Enhancement of catalytic activity of titanosilicalite-1 - sulfated zirconia combination towards epoxidation of 1-octene with aqueous hydrogen peroxide

Summary Titanosilicalite-1 (TS-1) in combination with sulfated zirconia efficiently catalyzes the epoxidation of 1-octene with aqueous hydrogen peroxide. The presence of both octahedral zirconium and sulfate species in the catalysts enhances the epoxidation rates.     

Nanomolar Determination of Methyldopa in the Presence of Large Amounts of Hydrochlorothiazide Using a Carbon Paste Electrode Modified with Graphene Oxide Nanosheets and 3‐(4′‐Amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic Acid

A novel electrochemical sensor for sensitive detection of methyldopa at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with graphene oxide nanosheets and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,′AA). Applying square wave voltammetry (SWV), in phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with two concentration intervals of methyldopa, one is 1.0×10^?8–1.0×10^?6 M and the other is 1.0×10^?6–4.5×10^?5 M. The detection limit (3σ) obtained by SWV was 9.0 nM. The modified electrode was successfully applied for simultaneous determination of methyldopa and hydrochlorothiazide. Finally, the proposed method was applied to the determination of methyldopa and hydrochlorothiazide in some real samples.     

An Eco‐friendly Three Component Manifold for the Synthesis of α‐Aminophosphonates under Catalyst and Solvent‐free Conditions,X‐ray Characterization and Their Evaluation as Anticancer Agents

A series of α‐aminophosphonates were synthesized through one‐pot condensation of aryl aldehydes, aryl amines and diethyl phosphite in the absence of any catalyst and organic solvents. All the synthesized α‐aminophosphonates were characterized by spectral and elemental analysis and in the case of compound 4j by X‐ray crystallography. Some of these new α‐aminophosphonate derivatives were found to have cytotoxic activity on the cancer cell line DU145 in vitro by the MTT method.     

An adaptive nonmonotone global Barzilai–Borwein gradient method for unconstrained optimization

The Barzilai–Borwein (BB) gradient method has received many studies due to its simplicity and numerical efficiency. By incorporating a nonmonotone line search, Raydan (SIAM J Optim. 1997;7:26–33) has successfully extended the BB gradient method for solving general unconstrained optimization problems so that it is competitive with conjugate gradient methods. However, the numerical results reported by Raydan are poor for very ill-conditioned problems because the effect of the degree of nonmonotonicity may be noticeable. In this paper, we focus more on the nonmonotone line search technique used in the global Barzilai–Borwein (GBB) gradient method. We improve the performance of the GBB gradient method by proposing an adaptive nonmonotone line search based on the morphology of the objective function. We also prove the global convergence and the R-linear convergence rate of the proposed method under reasonable assumptions. Finally, we give some numerical experiments made on a set of unconstrained optimization test problems of the CUTEr collection. The results show the efficiency of the proposed method in the sense of the performance profile introduced (Math Program. 2002;91:201–213) by Dolan and Moré.     

An adaptive wavelet space‐time SUPG method for hyperbolic conservation laws

This article concerns with incorporating wavelet bases into existing streamline upwind Petrov‐Galerkin (SUPG) methods for the numerical solution of nonlinear hyperbolic conservation laws which are known to develop shock solutions. Here, we utilize an SUPG formulation using continuous Galerkin in space and discontinuous Galerkin in time. The main motivation for such a combination is that these methods have good stability properties thanks to adding diffusion in the direction of streamlines. But they are more expensive than explicit semidiscrete methods as they have to use space‐time formulations. Using wavelet bases we maintain the stability properties of SUPG methods while we reduce the cost of these methods significantly through natural adaptivity of wavelet expansions. In addition, wavelet bases have a hierarchical structure. We use this property to numerically investigate the hierarchical addition of an artificial diffusion for further stabilization in spirit of spectral diffusion. Furthermore, we add the hierarchical diffusion only in the vicinity of discontinuities using the feature of wavelet bases in detection of location of discontinuities. Also, we again use the last feature of the wavelet bases to perform a postprocessing using a denosing technique based on a minimization formulation to reduce Gibbs oscillations near discontinuities while keeping other regions intact. Finally, we show the performance of the proposed combination through some numerical examples including Burgers’, transport, and wave equations as well as systems of shallow water equations.© 2017 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 2062–2089, 2017     

Fabrication of a nanostructure-based electrochemical sensor for simultaneous determination of N-acetylcysteine and acetaminophen

A carbon-paste electrode modified with 2,7-bis(ferrocenyl ethyl)fluoren-9-one (2,7-BF) and carbon nanotubes (CNTs) was used for the sensitive and selective voltammetric determination of N-acetylcysteine (NAC). The mediated oxidation of NAC at the modified electrode was investigated by cyclic voltammetry (CV). Also, the values of catalytic rate constant (k), and diffusion coefficient (D) for NAC were calculated. Differential pulse voltammetry (DPV) of NAC at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 52.0 nmol L⁻¹. DPV was used for simultaneous determination of NAC and acetaminophen (AC) at the modified electrode, and quantitation of NAC and AC in some real samples by the standard addition method.     

