Synthesis,spectral investigation and development of tetrahedral copper(II) complexes as artificial metallonucleases and antimalarial agents

Seven new copper(II) complexes of type [Cu(A)(L)]?H₂O (A = sparfloxacin, ciprofloxacin, levofloxacin, gatifloxacin, pefloxacin, ofloxacin, norfloxacin; L = 5‐[(3‐chlorophenyl)diazenyl]‐4‐hydroxy‐1,3‐thiazole‐2(3H)‐thione) were synthesized and characterized using elemental and thermogravimetric analyses, and electronic, electron paramagnetic resonance (EPR), Fourier transform infrared and liquid chromatography–mass spectroscopies. Tetrahedral geometry around copper is assigned in all complexes using EPR and electronic spectral analyses. All complexes were investigated for their interaction with herring sperm DNA utilizing absorption titration (K_b = 1.27–3.13 × 10⁵ M^?1) and hydrodynamic volume measurement studies. The studies suggest the classical intercalative mode of DNA binding. The cleavage reaction on pUC19 DNA was monitored by agarose gel electrophoresis. The results indicate that the Cu(II) complexes can more effectively promote the cleavage of plasmid DNA. The superoxide dismutase mimic activity of the complexes was evaluated by nitroblue tetrazolium assay, and the complexes catalysed the dismutation of superoxide at pH = 7.8 with IC₅₀ values in the range 0.597–0.900 μM. The complexes were screened for their in vitro antibacterial activity against five pathogenic bacteria. All the complexes are good cytotoxic agents and show LC₅₀ values ranging from 5.559 to 11.912 µg ml^?1. All newly synthesized Cu(II) complexes were also evaluated for their in vitro antimalarial activity against Plasmodium falciparum strain (IC₅₀ = 0.62–2.0 µg ml^?1). Copyright © 2015 John Wiley & Sons, Ltd.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Antimicrobial activity on the copolymers of 2,4‐dichlorophenyl methacrylate with methyl methacrylate: Synthesis and characterization

Copolymers of monomers 2,4‐dichlorophenyl methacrylate (2,4‐DMA) and methyl methacrylate (MMA) were synthesized with different monomer feed ratios using toluene as a solvent and 2,2′‐azobisisobutyronitrile (AIBN) as an initiator at 70 °C. The copolymers were characterized by IR‐spectroscopy, and copolymer composition was determined with UV‐spectroscopy. The linearization method of Fineman–Ross was employed to obtain the monomer reactivity ratios. The molecular weights and polydispersity indexes were determined by gel permeation chromatography (GPC). Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. The homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5227–5234, 2004     

Are large firms internationalizing the generation of technology?Some new evidence

Internationalization of technology remains a subject of considerable interest to analysts and policy makers in the 1990s. This paper is a modest attempt at providing some new empirical observations for debate and discussion on one dimension of the subject, namely, the nature and extent of the production of technology undertaken by large firms outside their home base. The evidence, based on the US patenting activities of the world's largest 539 firms (based in 13 countries and covering 16 product groups), shows that for an overwhelming majority of them technology production remains close to the home base. It also shows that firms devoting a large proportion of their resources to technology are amongst the least internationalized. When these firms do go abroad, there is no systematic relationship between their relative presence in a technical field and the relative strength of the host country. The analysis points to the dangers of generalizing on the basis of anecdotal evidence from a small sample of firms from a particular country or sector     

An efficient electrophilic N-amination utilizing in situ generated chloramine under phase transfer conditions

An efficient, one-pot, phase transfer N-amination technology was developed. The protocol utilizes chloramine, an inexpensive and safe electrophilic aminating agent potentially viable for commercial manufacturing.     

Diastereoselective formation of 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines: An X-ray crystallographic and H NMR study

N-Arylsulfonamides of (R)- and (S)-2-amino-1-butanol, on condensation with aromatic aldehydes produced diastereomerically pure 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines. The absolute configurations of one enantiomeric pair have been determined from two fully refined X-ray structures, supplemented by nmr data.     

The case of missing incommensurate smectic A phases

Two binary mixtures of polar liquid crystal materials were previously reported to exhibit three incommensurate smectic A phases predicted for such materials on the basis of phenomenological theory. Results of our recent high-resolution X-ray scattering experiments show that no incommensurate phases exist in the two systems. Wide coexistence regions are found at first order transitions between various frustrated smectic phases of these mixtures. These regions were previously identified as the incommensurate smectic A phases. The phase diagrams of the two systems determined with high-resolution X-ray technique are shown to be in excellent agreement with Baroisa-Prost-Lubensky theory.     

Kinetics of solvolysis of 2-chloroquinoxaline

Pseudo-first-order rate constants and activation parameters have been measured for the solvolysis of 2-chloroquinoxaline in various aquo-organic mixtures using methanol, ethanol, and isopropanol as the organic solvent. Excellent linear correlations are found between lnk and the mol fraction of cosolvent and ln[H₂O]. The medium effect on the rates of solvolysis is assessed by Grunwald–Winstein's mY correlationship. The estimated values of m (0.55–0.72) and the entropy of activation (148–212 J deg^?1 mol^?1) for the reactions are well in the range for a bimolecular aromatic substitution reactions. © 1994 John Wiley & Sons, Inc.     

Comparison of stochastic approaches to the transportation problem:a case study

The objective of this case study is to provide insight to practitioners about the methodology of using the space-time autoregressive integrated moving average (STARIMA) class of models to formulate stochastic demand of the transportation problem. While providing insight, two other methods-expected value (EV) and stochastic approximation (SA)-are also employed to formulate demand. A comparative evaluation of the methods using brewery data for the distribution of four products from five production plants to 64 distribution centers is presented. It is shown that the demand characterized by the STARIMA approach results in a lower total cost of transportation. This occurs because the STARIMA approach results in better forecasts. Based upon the case study, the cost analysis indicated that the STARIMA method when used without (with) updating resulted in a 9.49% (10.5%) increase in the Company's net profit as compared with the SA method. Similarly, the STARIMA approach when used without (with) updating resulted in an 11.36% (12.37%) increase in the net profit as compared with the EV method. For the STARIMA approach, computations for a large size problem are shown to be identical to those of the deterministic transportation problem given the demand forecasts. Extra computation effort for producing STARIMA forecasts are easily justified in terms of the increased profit margin     

Analysis of a simple successive interference cancellation scheme ina DS/CDMA system

Compensating for near/far effects is critical for satisfactory performance of DS/CDMA systems. So far, practical systems have used power control to overcome fading and near/far effects. Another approach, which has a fundamental potential in not only eliminating near/far effects but also in substantially raising the capacity, is multiuser detection and interference cancellation. Various optimal and suboptimal schemes have been investigated. Most of these schemes, however, get too complex even for relatively simple systems and rely on good channel estimates. For interference cancellation, estimation of channel parameters (viz. received amplitude and phase) is important. We analyze a simple successive interference cancellation scheme for coherent BPSK modulation, where the parameter estimation is done using the output of a linear correlator. We then extend the analysis for a noncoherent modulation scheme, namely M-ary orthogonal modulation. For the noncoherent case, the needed information on both the amplitude and phase is obtained from the correlator output. The performance of the IC scheme along with multipath diversity combining is studied