Metal complexes of sulfur-nitrogen chelating agents. Part 12. The chemistry of nickel(II), palladium(II), cobalt(II) and copper(II) complexes of N2S2 and N3S2 donor systems

Summary Nickel(II), palladium(II), cobalt(II) and copper(II) complexes of the ligandN,N-1,2-propane-bis(methyl 2-amino-cyclopent-1-ene-dithiocarboxylate) (H₂L¹),N,N-1,3-propane-bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate) (H₂L²) andN,N-[bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate)] diethylenetriamine (H₂L³) have been synthesised. Both H₂L¹ and H₂L² form complexes of the type ML, and all but the copper(II) complexes, are square planar. In the copper(II) complexes tetrahedral distortion is significantly more with CuL². From H₂L³ square planar complexes of the type [M(HL³)X] (M=Ni, X=Cl, Br, I or SCN; M=Pd, X=Cl or Br) have been obtained in which the donor unit involved is N₂SX. The composition of the cobalt(II) and copper(II) complexes is [M(H₂L³)X₂] (X=Cl or Br) which contain the chromophore [MN₃X₂].     

Chemistry of oxomolybdenum(V) and (VI) complexes incorporating oxygen,nitrogen and/or sulfur donor atoms. Part 1. Synthesis and characterization of [Mo2O3L4] (LH = HSCH2CH2CO2H,HSCH2CO2Me or HSCH2CH2CO2Me) and [MoO2L′2] (L′H = HOC6H4NH2, HOCH2C6H4NH2, HOC6H4CHO or HOC10H8N)

Reactions of an acidified aqueous solution of Na₂MoO₄ · 2H₂O with 3-mercaptopropionic acid, 2-mercaptomethylethanoate and 3-mercaptomethyl propanate yield blue oxo-bridged Mo^V complexes of the type [Mo₂O₃L₄], whereas corresponding reactions with 2-aminophenol, 2-aminobenzyl alcohol, salicylaldehyde and 2-methyl-8-hydroxyquinoline, yield yellow dioxomolybdenum(VI) complexes, [MoO₂L′₂]. All these coloured solids are sparingly soluble, even in coordinating solvents. They have been characterized by elemental and spectroscopic analysis.     

Atomic-scale study of in situ metal nanoparticle synthesis in a Ni/TiO2 system

The nucleation and evolution of Ni nanoparticles during reduction of a Ni(NO3)2.6H2O precursor supported on a commercial titania substrate have been studied in situ at atomic resolution using environmental transmission electron microscopy. An incipient wetness technique was used to prepare the starting unreduced material (10 wt % Ni precursor on titania). The Ni precursor, before reduction, shows a nonuniform distribution over the titania support. It is observed that upon reduction, the initial Ni "seed" crystal nucleates within the precursor patch. The distribution and size of the Ni nanoparticles thus generated are influenced by the distribution and size of the precursor patches. In this system, we see no evidence of preferential nucleation of Ni particles on anatase or rutile. At 350 degrees C with CO as the reducing agent, the {111} surface facets of the Ni nanoparticles are predominant during the initial stage of nucleation and growth. However, the {111} facets are partially consumed with time, indicating that they are not thermodynamically favored in the CO atmosphere. In CO and H2 atmospheres, Ni particles show a nonwetting morphology on titania, while in a mild oxidizing environment, a thin layer of NiOx is formed, thus giving rise to a morphology that is indicative of wetting of the support. This work provides fundamental information on understanding and controlling the important parameters involved in the preparation of a well-designed supported Ni catalyst using the incipient wetness technique.     

Response Surface Methodology-Based Optimisation of Agarose Gel Electrophoresis for Screening and Electropherotyping of Rotavirus

Management of rotavirus diarrhoea cases and prevention of nosocomial infection require rapid diagnostic method at the patient care level. Diagnostic tests currently available are not routinely used due to economic or sensitivity/specificity constraints. Agarose-based sieving media and running conditions were modulated by using central composite design and response surface methodology for screening and electropherotyping of rotaviruses. The electrophoretic resolution of rotavirus genome was calculated from input parameters characterising the gel matrix structure and running conditions. Resolution of rotavirus genome was calculated by densitometric analysis of the gel. The parameters at critical values were able to resolve 11 segmented rotavirus genome. Better resolution and electropherotypic variation in 11 segmented double-stranded RNA genome of rotavirus was detected at 1.96% (w/v) agarose concentration, 0.073 mol l⁻¹ ionic strength of Tris base–boric acid–ethylenediamine tetraacetic acid buffer (1.4×) and 4.31 h of electrophoresis at 4.6 V cm⁻¹ electric field strength. Modified agarose gel electrophoresis can replace other methods as a simplified alternative for routine detection of rotavirus where it is not in practice.     

Field-dependent mobility characteristics of a two-dimensional electron gas due to quasi-elastic interaction with intravalley acoustic phonons

The field-dependent mobility characteristics of the carriers in a two-dimensional electron gas (2DEG) are obtained considering the finite energy of phonons in the energy balance equation of electron-phonon system for quasi-elastic interaction with intravalley acoustic phonons. Both the high- and low-field mobility characteristics turn out to be significantly different from those that follow from the traditional approximation. The numerical results are presented for Si and GaAs. The inadequacies of the theory are pointed out and the scope for further refinement is discussed.     

