Structural elucidation of nitro-substituted five-membered aromatic heterocycles utilizing GIAO DFT calculations

The GIAO (Gauge Including Atomic Orbitals) DFT (Density Functional Theory) method is applied at the B3LYP/6-31+G(d,p)//B3LYP/6-31+G(d), B3LYP/6-311++G(d,p)//B3LYP/6-31+G(d), B3LYP/6-311+G (2d,p)//B3LYP/6-31+G(d) and B3LYP/6-311++G(d,p)//B3LYP/6-311++G(d,p) levels of theory for the calculation of proton and carbon chemicals shifts and coupling constants for 25 nitro-substituted five-membered heterocycles. Difference (1D NOE) spectra in combination with long-range gHMBC experiments were used as tools for the structural elucidation of nitro-substituted five-membered heterocycles. The assigned NMR data (chemical shifts and coupling constants) for all compounds were found to be in good agreement with theoretical calculations using the GIAO DFT method. The magnitudes of one-bond (1JCH) and long-range (nJCH, n>1) coupling constants were utilized for unambiguous differentiation between regioisomers of nitro-substituted five-membered heterocycles.     

Determination of Total Reduced Thiol Levels in Plasma Using a Bromide Substituted Quinone

The exploitation of 2‐bromo‐1,4‐naphthoquinone (NQBr) as a selective redox label for the determination of reduced thiol functionalities (RSH) has been investigated. The system is selective for RSH functionality, giving distinct voltammetric signals for glutathione and cysteine but can also be adapted for broad spectrum thiol detection. Ion chromatographic protocols based on conductimetric detection enable total RSH analysis (protein and monomolecular moieties) within human plasma. Bromide released through the reaction can be easily quantified and integrated within normal IC measurements. The efficacy of the approach has been assessed and the response validated through comparison with the standard colorimetric technique.     

A high yielding, one-pot synthesis of O,S-dialkyl dithiocarbonates from alcohols using Mitsunobu’s reagent

A novel Mitsunobu-based protocol has been developed for the synthesis of O,S-dialkyl dithiocarbonates from a variety of primary, secondary and tertiary alcohols using carbon disulfide, in good to excellent yields. This protocol is mild and efficient compared to other reported methods.     

Oxomolybdenum(VI) and (IV) complexes of pyrazole derived ONO donor ligands – synthesis,crystal structure studies and spectroelectrochemical correlation

Four cis-dioxomolybdenum complexes of general formula [MoO₂(Lⁿ)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L⁴)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh₃. The complexes are characterized by elemental analysis, electronic spectra, IR, ¹H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO₅ donor environment.     

Evaluation ofwaste perlite fines in the production of construction materials

The use of supplementary cementitious materials (SCM) is a well established practice worldwide in the manufacture of Portland cement (PC)-based construction materials. While utilisation of industrial by-products has been successful, the potential of mining wastes is yet to receive adequate attention in the context of construction materials. In an expanded form perlite, which is a naturally occurring, hydrated volcanic siliceous glass, is an ideal material as a lightweight aggregate for use in a wide range of construction materials including concrete. The mining and processing of the grades of perlite required for the production of lightweight aggregate results in the creation of a fine grained waste which currently has no economic value. This paper reports preliminary data on the utilisation of waste perlite fines as a SCM in calcium silicate-based construction material and discusses the potential of this mining waste to reduce the environmental impact of the production of conventional cement-based construction materials.     

Dipyridyl bridged coordination polymers of Cu(II): Synthesis,crystal structure and magnetic study

Two coordination polymers, [Cu(bpp)(H₂O)₂(ClO₄)₂]_n (1) and {[Cu(bpds)₂(ClO₄)₂] · 1.5(H₂O)}_n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,4′-bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement. Both the coordination polymers display 1D chains with perchlorate anions acting as pendant ligands. In 1 undulated polymers are built by Cu(H₂O)₂(ClO₄)₂ units connected by single bpp and in complex 2 Cu(ClO₄)₂ fragments are linked by pairs of bpds ligands to form a double-stranded chain. The crystal packing evidences polymers of 1 involved in weak H-bonding interactions leading to a 3D supramolecular network. Magnetic study reveals weak antiferromagnetic interactions in both complexes.     

Where is the sodium in self-assembled monolayers of single-stranded DNA?

Monolayers of single-stranded DNA (ssDNA) immobilized on surfaces form the basis of a number of important biotechnology applications, including DNA microarrays and biosensors. The organization of ssDNA as layer on a solid substrate allows one to investigate various properties of the DNA in a controlled manner and to use DNA for analytical applications as well as for exploring futuristic schemes for molecular electronics. It is commonly assumed that the adsorbed DNA layer contains some structural water and the cations. Here we show, based on XPS studies, that when monolayers of ssDNA are formed from sodium phosphate buffer and washed thoroughly, no Na+ signal is detected. A finite concentration of ions is observed when the DNA is made from a solution of Mg2+ ions, but it is still only a fifth of what it would be if all the phosphate ions were fully neutralized by the metal cations.     

Characterization of framework and extra-framework aluminum species in non-hydrated zeolites Y by 27Al spin-echo, high-speed MAS, and MQMAS NMR spectroscopy at B0 = 9.4 to 17.6 T

27Al spin-echo, high-speed MAS (nu(rot) = 30 kHz), and MQMAS NMR spectroscopy in magnetic fields of B0 = 9.4, 14.1, and 17.6 T were applied for the study of aluminum species at framework and extra-framework positions in non-hydrated zeolites Y. Non-hydrated gamma-Al2O3 and non-hydrated aluminum-exchanged zeolite Y (Al,Na-Y) and zeolite H,Na-Y were utilized as reference materials. The solid-state 27Al NMR spectra of steamed zeolite deH,Na-Y/81.5 were found to consist of four signals. The broad low-field signal is caused by a superposition of the signals of framework aluminum atoms in the vicinity of bridging hydroxyl protons and framework aluminum atoms compensated in their negative charge by aluminum cations (delta(iso) = 70 +/- 10 ppm, C(QCC) = 15.0 +/- 1.0 MHz). The second signal is due to a superposition of the signals of framework aluminum atoms compensated by sodium cations and tetrahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 65 +/- 5 ppm, C(QCC) = 8.0 +/- 0.5 MHz). The residual two signals were attributed to aluminum cations (delta(iso) = 35 +/- 5 ppm, C(QCC) = 7.5 +/- 0.5 MHz) and octahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 10 +/- 5 ppm, C(QCC) = 5.0 +/- 0.5 MHz). By chemical analysis and evaluating the relative solid-state 27Al NMR intensities of the different signals of aluminum species occurring in zeolite deH,Na-Y/81.5 in the non-hydrated state, the aluminum distribution in this material was determined.     

Computational study of the reaction of N(2D) atoms with CH2F radicals: an example of a barrier-free reaction involving very high internal energies

The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order M?ller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(4S) with CH2F(2A') has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(4S) with CH2F(2A') should proceed on the triplet surface without spin change.