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].     

Differential thermal analysis studies on the crystallization of strontium tungstate from sodium tungstate melt. Nucleation mechanism and induction periods

The nucleation mechanism, kinetics and induction periods in strontium tungstate crystallization from sodium tungstate melt in platinum crucibles were investigated by differential thermal analysis. Heterogeneous nuclei first formed on the metal platinate particles within the solution during the induction periods (¯t); the main crystal growth started only after ¯t and few new nuclei were then formed. At any crystallization temperature, ¯t varied inversely with the cooling rate (R _T), and with the rate (R_C) of development of excess solute concentration according to the relation ¯t = 1/(k ₁ R _c ), wherek ₁ and are constants. The critical temperature (¯T), critical supersaturation(¯ S), k ₁ and were evaluated.

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Zusammenfassung Der Keimbildungsmechanismus, sowie die Kinetik und die Induktionsperioden wurden bei der Kristallisation von Strontiumwolframat aus Natriumwolframatschmelzen in Platintiegeln durch Differentialthermoanalyse untersucht. Die heterogenen Kristallkeime wurden zuerst während der Induktionsperiode () an den Metallplatinat-Teilchen in der Lösung gebildet: das Hauptkristallwachstum begann erst nach und nachfolgend wurden einige neue Keime gebildet. Bei jeder Kristallisationstemperatur änderte sich umgekehrt proportional zu den Abkühlungsgeschwindigkeiten (R _T) und den Geschwindigkeiten (R _c) der Bildung überschüssig gelösten Materials, entsprechend der Gleichung = 1/(k ₁ R _c , wobeik ₁ und Konstanten sind. Die kritische Temperatur (¯T), die kritische Übersättigung (¯S),k ₁ und wurden bewertet.

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Résumé On a étudié par analyse thermique différentielle le mécanisme de nucléation ainsi que la cinétique et les périodes d'induction de la cristallisation du tungstate de strontium, à partir des bains fondus de tungstate de sodium, dans des creusets de platine. Des noyaux hétérogènes se forment d'abord sur les particules de platinate métallique dans la solution, au cours des périodes d'induction (): la croissance principale des cristaux ne commence qu'après et il se forme alors quelques noyaux nouveaux. A une température quelconque de cristallisation, varie de façon inverse avec les vitesses de refroidissement (R _T) et les vitesses de développement (R _c ) de concentrations de sursaturation de la substance en solution, selon la relation = 1/(k ₁ R _c , oùk ₁ et sont des constantes. On a évalué la température critique (¯T), la sursaturation critiques (¯S),k ₁ et.

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, . - (¯ t). ¯t . - ,¯t (R _T), (R _c) ¯t=1/(K₁ R _c ), ₁ — . (¯), (_-S), K₁ .

     

Influence of methanol as a buffer additive on the mobilities of organic cations in capillary electrophoresis

The mobilities of a series of aromatic ammonium ions, ranging in charge from +1 to + 3, were investigated by capillary electrophoresis using buffers consisting of 0-75% v/v methanol. This is an extension of our previous studies involving anion mobility in methanol-water media [1]. Absolute mobilities were determined by extrapolation of the effective mobilities to zero ionic strength according to the Pitts' equation. For all of the buffer compositions studied, the ionic strength effect increased with increasing cation charge, and varied as a function of solvent 1/eta epsilon (1/2) as predicted by the electrophoretic term within the Pitts' equation. In the presence of methanol, the ionic strength effects became more dramatic. The absolute mobilities of the cations were altered by the addition of methanol to the electrophoretic media. For example, at 75% MeOH, a migration order reversal was observed between the + 2 and + 3 ammonium ions. These solvent-induced selectivity changes are attributed to dielectric friction. As predicted by the Hubbard-Onsager dielectric friction model, dielectric friction increased with increasing methanol content and with increasing analyte charge. Further, the changes in cation mobility correlated to the changes in solvent relaxation time (tau), epsilon and eta. Although not predicted by the Hubbard-Onsager theory, the + 3 ammonium ion experienced more dielectric friction than the - 3 sulfonate and - 3 carboxylate investigated previously [1]. This apparent failure of the Hubbard-Onsager model results from its continuum nature, whereby ion-solvent interactions are not taken into account.     

Synthesis and characterization of copper(I) amidinates as precursors for atomic layer deposition (ALD) of copper metal

A series of copper(I) amidinates of the general type [(R'NC(R)NR')Cu](2) (R' and R' = n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; R = methyl, n-butyl) have been synthesized and characterized. These compounds are planar dimers, bridged by nearly linear N-Cu-N bonds. Their properties (volatility, low melting point, high thermal stability, and self-limited surface reactivity) are well-suited for atomic layer deposition (ALD) of copper metal films that are pure, highly conductive, conformal, and strongly adherent to substrates.     

