Oxovanadium(IV) complexes with cephradine: Synthesis, Semi-Empirical study, spectroscopy, potentiometric study and antimicrobial activity

The reactions between cephradine and VOSO₄.3H₂O in 1:1, 1:2 and 1:3 molar ratios in methanol were investigated at room temperature, 0 °C and ?10 °C. In various pH conditions, the different complexes formulated as VO(H₂O)₃L^2?, VO(H₂O)L₂ ^2? and VL₃ ^? were formed by titration of VOSO₄.3H₂O and cephradine with NaOH. These complexes were characterized by elemental analysis and IR spectroscopy. IR spectra of all the complexes show the disappearance of ν(O-H) band of cephradine, which confirms complexation. Estimation of vanadium in the complexes was carried out by ICP-AES. The stability constants of each complex were calculated on the basis of which a general mechanism is hereby proposed with regard to the formation of these complexes. In complex (1) the cephradine ligand bind in bidentate [O,O] fashion together with a terminal oxo ligand and water molecules complete the metal coordination sphere. In complex (2) the cephradine ligands bind in bis-bidentate [O,O] fashion and the axial positions are occupied by the oxo ligand and a trans-water molecule. Biological screening tests show significant antibacterial and anti-fungal activities against various bacterial and fungal strains.     

Smaller Coresets for k-Median and k-Means Clustering

In this paper we show that there exists a -coreset for k-median and k-means clustering of n points in which is of size independent of n. In particular, we construct a -coreset of size for k-median clustering, and of size for k-means clustering.     

An analytical model for the prediction of the dynamic response of premixed flames stabilized on a heat-conducting perforated plate

The dynamic response of a premixed flame stabilized on a heat-conducting perforated plate depends critically on their coupled thermal interaction. The objective of this paper is to develop an analytical model to capture this coupling. The model predicts the mean flame base standoff distance; the flame base area, curvature and speed; and the burner plate temperature given the operating conditions; the mean velocity, temperature and equivalence ratio of the reactants; thermal conductivity and the perforation ratio of the burner. This coupled model is combined with our flame transfer function (FTF) model to predict the dynamic response of the flame to velocity perturbations. We show that modeling the thermal coupling between the flame and the burner, while accounting for the two-dimensionality of the former, is critical to predicting the dynamic response characteristics such as the overshoot in the gain curve (resonant condition) and the phase delay. Good agreement with the numerical and experimental results is demonstrated over a range of conditions.     

Palladium polyether diphosphinite complex anchored in polyethylene glycol as an efficient homogeneous recyclable catalyst for the Heck reactions

Palladium polyether diphosphinite complex anchored on polyethylene glycol is reported as an efficient catalyst for Heck coupling reactions. The catalyst is soluble in the solvent with reactants and products during reaction and can be separated from reaction media in biphasic form by the addition of anti-solvent like n-hexane and further recycled. The developed methodology offers mild reaction condition, short reaction time with an excellent recyclability of the catalyst. Aryl iodides as well as aryl bromides are well tolerated giving excellent yields.     

Synthesis, molecular modeling and spectroscopic characterization of nickel(II), copper(II), complexes of new 16-membered mixed-donor macrocyclic schiff base ligand incorporating a pendant alcohol function

Complexes of Cu(II) and Ni(II) of the composition [M(L)X] [where M=Ni(II), Cu(II) and X=Cl-, NO3-, CH3COO-] were synthesized with 1,5-dioxo-9,10-diaza-3,ol-tribenzo-(7,6,10,11,14,15) peptadecane, a N2O2 macrocyclic ligand. The complexes were characterized by elemental analysis, molar conductance measurements, UV-vis, IR, 1H NMR, 13C NMR, EPR and molecular modeling studies. All the complexes are non-electrolyte in nature. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes and a tetragonal geometry for Cu(II) complexes.     

Understanding stress-induced disorder and breakage in organic crystals: beyond crystal structure anisotropy

