Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles

An efficient palladium-catalyzed AAA reaction with a simple α-sulfonyl carbon anion as nucleophiles is presented for the first time. Allyl fluorides are used as superior precursors for the generation of π-allyl complexes that upon ionization liberate fluoride anions for activation of silylated nucleophiles. With the unique bidentate diamidophosphite ligand ligated palladium as catalyst, the in situ generated α-sulfonyl carbon anion was quickly captured by the allylic intermediates, affording a series of chiral homo-allylic sulfones with high efficiency and selectivity. This work provides a mild in situ desilylation strategy to reveal nucleophilic carbon centers that could be used to overcome the pK_a limitation of “hard” nucleophiles in enantioselective transformations.

A variety of “hard” α-sulfonyl carbanions of aryl, heteroaryl and alkyl sulfones were successfully employed as nucleophiles in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities.     

Strong and Weak Solutions to Second Order Differential Inclusions Governed by Monotone Operators

In this paper we introduce the concept of a weak solution for second order differential inclusions of the form u″(t) ∈ Au(t) + f(t), where A is a maximal monotone operator in a Hilbert space H. We prove existence and uniqueness of weak solutions to two point boundary value problems associated with such kind of equations. Furthermore, existence of (strong and weak) solutions to the equation above which are bounded on the positive half axis is proved under the optimal condition tf(t) ∈ L ¹(0, ∞; H), thus solving a long-standing open problem (for details, see our comments in Section 3 of the paper). Our treatment regarding weak solutions is similar to the corresponding theory related to the first order differential inclusions of the form f(t) ∈ u′(t) + Au(t) which has already been well developed.     

Row–column interaction models,with an R implementation

We propose a family of models called row–column interaction models (RCIMs) for two-way table responses. RCIMs apply some link function to a parameter (such as the cell mean) to equal a row effect plus a column effect plus an optional interaction modelled as a reduced-rank regression. What sets this work apart from others is that our framework incorporates a very wide range of statistical models, e.g., (1) log-link with Poisson counts is Goodman’s RC model, (2) identity-link with a double exponential distribution is median polish, (3) logit-link with Bernoulli responses is a Rasch model, (4) identity-link with normal errors is two-way ANOVA with one observation per cell but allowing semi-complex modelling of interactions of the form  \(\mathbf{A}\mathbf{C}^T\) , (5) exponential-link with normal responses are quasi-variances. Proposed here also is a least significant difference plot augmentation of quasi-variances. Being a special case of RCIMs, quasi-variances are naturally extended from the \(M=1\) linear/additive predictor  \(\eta \) case (within the exponential family) to the \(M>1\) case (vector generalized linear model families). A rank-1 Goodman’s RC model is also shown to estimate the site scores and optimums of an equal-tolerances Poisson unconstrained quadratic ordination. New functions within the VGAM R package are described with examples. Altogether, RCIMs facilitate the analysis of matrix responses of many data types, therefore are potentially useful to many areas of applied statistics.     

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%).