Synthesis and structural studies of peptides containing a glucose-derived furanoid sugar amino acid

Conformational analysis of peptides containing a glucose-derived furanoid sugar amino acid (Gaa) by detailed NMR and constrained MD studies revealed that peptides with repeating Gaa-Leu-Val units had conformational signatures very similar to those of linear homooligomers of Gaa.     

Nonclassical 5-substituted tetrahydroquinazolines as potential inhibitors of thymidylate synthase

Classical inhibitors of thymidylate synthase such as N^l0-propargyl-5,8-dideazafolic acid (1), N-(5-[N-(3,4-dihydro-2-methyl-4-oxoquinazolin-6-ylmethyl)-N-methylamino]-2-thenoyl)-L-glutamic acid (ZD1694, 2) and N-[2-amino-4-oxo-3,4-dihydro(pyrrolo[2,3-d]pyrintidin-5-yl)ethylbenzoyl]-L-glutamic acid (LY231514, 3) while potent, suffer from a number of potential disadvantages, such as impaired uptake due to an alteration of the active transport system required for their cellular uptake, as well as formation of long acting, non-effluxing polyglutamates via the action of folylpolyglutamate synthetase, which are responsible for toxicity. To overcome some of the disadvantages of classical inhibitors, there has been considerable interest in the synthesis and evaluation of nonclassical thymidylate synthase inhibitors, which could enter cells via passive diffusion. In an attempt to elucidate the role of saturation of the B-ring of non-classical, quinazoline antifolate inhibitors of thymidylate synthase, analogues 7-17 were designed. Analogues 13-17 which contain a methyl group at the 7-position, were synthesized in an attempt to align the methyl group in an orientation which allows interaction with tryptophan-80 in the active site of thymidylate synthase. The synthesis of these analogues was achieved via the reaction of guanidine with the appropriately substituted cyclohexanone-ketoester. These ketoesters were in turn synthesized via a Michael addition of the appropriate thiophenol with 2-carbethoxycyclohexen-1-one or 5-methyl-2-carbethoxycyclo-hexen-1-one to afford a mixture of diastereomers. The most inhibitory compound was the 3,4-dichloro, 7-methyl derivative 17 which inhibited the Escherichia coli and Pneumocystis carinii thymidylate syntheses 50% at 5 × 10⁵ M. Our results confirm the importance of the 7-CH₃ group and electron withdrawing groups on the aromatic side chain for thymidylate synthase inhibition.     

Nuclear magnetic resonance and optosensing properties of di-2-thienyl ketone p-nitrophenylhydrazone (DSKNPH) in non-aqueous media

The compound di-2-thienyl ketone p-nitrophenylhydrazone (DSKNPH) melting point 168-170 °C was isolated in good yield from the reaction between di-2-thienyl ketone (DSK) and p-nitrophenylhydrazine in refluxing ethanol containing a few drop of concentrated HCl. Nuclear magnetic resonance studies on DSKNPH in non-aqueous solvents revealed strong solvent and temperature dependence due to solvent-solute interactions. Optical measurements on DSKNPH in DMSO in the presence and absence of KPF₆ gave extinction coefficients of 83,300±2000 and 25,600±2000 M⁻¹ cm⁻¹ at 612 and 427 nm at 295 K. In CH₂Cl₂, extinction coefficient of 34,000±2000 M⁻¹ cm⁻¹ was calculated at 422 nm. When DMSO solutions of DSKNPH were allowed to interact with DMSO solutions of NaBH₄ the low energy electronic state becomes favorable and when DMSO solutions of DSPKNPH where allowed to interact with DMSO solutions of KPF₆ or NaBF₄, the high energy electronic state becomes favorable. The reversible BH₄⁻/BF₄⁻ interconversion points to physical interactions between these species and DSKNPH and hints to the possible use of DSKNPH as a spectrophotometric sensor for a variety of physical and chemical stimuli. Thermo-optical measurements on DSKNPH in DMSO confirmed the reversible interconversion between the high and low energy electronic states of DSKNPH and allowed for the calculations of the thermodynamic activation parameters of DSKNPH. Changes in enthalpy (ΔH^∅) of +57.67±4.20; 27.15±0.90 kJ mol⁻¹, entropy (ΔS^∅) of +160±12.88; 83±2.91 J mol⁻¹ and free energy (ΔG^∅) of −8.52±0.40; 2.66±0.25 kJ mol⁻¹ were calculated at 295 K in the absence and presence of NaBH₄, respectively. Manipulation of the equilibrium distribution of the high and low energy electronic states of DSKNPH allowed for the use of these systems (DSKNPH and surrounding solvent molecules) as molecular sensors for group I and II metal ions. Group I and II metal ions in concentrations as low as 1.00×10⁻⁵ M can be detected and determined using DSKNPH in DMSO.     

