The photochemistry of proaporphines: a new route to the aporphines

Proaporphines undergo light catalyzed rearrangement. Pakistanamine ($\text{1}$) is thus converted into lumipakistanine ($\text{2}$), while pronuciferine ($\text{7}$) and N-acetylnorpronuciferine ($\text{8}$) afford the corresponding C-9 hydroxylated aporphines $\text{9}$ and $\text{10}$. Possible biogenetic schemes for the formation of C-8, C-9-, and C-8,9-substituted aporphines are presented.     

Thermodynamic studies on the recognition of flexible peptides by transition-metal complexes

Strong and selective binding to a trihistidine peptide has been achieved employing Cu(2+)-histidine interactions in aqueous medium (25 mM HEPES buffer, pH 7.0). When the pattern of cupric ions on a complex matched with the pattern of histidines on the peptide, a strong and selective binding was observed. UV-vis spectroscopic studies show that the cupric ions coordinate to the histidines of the peptides. Thermodynamic studies reveal that the binding process is enthalpy driven over the entire range of working temperature (25-40 degrees C). An enthalpy-entropy compensation effect was also observed.     

Self‐Assembled Heteroleptic Zn(II) Dithiocarbamate‐Based 2D‐Interwoven Supramolecular Giant Macrocycles and Their Redox Properties

This article presents a new heteroleptic Zn(II) dithiocarbamate ( 1 ) having molecules linked together via H···H and π···π interactions to form a giant hexanuclear macrocycle. These macrocycles are connected together through S···H interactions to offer a unique two‐dimensional cloth‐like interwoven architecture in the solid state. The redox behavior of the complex deposited on the surface of a glassy carbon electrode was investigated in different pH media. The analyte was found to oxidize and reduce in a pH‐dependent irreversible manner. On the basis of the electrochemical findings, redox mechanistic pathways were proposed.     

On certain properties of linear iterative equations

An expression for the coefficients of a linear iterative equation in terms of the parameters of the source equation is given both for equations in standard form and for equations in reduced normal form. The operator that generates an iterative equation of a general order in reduced normal form is also obtained and some other properties of iterative equations are established. An expression for the parameters of the source equation of the transformed equation under equivalence transformations is obtained, and this gives rise to the derivation of important symmetry properties for iterative equations. The transformation mapping a given iterative equation to the canonical form is obtained in terms of the simplest determining equation, and several examples of application are discussed.     

Understanding the interactions in acrylic copolymer/1‐butyl‐3‐methylimidazolium chloride from solution rheology

The effects of the type and content of comonomers on the rheological properties of acrylic copolymers in 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) were explored. According to the de Gennes scaling law for solution, comparison of intrinsic viscosity and scaling analysis of the exponent in the specific viscosity‐ and relaxation time‐concentration power law indicated that solution of both polyacrylonitrile (PAN) homo‐polymer and copolymer poly(acrylonitrile‐co‐methyl acrylate) (poly(AN‐co‐MA)) in [BMIM]Cl behave in the same manner as neutral polymer in a θ‐solvent. However, [BMIM]Cl acts as a more good solvent for poly(acrylonitrile‐co‐acrylamide) (poly(AN‐co‐AM)). The dissolution and unique rheological behavior of such solutions have been attributed to the interactions between copolymer chains and [BMIM]Cl. The interactions between nitrile group (?C≡N) and 1‐butyl‐3‐methylimidazolium cation ([BMIM]⁺) should interrupt and break the dipolar‐dipolar interactions of PAN resulting in the subsequent dissolution of the polymer in [BMIM]Cl. Such interactions between ?C≡N and [BMIM]⁺ ion are still dominated by the solvating ability of poly(AN‐co‐MA) in [BMIM]Cl, even though carbonyl group (C=O) in MA repeating unit could coordinate to cation of the ionic liquid. The salvation capacity of [BMIM]Cl for poly(AN‐co‐AM) can be evidently improved due to the extra hydrogen bond interactions between ?NH₂ group of AM and anion of [BMIM]Cl. Copyright © 2012 John Wiley & Sons, Ltd.     