Chemical Characterization of Cultivated Tagetes minuta L. by Use of Ultrasound-Assisted Head Space SPME and GC–MS

Ultrasound-assisted headspace solid-phase microextraction (UA-HS-SPME) coupled to gas chromatography–mass spectrometry (GC–MS) has been used for analysis of volatile compounds in dry Tagetes minuta L. The highest extraction efficiency was achieved with a 100-μm polydimethylsiloxane (PDMS) fiber. Different experimental conditions, for example, type of fiber coating, sonication time, extraction time and temperature, and desorption time, were investigated. Thirty compounds were identified by use of this UA-HS-SPME–GC–MS method. Comparison of the method with the commonly used hydrodistillation (HD) method showed that the proposed method is simpler, needs much less sample, requires shorter extraction time and lower temperature, has high trapping ability, and extracts more volatile and thermally sensitive compounds. The major components identified by use of the method were e-ocimenone (10.3%), cis-β-ocimene (4.8%), α-terpinolene (8.4%), trans-caryophyllene (19.7%), germacrene-d (10.0%), and camphor (3.6%).     

Pseuduvarines A and B, two new cytotoxic dioxoaporphine alkaloids from Pseuduvaria rugosa

Pseuduvarines A (1) and B (2), two new dioxoaporphine alkaloids with an amino moiety, were isolated from the stem bark of Pseuduvaria rugosa and their structures were elucidated by combination of 2D-NMR spectroscopic analysis. Pseuduvarines A (1) and B (2) showed cytotoxicity against MCF7, HepG2, and HL-60 (1: IC??, 0.9, 21.7, and >50.0 μM, respectively, 2: IC?? >50.0, 15.7, and 12.4 μM, respectively).     

The extent of molecular orientation at liquid/vapor interface of pyridine and its alkyl derivatives by molecular dynamics simulation

In this paper, molecular dynamics simulation was performed to investigate the liquid∕vapor interfacial structure of neat polar liquids. Large-scale ensembles of liquid pyridine and its alkyl derivatives, 4-methylpyridine and 4-ethylpyridine, were simulated by classical molecular dynamics at 298 K. For the liquid system of low polarity, the surface density profile of the atoms meet exactly at the middle of interfacial region, and atoms of hydrophobic nature can be hardly discriminated from hydrophilic ones in either vapor or liquid sides. For a liquid system of high polarity, the density profile of atoms with different nature is highly discriminated all over the interfacial region, and as the polarity increases, a dense region of atomic density is clearly developed in the subsurface region. The recognized bivariate method was also used to study the molecular orientational distribution quantitatively. Orientational analysis of the three liquid systems indicates that the pyridine ring plane in the outmost surface tends to be vertical. Its tendency in the innermost interfacial region is parallel. The orientational states available to 4-ethylpyridine and pyridine are discriminated by predicting the possibility of a bisector-wise tumbling for the ring plane in pyridine and a side-wise tumbling in 4-ethylpyridine. The orientational distribution maps explain the trend of experimental surface tension and surface entropy. As the dipole moment of these liquids increases with the alkyl chain length, the surface structural profile changes from a regular definite one to a surface of complex atomic structure involving a dense phase near the interface. The development of dense region in alkyl derivatives is the result of segregation of molecules due to the alkyl group, which is captured and discriminated by molecular dynamics simulation even when the length of a short alkyl chain is increased by one carbon atom.     

Allylpalladium dimers with metals connected by binucleating dithiooxamidates in two different coordination modes: solution behavior and solid-state structure

A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N](2-) [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η(3)-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η(3)-allyl)PdCl](2) in chloroform. At low temperature (20 °C), the bimetallic complexes [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N',S' Pd') (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η(3)-allyl)Pd(N^N) frame of kinetic compounds or in the (η(3)-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N](2-), when engaged in a κ-N,S Pd, κ-N',S' Pd' coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η(3)-allyl)Pd](2)(μ-diethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), [(η(3)-allyl)Pd](2)(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), and [(η(3)-allyl)Pd](2)(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') are reported.