Reclaiming of ground rubber tire (GRT) by a novel reclaiming agent

The present paper describes the mechanical reclaiming of ground rubber tire (GRT) by tetra methyl thiuram disulfide (TMTD), a multi-functional reclaiming agent. The versatility of the proposed agent is that it acts as a reclaiming agent during reclaiming and as a curing agent during revulcanization of the reclaimed sample. Reclaiming of GRT was carried out on an open two roll mixing mill at various time intervals and different concentrations of the reclaiming agent (TMTD). The degree of reclaiming was evaluated by measurement of the gel content, inherent viscosity of sol rubber, Mooney viscosity of the reclaimed rubber, crosslink density, swelling ratio and molecular weight between two crosslink bonds as a function of milling time. Also, the influence of the gel content on crosslink density at various time intervals on the open two roll mixing mill was determined. A unique correlation between gel fraction and crosslink density obtained at various time intervals and concentrations of reclaiming agent indicated that an optimization of the concentration of TMTD and milling time has a positive influence on improving the efficiency of reclaiming. The reclaiming conditions have been optimized in view of the mechanical properties of the revulcanized GRT and the aging resistance properties of the revulcanized reclaim. The influence of the concentration of sulfur on the mechanical properties in the revulcanized reclaim was also studied. Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the revulcanized reclaim rubber when reclamation is carried out by optimum concentration of TMTD after maximum time of reclaiming.     

Mass transfer of a neutral solute in polyelectrolyte grafted soft nanochannel with porous wall

A soft nanochannel involves a soft interface that contains a polyelectrolyte layer (PEL) sandwiched between a rigid surface and a bulk electrolyte solution. Mass transfer of a neutral solute in a combined electroosmotic and pressure driven flow through a polyelectrolyte grafted charged nanochannel with porous wall is presented in this work. Assuming the PEL as fixed charged layer and PEL-electrolyte interface as a semi-penetrable membrane, analytical solutions were obtained for potential distributions (for small wall potential). Velocity profiles were also derived in the same domains, for both inside and outside the PEL. Convective-diffusive species balance equation was semi-analytically solved inside the PEL. Expression of length averaged Sherwood number was also obtained and effects of different parameters, namely, drag parameter (α), Debye parameter , and PEL thickness were studied in detail. The variation of permeate concentration and permeation flux across the porous wall was obtained.     

Upper bounds on the fine structure constant and on nucleon magnetic moments in terms of Compton scattering cross sections

We derive and compare with experimental data the bound

$\text{α??λm}{}_{\mathrm{<mtext>p</mtext>}}\text{?m}{}_{\mathrm{<mtext>p</mtext>}}\text{ν}{}^2{}_1\text{2π}{}^2\text{∫}\text{ν}{}_0\text{∞}\text{d}\text{ν′σ}{}_{\mathrm{<mtext>tot</mtext>}}\text{(ν′)}\text{(ν′}{}^2\text{+ν}{}^2{}_1\text{)}\text{+2πm}{}_{\mathrm{<mtext>p</mtext>}}\text{∫}\text{ν}{}_0\text{∞}\text{ν′}{}^2\text{d}\text{ν′σ}{}_{\mathrm{<mtext>tot</mtext>}}\text{(ν′)}\text{(ν′}{}^2\text{+ν}{}^2{}_1\text{){ν′}{}^2\text{(}\text{d}\text{σ}\text{d}\text{t)}{}_0\text{+πλ}{}^2\text{+2ν′|λ|}\text{π}\text{(}\text{d}\text{σ}\text{d}\text{t)}{}_0\text{?}\text{σ}{}^2{}_{\mathrm{<mtext>tot</mtext>}}\text{16π}\text{}}{}^{\mathrm{?1}}$

, where α is the fine-structure constant, m_p the proton mass, ν₀ the photo-pion production threshold, σ_tot and $\text{(}\text{d}\text{σ}\text{d}\text{t}\text{)}{}_0$ are the unpolarized total hadronic photo-absorption cross section on protons and the unpolarized forward differential cross section for proton Compton scattering at photon-lab energy ν′, and λ and ν₁ are any real numbers. We derive similar bounds on proton and neutron magnetic moments.