pure ZnSb phase and drop solution experiments were performed at 665 and at 974 K. The standard enthalpy of formation values derived from these experiments are − 6.1±2.5 kJ mol of atoms⁻¹ for the ZnSb sample prepared by ball milling and − 7.9±0.4 kJ mol of atoms⁻¹ for the ZnSb sample prepared by melting. These results are discussed and compared to literature data.     

Dielectric and piezoelectric properties of [0 0 1] and [0 1 1]-poled relaxor ferroelectric PZN–PT and PMN–PT single crystals

The properties of PZN–PT and PMN–PT single crystals of varying compositions and orientations have been investigated. Among the various compositions studied, [0 0 1]-optimally poled PZN-(6–7)%PT and PMN-30%PT exhibit superior dielectric and piezoelectric properties, with K^T ≈ 6800–8000, d₃₃ ≈ 2800 pC/N, d₃₁ ≈ −(1200–1800) pC/N for PZN-(6–7)%PT; and K^T = 7500–9000, d₃₃ = 2200–2500 pC/N and d₃₁ = −(1100–1400) pC/N for PMN-30%PT. These two compositions are also fairly resistant to over-poling. The [0 0 1]-poled electromechanical coupling factors (k₃₃, k₃₁ and k_t) are relatively insensitive to crystal composition. [0 1 1]-optimally poled PZN-7%PT single crystal also exhibits extremely high d₃₁ values of up to −4000 pC/N with k₃₁ ≈ 0.90–0.96. While [0 1 1]-poled PZN-7%PT single crystal becomes over-poled with much degraded properties when poled at and above 0.6 kV/mm, PZN-6%PT crystal shows no signs of over-poling even when poled to 2.0 kV/mm. The presence of a certain amount (i.e., 10–15%) of orthorhombic phase in a rhombohedral matrix has been found to be responsible for the superior transverse piezoelectric properties of [0 1 1]-optimally poled PZN-(6–7)%PT. The present work shows that flux-grown PZN–PT crystals exhibit superior and consistent properties and improved over-poling resistance to flux-grown PMN–PT crystals and that, for or a given crystal composition, flux-grown PMN–PT crystals exhibit superior over-poling resistance to their melt-grown counterparts.     

A comparative study based on docking and molecular dynamics simulations over HDAC-tubulin dual inhibitors

Nowadays the ability to prediction of complex behavior rationally based on the computational approaches has been a successful technique in drug discovery. In the present study interactions of a new series of hybrids, which were made by linking colchicine as a tubulin inhibitor and suberoylanilide hydroxamic acid (SAHA) as a HDAC inhibitor, with HDAC8 and HDAC1 were investigated and compared. This research has been facilitated by the availability of experimental information besides employing docking methodology as well as classical molecular dynamics simulations and binding free energy calculation were performed. The obtained findings indicate different modes of interactions and inhibition strengths of the studied inhibitors for HDAC8 and HDAC1. HDAC8 binding free energies (−34.35 to −26.27 kcal/mol) revealed higher binding affinity to HDAC8 compared to HDAC1 (−33.17 to −7.99 kcal/mol). The binding energy contribution of each residue with the hybrid compounds 4a-4e within the active site of HDAC1 and HDAC8 was analyzed and the results confirmed the rule of key amino acids in interaction with the hybrid compounds.     

Fabrication and frequency response of dual-element ultrasonic transducer using PZT-5A thick film

Ultrasonic transducers based on PZT-5A thick films deposited onto polycrystalline Al₂O₃ substrates using screen-printing were successfully fabricated. Considering the relatively high sintering temperature of PZT-5A thick films and better impedance matching characteristics with PZT-5A, polished polycrystalline Al₂O₃ were used as substrates. For electrodes, high quality platinum (Pt) was deposited by a thin film process, because the surface state of electrodes greatly affects the quality of piezoelectric films. Applying Pt/PZT-5A/Pt/Al₂O₃ structures, dual-element ultrasonic transducers were assembled. The assembled transducers included a wear plate (normally alumina with 40.21 × 10⁶ kg/m² s of impedance), backing (tungsten carbide-epoxy), electrical matching, an epoxy glue layer, and a housing. The optimum measurement ranges of 5 and 10 MHz ultrasonic transducers were 2.51–300.2 and 2.50–250.1 mm, respectively. From the time and frequency response measurements of the assembled 10 MHz DEUTs, the value of −20 dB level waveform duration and the −6 dB bandwidth was 481.8 ns and 34.4%, respectively. Also, the measurement accuracies of both 5 and 10 MHz DEUTs assembled in this study were below 0.1 and 0.4%, respectively.     

Consensus scoring model for the molecular docking study of mTOR kinase inhibitor

The discovery of mammalian target of rapamycin (mTOR) kinase inhibitors has always been a research hotspot of antitumor drugs. Consensus scoring used in the docking study of mTOR kinase inhibitors usually improves hit rate of virtual screening. Herein, we attempt to build a series of consensus scoring models based on a set of the common scoring functions. In this paper, twenty-five kinds of mTOR inhibitors (16 clinical candidate compounds and 9 promising preclinical compounds) are carefully collected, and selected for the molecular docking study used by the Glide docking programs within the standard precise (SP) mode. The predicted poses of these ligands are saved, and revaluated by twenty-six available scoring functions, respectively. Subsequently, consensus scoring models are trained based on the obtained rescoring results by the partial least squares (PLS) method, and validated by Leave-one-out (LOO) method. In addition, three kinds of ligand efficiency indices (BEI, SEI, and LLE) instead of pIC₅₀ as the activity could greatly improve the statistical quality of build models. Two best calculated models 10 and 22 using the same BEI indice have following statistical parameters, respectively: for model 10, training set R² = 0.767, Q² = 0.647, RMSE = 0.024, and for test set R² = 0.932, RMSE = 0.026; for model 22, raining set R² = 0.790, Q² = 0.627, RMSE = 0.023, and for test set R² = 0.955, RMSE = 0.020. These two consensus scoring model would be used for the docking virtual screening of novel mTOR inhibitors.     

