A supramolecular spin crossover Fe(III) complex and its Cr(III) isomer: stabilization of water-chloride cluster within supramolecular host

The metal complexes, [M(Hdammthiol)(2)]Cl·3H(2)O [M = Cr(III) (1), Fe(III) (2)] [where H(2)dammthiol is the thiol form of the ligand, diacetylmonoxime morpholine N-thiohydrazone] were synthesized by metal template reactions of diacetylemonoxime with morpholine N-thiohydrazide in the presence of CrCl(3)·6H(2)O and FeCl(3)·6H(2)O. Both the complexes (1 and 2) were characterized by single crystal X-ray crystallography, spectroscopic (IR and UV-vis), M?ssbauer and TGA analyses. The single crystal X-ray studies of both complexes show that the supramolecular hosts, constructed by the discrete mononuclear complexes, form supramolecular channels along the c-axis which are filled up by water-chloride clusters. In both complexes, the 1D water-chloride chain with chair-like architecture within the supramolecular hosts presents novelty. The magnetic measurement study of Fe(III) complex shows a spin crossover from S = 1/2 at 2.5 K to S = 5/2 at 300 K. At very low temperature, the presence of strong cooperative hydrogen bonding interactions stabilizes the S = 1/2 state.     

Modulation in comprehensive two-dimensional gas chromatography: 20 years of innovation

With almost 20 years having passed since John B. Phillips described the first comprehensive two-dimensional gas chromatography (GC × GC) separation, much has occurred in this ever-expanding field of separation science. GC × GC is currently one of the most effective techniques for the separation and analysis of complex mixtures, offering significantly greater peak capacities than conventional chromatographic methods. The technique is generally based upon separations performed on two chromatographic columns characterized by considerably different selectivities, joined together through a modulating interface. The modulator periodically traps or samples the primary column effluent, usually refocuses it into a narrow chromatographic band and injects the focused fraction into the secondary column. The modulator is often referred to as the ‘heart’ of the instrument, since a GC × GC separation is impossible without its use. This article reviews major innovations in GC × GC modulator development since its first use by Phillips in 1991. Emphasis has been placed on modulator design and function.     

In vitro cytotoxic evaluation of some new heterocyclic sulfonamide derivatives

Sulfonamide‐bearing compounds posses many types of biological activities and have been recently reported to show substantial antitumor activity in vitro and/or in vivo. There are a variety of mechanisms for the anticancer activity, and the most prominent mechanism is the inhibition of carbonic anhydrase isozymes. This work reports the synthesis of some new quinoline, pyrimido[4,5‐b]quinoline and 3,1‐oxazinoquinoline derivatives bearing a sulfonamide moiety. All the newly synthesized compounds were evaluated for their in vitro anticancer activity against Ehrlich ascites carcinoma cells. Compounds 10 , 13 , and 26 were the most active compounds with IC₅₀ values of 6.1 μM, 6.8 μM, and 6.4 μM, respectively, and exhibited better activities than the reference drug doxorubicin (IC₅₀ = 68.1 μM). J. Heterocyclic Chem., 2011.     

The impact of protonation and deprotonation of 3-methyl-2'-deoxyadenosine on N-glycosidic bond cleavage

The enzyme-substrate contacts that are believed to be involved in depurination by proton transfer have been modelled by protonation and deprotonation of 3-methyl-2'-deoxyadenosine (3-MDA) using quantum mechanical calculations in the gas-phase and solution media. The change in the charge distribution on the sugar ring and nucleobase that is introduced by the protonation and deprotonation strongly affects the N-glycosidic bond length. The unimolecular cleavage and hydrolysis of the N-glycosidic bond, involving D(N)*A(N) and A(N)D(N) pathways, have been considered at several levels of theory. The trend in the energy barriers is A(N)D(N) > cleavage > D(N)*A(N). All probable proton transfer reactions resulting from enzyme-substrate contacts do not facilitate the N-glycosidic bond cleavage of 3-MDA. The deprotonation of 3-MDA that may result from the interaction between H6 and enzyme do not facilitate bond cleavage. The protonation at N7 induces more positive charge on the sugar ring and further facilitates the depurination relative to the protonation at N1. The changes in the charges calculated on the ribose and nucleobase are in good relationship with the C1'-C2', C1'-O4', and N-glycosidic bond lengths along the cleavage. The change in energy barrier ΔE of glycosidic bond cleavage from the gas-phase to solution media strongly depends on the charge of the species.     