Molybdenum(0) and Tungsten(0) Complexes with P,S and P,Se Monooxidized Bis(phosphanyl)amine Ligands

Reactions of monooxidized thioyl and selenoyl bis(phosphanyl)amine ligands C₁₀H₇‐1‐N(P(E)Ph₂)(PPh₂) [E = S ( 1 ), Se ( 2 )] with Mo(CO)₄(pip)₂ and W(CO)₄(cod) afforded the complexes [M(CO)₄{ 1 ‐κ²P,S}] [M = Mo ( 3 ), W ( 4 )] and [M(CO)₄{ 2 ‐κ²P,Se}] [M = Mo ( 5 ), W ( 6 )]. Complexes 3 – 6 were characterized by multinuclear NMR (¹H, ¹³C, ³¹P, and ⁷⁷Se NMR) and IR spectroscopy. Crystal‐structure determinations were carried out on 3 , 5 , and 6 , which represent the first examples of structurally characterized complexes of such ligands with group‐6 metal carbonyls.     

Effect of displacement on resistance and capacitance of polyaniline film

This paper investigates the properties of displacement sensors based on polyaniline (PANI) films. About 1 wt% of PANI micropowder is mixed and stirred in a solution of 90 wt% water and 10 wt% alcohol at room temperature. The films of PANI are deposited from solution by drop-casting on Ag electrodes,which are preliminary deposited on glass substrates. The thicknesses of the PANI films are in the range of 20 μm-80 μm. A displacement sensor with polyaniline film as an active material is designed and fabricated. The investigations showed that,on average,the AC resistance of the sensor decreases by 2 times and the capacitance accordingly increases by 1.6 times as the displacement changes in the range of 0 mm-0.5 mm. The polyaniline is the only active material of the displacement sensor. The resistance and capacitance of the PANI changes under the pressure of spring and elastic rubber,and this pressure is created by the downward movement of the micrometer.     

Low temperature M?ssbauer and DC magnetization studies in nano-sized Ni substituted Co�CZn ferrites

Studies in the series of nano ferrites pertaining to the stoichiometry Ni_xCo_0.5???xZn_0.5Fe₂O₄, (0?? x ??0.5) show that contrary to the trend in bulk Co?CZn and Ni?CZn ferrites, the observed saturation magnetization of Ni?CZn ferrite (x = 0.5) is larger than Co?CZn ferrite (x = 0) and are due to finite size effects. This is evident from calculations which show that the magnetic particle sizes are 1.6 nm for Co?CZn ferrite and 2.4 nm for Ni?CZn whereas their average crystallite sizes are 5 to 3 nm respectively. Low temperature Mössbauer spectroscopic studies show that this can be attributed to an increase in an ordered core with the increase in Ni content which is reflected as a corresponding increase in the saturation magnetization.     

Regioselective organocadmium alkylations of substituted quinones.

A series of substituted quinones was alkylated with diethylcadmium. Regiochemistry of addition shifted from quinol formation to conjugate addition as a function of the steric and electronic effects of the substituents.     

Synthesis and biological evaluation of bile acid dimers linked with 1,2,3-triazole and bis-beta-lactam

We report herein the synthesis and biological evaluation of bile acid dimers linked through 1,2,3-triazole and bis-beta-lactam. The dimers were synthesized using 1,3-dipolar cycloaddition reaction of diazido bis-beta-lactams , and terminal alkynes derived from cholic acid/deoxycholic acid in the presence of Cu(i) catalyst (click chemistry). These novel molecules were evaluated in vitro for their antifungal and antibacterial activity. Most of the compounds exhibited significant antifungal as well as antibacterial activity against all the tested fungal and bacterial strains. Moreover, their in vitro cytotoxicities towards HEK-293 and MCF-7 cells were also established.