Crystal engineering has advanced the strategies for design and synthesis of organic solids with the main focus being on customising the properties of the materials. Research in this area has a significant impact on large-scale manufacturing, as industrial processes may lead to the deterioration of such properties due to stress-induced transformations and breakage. In this work, we investigate the mechanical properties of structurally related labile multicomponent solids of carbamazepine (CBZ), namely the dihydrate (CBZ·2H₂O), a cocrystal of CBZ with 1,4-benzoquinone (2CBZ·BZQ) and the solvates with formamide and 1,4-dioxane (CBZ·FORM and 2CBZ·DIOX, respectively). The effect of factors that are external (e.g. impact stressing) and/or internal (e.g. phase transformations and thermal motion) to the crystals are evaluated. In comparison to the other CBZ multicomponent crystal forms, CBZ·2H₂O crystals tolerate less stress and are more susceptible to breakage. It is shown that this poor resistance to fracture may be a consequence of the packing of CBZ molecules and the orientation of the principal molecular axes in the structure relative to the cleavage plane. It is concluded, however, that the CBZ lattice alone is not accountable for the formation of cracks in the crystals of CBZ·2H₂O. The strength and the temperature-dependence of electrostatic interactions, such as hydrogen bonds between CBZ and coformer, appear to influence the levels of stress to which the crystals are subjected that lead to fracture. Our findings show that the appropriate selection of coformer in multicomponent crystal forms, targetting superior mechanical properties, needs to account for the intrinsic stress generated by molecular vibrations and not solely by crystal anisotropy. Structural defects within the crystal lattice, although highly influenced by the crystallisation conditions and which are especially difficult to control in organic solids, may also affect breakage.

Crystal engineering has advanced the strategies of design and synthesis of organic solids with the main focus being on customising the properties of the materials.     

Self-assembled monolayers of Aβ peptides on Au electrodes: an artificial platform for probing the reactivity of redox active metals and cofactors relevant to Alzheimer's disease

The water-soluble hydrophilic part of human Aβ peptide has been extended to include a C-terminal cysteine residue. Utilizing the thiol functionality of this cysteine residue, self-assembled monolayers (SAM) of these peptides are formed on Au electrodes. Atomic force microscopy imaging confirms formation of small Aβ aggregates on the surface of the electrode. These aggregates bind redox active metals like Cu and cofactors like heme, both of which are proposed to generate toxic partially reduced oxygen species (PROS) and play a vital role in Alzheimer's disease. The spectroscopic and electrochemical properties of these Cu and heme bound Aβ SAM are similar to those reported for the soluble Cu and heme bound Aβ peptide. Experiments performed on these Aβ-SAM electrodes clearly demonstrate that (1) heme bound Aβ is kinetically more competent in reducing O(2) than Cu bound Aβ, (2) under physiological conditions the reduced Cu site produces twice as much PROS (measured in situ) than the reduced heme site, and (3) chelators like clioquinol remove Cu from these aggregates, while drugs like methylene blue inhibit O(2) reactivity of the heme cofactor. This artificial construct provides a very easy platform for investigating potential drugs affecting aggregation of human Aβ peptides and PROS generation by its complexes with redox active metals and cofactors.     

Pillar[5]arenes: fascinating cyclophanes with a bright future

Pillar[5]arenes are [1(5)]paracyclophane derivatives consisting of 1,4-disubstituted hydroquinones linked by methylene bridges in the 2,5-positions. The first report of these novel macrocycles was in 2008, when 1,4-dimethoxypillar[5]arene was prepared in 22% yield, and subsequent improvements in synthetic methods have allowed the number of derivatives to expand significantly. In addition to D(5) symmetric pillar[5]arenes, asymmetric pillar[5]arenes with two different substituents in the 1- and 4-positions and copillar[5]arenes consisting of two different repeat units in a 4 : 1 ratio have been synthesised. Crystallographic, computational and spectroscopic studies are starting to shed light on the compounds' unusual inclusion phenomena, from gelation and transportation of water through nanotubes to the formation of chromogenic rotaxanes. Applications as molecular sensors are starting to appear with a focus on guest detection by fluorescence quenching. This tutorial review will provide a summary of research into the pillar[5]arenes since their recent discovery.     

Systematic study of deformation effects on fusion cross-sections using various proximity potentials

The influence of static quadrupole and hexadecapole (positive & negative) deformation of targets are studied using eleven different versions of nuclear potentials. The height and position of the interaction barrier for the reactions induced by spherical projectile (¹⁶O) on the deformed targets such as ¹⁶⁶Er, ¹⁵⁴Sm and ¹⁷⁶Yb have been estimated. It is found that the nucleus-nucleus potential strongly depends on the value of the deformation parameters and orientation of the target. The experimental fusion cross-section of the reactions ¹⁶O + ¹⁷⁶Yb, ¹⁶O +¹⁶⁶Er and ¹⁶O +¹⁵⁴Sm are investigated by applyingWong’s formula using various parameterizations of the proximity potential as well as an assessment of the results of a multi-dimensional barrier penetration model (BPM). The fusion cross-sections by Prox 77, Prox 88, Prox 00, Prox 00DP, Denisov DP, Bass 80, CW 76 and AW 95 potentials are found to be better than the rest in comparison to experimental data.