A collocation method of lines for two‐sided space‐fractional advection‐diffusion equations with variable coefficients

We present the method of lines (MOL), which is based on the spectral collocation method, to solve space‐fractional advection‐diffusion equations (SFADEs) on a finite domain with variable coefficients. We focus on the cases in which the SFADEs consist of both left‐ and right‐sided fractional derivatives. To do so, we begin by introducing a new set of basis functions with some interesting features. The MOL, together with the spectral collocation method based on the new basis functions, are successfully applied to the SFADEs. Finally, four numerical examples, including benchmark problems and a problem with discontinuous advection and diffusion coefficients, are provided to illustrate the efficiency and exponentially accuracy of the proposed method.     

Comparison between standard and counterpoise-corrected optimization using some hydrogen and halogen bonded systems

The effect of the counterpoise correction on the geometries, stabilization energies, and vibrational harmonic frequencies of some hydrogen- and halogen-bonded systems (B?=?CH₃CN,?HCN,?NH₃,?N₂,?CO,?H₂O,?H₂S,?PH₃;?HX?=?HF,?HCl,?HBr,?HCN,?HCF₃; XY?=?Br₂,?BrCl,?BrF,?Cl₂,?ClF,?F₂) has been analysed at the MP2 level of theory using the popular 6-311++G(d,p) basis set. The optimized B?···?H and B?···?X bond lengths increase with counterpoise (CP) correction. In some cases standard values and in other cases CP-corrected values are close to experimental data. The absolute values of complexation energies of CP-corrected structures are higher than standard by inclusion of BSSE correction. The effect of CP correction on intermolecular bond lengths and complexation energies of B?···?XY series are usually higher than B?···?HX. Also, this effect is higher for H₂S and PH₃ groups. The CP correction changes the vibrational harmonic frequencies by 0–100%. The changes are frequently lower than 20% for frequencies higher than 300?cm^?1.     

Optimization of two parallel wires of laser plasma filaments for channeling electromagnetic energy

We theoretically investigated the electromagnetic wave (EMW) transmission along two parallel wires of laser plasma filaments produced by the filamentation of ultrafast laser pulses in air. Many factors, such as wire diameter and separation, electron density, and operating frequency are shown to influence the propagation loss. By taking into consideration the radiation and transmission effects of the wires, the calculations of the two parallel filament wires reasonably agrees with that of the standard commercial twin-lead wire. Specifically, the optimum separation of the two wires is determined for a given frequency and an effective electron density of the wires. When compared with free-space propagation, transmission enhancement of tens dB is obtained using optimized wire configurations. Thus, the two plasma wires may be a potential channel for point to point directed delivery of EM energy or communication of pulsed-modulated EM radiation.     

Microstructure dependence of yielding and fracture in Cd-Zn alloys

The coefficient of logarithmic work-hardening, the yield stress and the fracture stress of Cd-2 wt. %Zn alloy of different grain diameters and of Cd-17·4 wt. %Zn alloy decrease with increasing working temperature. Two relaxation temperature regions have been found, the low-temperature region of relaxation (below 483 K) and the high-temperature region (above 483 K). The fracture surface energy for Cd-2 wt. % Zn alloy has been calculated and found to be 1·2 J/m² at the two temperature regions of relaxation. X-ray investigations show that the residual internal strains in the deformed samples increase with increasing working temperature and exhibit a peak value at 483 K.     

Characterization and elimination of the interfering effects of foreign species in the atomic absorption spectrometry of chromium

In the atomic absorption spectrometric determination of chromium(III), the interfering effects of different complexing agents can be completely eliminated by addition of excess of cyanide, boric acid or sulphosalicyclic acid. The effect of some complexing agents on the production of chromium atoms is discussed, and the mechanism of cyanide interaction is investigated in detail.     

Generalized inverses and the maximal radius of regularity of a Fredholm operator

Operators possessing analytic generalized inverses satisfying the resolvent identity are studied. Several characterizations and necessary conditions are obtained. The maximal radius of regularity for a Fredholm operatorT is computed in terms of the spectral radius of a generalized inverse ofT. This provides a partial answer to a conjecture of J. Zemánek.