Recent Progress in Bioconjugation Strategies for Liposome-Mediated Drug Delivery

In nanoparticle (NP)-mediated drug delivery, liposomes are the most widely used drug carrier, and the only NP system currently approved by the FDA for clinical use, owing to their advantageous physicochemical properties and excellent biocompatibility. Recent advances in liposome technology have been focused on bioconjugation strategies to improve drug loading, targeting, and overall efficacy. In this review, we highlight recent literature reports (covering the last five years) focused on bioconjugation strategies for the enhancement of liposome-mediated drug delivery. These advances encompass the improvement of drug loading/incorporation and the specific targeting of liposomes to the site of interest/drug action. We conclude with a section highlighting the role of bioconjugation strategies in liposome systems currently being evaluated for clinical use and a forward-looking discussion of the field of liposomal drug delivery.     

Effects of screening of the interaction potential on the mobility characteristics of degenerate surface layers in compound semiconductors at low lattice temperatures

The rates of scattering of the conduction electrons in degenerate two-dimensional electron gas in the surface of compound semiconductors at low lattice temperatures have been obtained for interaction with the piezoelectric and deformation potential acoustic phonons, under different prevailing conditions. The calculations have been carried out taking due account of the screening of the interaction potential at low temperatures where again the phonon energy cannot be neglected in comparison to the average thermal energy of the electrons and, as a result, the equipartition approximation for the phonon distribution can hardly be valid. The scattering rates thus obtained for inversion layers in GaAs and ZnO are found to depend upon the carrier energy, the lattice temperature and the level of degeneracy in quite involved manners, which are very different from what follows if one makes the simplifying approximation of negligible phonon energy or disregards the effects of screening. The mobility characteristics are then obtained using these scattering rates. The results show how the screening of the interaction potential and the finite energy of the intravalley acoustic and piezoelectric phonons significantly change the mobility characteristics of the degenerate surface layers at low lattice temperatures. The inadequacies of the present theory are pointed out and recommendations for possible refinements are discussed.     

Mathematical modelling of heat conduction in certain functionally graded composites

The aim of contribution is to formulate a certain extended version of the tolerance modelling technique for functionally graded composites. For the sake of simplicity, the considerations are restricted to the bidirectionally graded heat conductors. It is shown that the proposed approach enables to determine an entire class of mathematical models for which applications can be found in various specific problems. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamic coupling between coordinates in a model for biomolecular isomerization

To understand a complex reaction, it is necessary to project the dynamics of the system onto a low-dimensional subspace of physically meaningful coordinates. We recently introduced an automatic method for identifying coordinates that relate closely to stable-state commitment probabilities and successfully applied it to a model for biomolecular isomerization, the C(7eq)-->alpha(R) transition of the alanine dipeptide [A. Ma and A. R. Dinner, J. Phys. Chem. B 109, 6769 (2005)]. Here, we explore approximate means for estimating diffusion tensors for systems subject to restraints in one and two dimensions and then use the results together with an extension of Kramers theory for unimolecular reaction rates [A. Berezhkovskii and A. Szabo, J. Chem. Phys. 122, 014503 (2005)] to show explicitly that both the potential of mean force and the diffusion tensor are essential for describing the dynamics of the alanine dipeptide quantitatively. In particular, the signficance of off-diagonal elements of the diffusion tensor suggests that the coordinates of interest are coupled by the hydrodynamic-like response of the bath of remaining degrees of freedom.     

22pi smaragdyrin molecular conjugates with aromatic phenylacetylenes and ferrocenes: Syntheses, electrochemical, and photonic properties

Syntheses, spectroscopic, electrochemical, and third-order nonlinear optical susceptibilities of a series of 22pi smaragdyrins and their corresponding Rh(I) derivatives bearing phenylacetylene substituents and ferrocene-containing substituents are reported. The synthetic strategy involved a [3 + 2] acid-catalyzed oxidative coupling reaction of the appropriate dipyrromethane and oxatripyrrane. The desired meso substituents, such as phenylacetylenylphenyl and the ferrocenes, were incorporated to the dipyrromethane unit prior to the oxidative coupling reaction. The optical absorption, emission characteristics, and the quantum yield of the smaragdyrin conjugates depends on the nature of the substituent, nature of linker group, and the spacer length. Theoretical studies at the DFT level suggest high delocalization of electrons confined to only four of the five available heterocyclic rings for the free bases. However, upon Rh(I) metalation, the pi-electron delocalization is extended to all the heterocyclic rings. The two-photon absorption cross section (TPA) values sigma(2) measured through the open aperture Z-scan method, increases linearly with enhanced pi-electron delocalization for the smaragdyrins containing phenylacetylene substituents. The meta branching of substituents decreases sigma(2) values. Introduction of Rh(I) to the smaragdyrin cavity enhances the sigma(2) values by about 3-10 orders of magnitude, attributed to the increased aromatic character upon Rh(I) insertion. The calculated molecular electrostatic potential (MESP) and harmonic oscillator model of aromaticity (HOMA) for the free bases and the Rh(I) derivatives justifies such a conclusion. A linear correlation observed for the second oxidation potential of Rh(I) derivatives and corresponding free bases also support the increased aromaticity upon Rh(I) insertion. The electrochemical data for ferrocene-containing smaragdyrins reveal easier ring oxidation by about 50-130 mV and harder ferrocene oxidation by 40-180 mV suggesting electron-donating nature of the ferrocene upon linking with the smaragdyrin system. The TPA cross section value of 88782 GM observed for 5g represents one of the highest values known for a metalloexpanded porphyrin derivative.