Rationalization of the behavior of M2(CH3CS2)4I (M = Ni,Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations

The electrical conductivities and plausible charge‐ordering states in the room temperature (r.t.) phase for MMX chains [Ni₂(dta)₄I]_∞ and [Pt₂(dta)₄I]_∞ (dta = CH₃CS) have been analyzed with periodic density functional theory (DFT) and correlated ab initio calculations combined with the effective Hamiltonian theory. Periodic DFT calculations show a more delocalized nature of the ground state in [Pt₂(dta)₄I]_∞ compared to [Ni₂(dta)₄I]_∞, which features a rather large energy gap between the occupied and empty bands, and charge polarized dimer units. A larger electrical conductivity for the Pt chain can be expected, especially because the Fermi level lies within a band with contributions from Pt and I orbitals. Electronic structure parameters extracted from ab initio cluster calculations show that the large difference between the observed conductivities at 300 K for Ni and Pt compounds, of 3 orders of magnitude, cannot be explained from the parameters extracted from an embedded M₂(dta)₄I₂ dimer fragment alone. When tetramer fragments are considered, we observe that the interdimer transfer integral (t) between neighboring M₂ units connected by an iodine atom at correlated level is comparable in both chains. On the other hand, the energy to transfer an electron from a dimer to the neighboring one (Coulomb repulsion U) is three times larger in the Ni compound with respect to the Pt chain, in line with the poor conductivity of the former. The electronic structure of the M₄(dta)₈I₃ fragment points to an alternate charge‐polarization state for Ni and an average valence state for Pt when the r.t. X‐ray structure is considered. © 2012 Wiley Periodicals, Inc.     

On nonparametric classification with missing covariates

General procedures are proposed for nonparametric classification in the presence of missing covariates. Both kernel-based imputation as well as Horvitz-Thompson-type inverse weighting approaches are employed to handle the presence of missing covariates. In the case of imputation, it is a certain regression function which is being imputed (and not the missing values). Using the theory of empirical processes, the performance of the resulting classifiers is assessed by obtaining exponential bounds on the deviations of their conditional errors from that of the Bayes classifier. These bounds, in conjunction with the Borel-Cantelli lemma, immediately provide various strong consistency results.     

An improved solvent-free synthesis of flunixin and 2-(arylamino) nicotinic acid derivatives using boric acid as catalyst

A simple solvent-free protocol for the preparation of flunixin, a potent non-narcotic, non-steroidal anti-inflammatory drugs is reported using boric acid as catalyst. Its salt, flunixin meglumine are then prepared under reflux in EtOH. This sustainable method are then extended for the synthesis of a series of 2-(arylamino) nicotinic acid derivatives. The present protocol combines non-hazardous neat conditions with associated benefits like excellent yield, straightforward workup, and use of readily available and safe catalyst in the absence of any solvent, which are important factors in the pharmaceutical industry. The pathway for catalytic activation of 2-chloronicotic acid with boric acid was also investigated using Gaussian 03 program package.

Open image in new window

     

Screen-printed electrodes for biosensing: a review (2008–2013)

Screen-printing is one of the most promising approaches towards simple, rapid and inexpensive production of biosensors. Disposable biosensors based on screen printed electrodes (SPEs) including microelectrodes and modified electrodes have led to new possibilities in the detection and quantitation of biomolecules, pesticides, antigens, DNA, microorganisms and enzymes. SPE-based sensors are in tune with the growing need for performing rapid and accurate in-situ analyses and for the development of portable devices. This review (with 226 refs.) first gives an introduction into the topic and then is subdivided into sections (a) on DNA sensors (including methods for the detection of hybridization and damage), (b) on aptasensors (for thrombin, OTA, immunoglobulins and cancer biomarkers), (c) on immunosensors (for microorganisms, immunoglobulins, toxins, hormones, lactoferrin and biomarkers), (d) on enzymatic biosensors (for glucose, hydrogen peroxide, various pharmaceuticals, neurotransmitters, amino acids, NADH, enzyme based sensors).

1,3-Dibromo-5,5-dimethylhydantoin as an efficient homogeneous catalyst for synthesis of benzoxazoles, benzimidazoles, and oxazolo[4,5-b]pyridines

Abstract  

A simple and highly efficient method for synthesis of benzoxazoles, benzimidazoles, and oxazolo[4,5-b]pyridines is described. Condensation of orthoesters with o-substituted anilines or 2-amino-3-hydroxypyridine was performed in the presence of catalytic amounts of commercially available, inexpensive, and moisture-stable 1,3-dibromo-5,5-dimethylhydantoin under solvent-free conditions. The corresponding heterocycles were obtained in good to excellent yields. The main advantages of the present procedure are mild reaction conditions, short reaction times, high yields of products, easy work-up, and absence of solvent.     

Synthesis and application of a novel solid-phase microextraction adsorbent: hollow fiber supported carbon nanotube reinforced sol-gel for determination of phenobarbital

The present study reports the development, validation and application of a new green liquid chromatographic method for the determination of glutathione (GSH) in vegetable samples. In this work we introduce—for the first time—ethyl propiolate (EP) as an advantageous post-column derivatization reagent for thiolic compounds. GSH (t_R = 6.60 min) and N-acetylcysteine (NAC, internal standard) (t_R = 11.80 min) were separated efficiently from matrix endogenous compounds by using a 100% aqueous mobile phase (0.1%, v/v CH₃COOH in 1 mmol L⁻¹ EDTA, Q_V = 0.5 mL min⁻¹) and a Prevail^® reversed phase column that offers the advantage of stable packing material in aqueous mobile phases. The parameters of the post-column reaction (pH, amount concentration of the reagent, flow rates, length of the reaction coil and temperature) were studied. The linear determination range for GSH was 1–200 μmol L⁻¹ and the LOD was 0.1 μmol L⁻¹ (S/N = 3). Total endogenous GSH was determined in broccoli, potato, asparagus and Brussels sprouts using the standards addition approach. The accuracy was evaluated by both recovery experiments (R = 91–110%) and comparison to an o-phthalaldehyde/glycine corroborative post-column derivatization fluorimetric method.