Electrochemical determination of ascorbic acid in fruits on a vanadium oxide polypropylene carbonate modified electrode

A novel vanadium oxide polypropylene carbonate modified glassy carbon electrode was developed and used for the measurement of ascorbic acid (AA). The electrode was prepared by casting a mixture of vanadium tri(isopropoxide) oxide (VO(OC₃H₇)₃) and poly(propylene carbonate) (PPC) onto the surface of a glassy carbon electrode. The electrochemical behavior of the VO(OC₃H₇)₃–PPC film modified glassy carbon electrode was investigated by cyclic voltammetry and amperometry. This modified electrode exhibited electrocatalytic response to the oxidation of ascorbic acid. Compared with a bare glassy carbon electrode, the modified electrode exhibits a 220 mV shift of the oxidation potential of ascorbic acid in the cathodic direction and a marked enhancement of the current response. The response current revealed a good linear relationship with the concentration of ascorbic acid in the range of 4 × 10⁻⁸ and 1 × 10⁻⁴ mol L⁻¹ and the detection limit of 1.5 × 10⁻⁸ mol L⁻¹ (S/N = 3) in the pH 8.06 Britton–Robinson solution. Quantitative recovery of the ascorbic acid in synthetic samples has been obtained and the interferences from different species have been studied. The method has been successfully applied to the determination of ascorbic acid in fruits. The concentrations of ascorbic acid measured by this method are in good agreement with the literature value. It is much promising for the modified films to be used as an electrochemical sensor for the detection of ascorbic acid.     

The effect of sinusoidal rolling ground motion on lifting biomechanics

The objective of this study was to quantify the effects of ground surface motion on the biomechanical responses of a person performing a lifting task. A boat motion simulator (BMS) was built to provide a sinusoidal ground motion (simultaneous vertical linear translation and a roll angular displacement) that simulates the deck motion on a small fishing boat. Sixteen participants performed lifting, lowering and static holding tasks under conditions of two levels of mass (5 and 10 kg) and five ground moving conditions. Each ground moving condition was specified by its ground angular displacement and instantaneous vertical acceleration: A): +6°, −0.54 m/s²; B): +3°, −0.27 m/s²; C): 0°, 0 m/s²; D): −3°, 0.27 m/s²; and E): −6°, 0.54 m/s². As they performed these tasks, trunk kinematics were captured using the lumbar motion monitor and trunk muscle activities were evaluated through surface electromyography. The results showed that peak sagittal plane angular acceleration was significantly higher in Condition A than in Conditions C, D and E (698°/s² vs. 612–617°/s²) while peak sagittal plane angular deceleration during lowering was significantly higher in moving conditions (conditions A and E) than in the stationary condition C (538–542°/s² vs. 487°/s²). The EMG results indicate that the boat motions tend to amplify the effects of the slant of the lifting surface and the external oblique musculature plays an important role in stabilizing the torso during these dynamic lifting tasks.     

Performance evaluation of a trace-moisture analyzer based on cavity ring-down spectroscopy: Direct comparison with the NMIJ trace-moisture standard

The performance of a moisture analyzer (MA) based on cavity ring-down spectroscopy (CRDS) was evaluated by direct comparison with the primary trace-moisture standard developed at the National Metrology Institute of Japan (NMIJ). The limit of detection for trace moisture in nitrogen gas by the CRDS-based MA, expressed in amount fraction (mole fraction), was estimated to be 1 nmol mol^?1 or less. The CRDS-based MA showed excellent performance in terms of linearity, accuracy, time response, stability, and reproducibility over four years. It was found for a moderate range of pressures and temperatures that we can measure trace moisture in nitrogen gas with a relative standard uncertainty of approximately 4% down to approximately 10 nmol mol^?1, even using a simple CRDS-based MA that measures only the peak intensity of the absorption line, provided that the MA is properly calibrated on the basis of a reliable trace-moisture standard.     

Curves of Genus 2 with (N,N) Decomposable Jacobians

Let C be a curve of genus 2 and ψ₁: C  −  → E ₁  a map of degree n, from C to an elliptic curveE₁ , both curves defined over C. This map induces a degree n map φ₁:P¹  −  → P ¹  which we call a Frey–Kani covering. We determine all possible ramifications for φ₁. If ψ₁:C  −  → E ₁  is maximal then there exists a maximal map ψ₂: C  −  → E ₂  , of degree n, to some elliptic curveE₂ such that there is an isogeny of degree n²from the JacobianJ_C to E₁ × E₂. We say thatJ_C is (n, n)-decomposable. If the degree n is odd the pair (ψ₂, E₂) is canonically determined. For n =  3, 5, and 7, we give arithmetic examples of curves whose Jacobians are (n, n)-decomposable.