Synthesis and Characterization of Push-Pull Porphyrins

A series of “push-pull” porphyrins with 4-nitrophenyl and 4-aminophenyl substituents were synthesized and separated by flash column chromatographic techniques. They were fully characterized by elemental analysis, FAB-MS, FTIR, UV-visible, and ¹H NMR spectroscopies. The unsymmetrical π-electron distribution of the porphyrins caused by the donor (amino) and acceptor (nitro) substituents were investigated by ¹H NMR technique. The pyrrole-H resonance positions can be correlated to the Hammett σ constants of the substituents. Although with strong donor and acceptor substituents, UV-visible spectra show the push-pull porphyrins have rather weak solvatochromism and hence limited intramolecular charge-transfer character.     

Applications of Macrocyclic Polyethers in Analytical Sensors and Ion Separation

Artificial macrocyclic polyethers were synthesized and applied as neutral carriers for ion-selective PVC membrane electrodes, ion-chromatographic packing materials, extractants and adsorbents for ion separation, coating materials for piezoeletrical membrane sensors for organic species, and ion-transport carriers through liquid membranes. Ion-selective electrodes such as those for K⁺ Na⁺, UO₂²⁺, Cs⁺, Pb²⁺, Fe³⁺, Hg²⁺ and Ag⁺ ions based on crown ether-phosphotungstic acid (PW) precipitates and dithio crown ethers respectively were prepared and showed good sensitivity and selectivity. Crown ether-PW precipitates were applied as adsorbents of rare-earth ions and some common heavy-metal ions. Some rare-earth ions were easily extracted with crown ethers, especially 15-crown-5. Poly(stytene/divinyl benzene) cryptand-22 resin was synthesized and applied as a bifunctional stationary phase of ion chromatography to separate bom cations and anions, even some organic carboxylate geometric isomers. Crown ethers such as mono-benzo-15-crown-5 was successfully applied as a coating material on piezoelectric quartz membrane sensors for some organic species. The oscillation frequency of the crown-ether quartz-membrane sensor was sensitive to organic vapours such as amines and alcohols. Upon adsorption of organic species on the crown-ether quartz membrane, the oscillation frequency of the sensor decreased obviously. Special crown ether such as dibenzo-16-crown-5-oxyacetic acid, decyl-cryptand-22 and 1, 4-dihydro-pyridine-18-crown-5 were synthesized and successfully applied as ion-transport carriers (ionophores) for transport of Na⁺ K⁺ and Mg²⁺ ions through liquid membranes.     

Selective benzylic lithiation of N-Boc-2-phenylpiperidine and pyrrolidine: expedient synthesis of a 2,2-disubstituted piperidine NK1 antagonist

Unlike the lithiation of N-Boc-2-alkylpiperidines, which occurs at the 6-position, N-Boc-2-phenylpiperidine and N-Boc-2-phenylpyrrolidine can be lithiated exclusively at the 2-position. The tertiary carbanions can be trapped with a variety of electrophiles. This chemistry was used for the synthesis of a potent NK₁ ligand (K_i = 0.3 nM). The bioactive configuration at the piperidine quaternary center was determined by X-ray analysis to be (S).     

Complexation of the triply-bonded dirhenium(II) complex Re(2)Cl(4)(mu-dppm)(2) (dppm = Ph(2)PCH(2)PPh(2)) by up to three acetylene molecules

The triply bonded dirhenium(II) synthons Re(2)X(4)(mu-dppm)(2) (X = Cl, Br; dppm = Ph(2)PCH(2)PPh(2)) react with acetylene at room temperature in CH(2)Cl(2) and acetone to afford the bis(acetylene) complexes Re(2)X(4)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH) (X = Cl (3), Br(4)). Compound 3 has been derivatized by reaction with RNC ligands in the presence of TlPF(6) to give unsymmetrical complexes of the type [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(CNR)]PF(6) (R = Xyl (5), Mes (6), t-Bu (7)), in which the RCN ligand has displaced the chloride ligand cis to the eta(2)-HCCH ligand. The reaction of 3 with an additional 1 equiv of acetylene in the presence of TlPF(6) gives the symmetrical all-cis isomer of [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(2)]PF(6) (8). The two terminal eta(2)-HCCH ligands in 8 are very labile and can be displaced by CO and XylNC to give the complexes [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(L)(2)]Y (L = CO when Y = PF(6) (9); L = CO when Y = (PF(6))(0.5)/(H(2)PO(4))(0.5) (10); L = XylNC when Y = PF(6) (11)). These substitution reactions proceed with retention of the all-cis stereochemistry. Single-crystal X-ray structure determinations have been carried out on complexes 3, 5, 8, 10, and 11. In no instance have we found that the acetylene ligands undergo reductive coupling reactions.     

Preparation of Functionalized Imidazolium Salts under Microwave Irradiation

A direct alkylation of a substituted imidazole to prepare the corresponding functionalized ionic liquid has been developed in excellent yields under microwave irradiation.     

Urinary d‐lactate levels reflect renal function in aristolochic acid‐induced nephropathy in mice

Urinary d ‐lactate is highly correlated to diabetic nephropathy – a progressive kidney disease in renal glomeruli. In this study, we used a C3H/3e mouse model to investigate the relationship between urinary d ‐lactate and aristolochic acid nephropathy where the glomerular structure is not affected. The nephropathy was induced using intravenous injections of aristolochic acid at a dosage of 10 mg/kg per day for 5 days and was characterized biochemically and histologically. The urinary excretions of proteins, N‐acetyl‐β‐d ‐glucosaminidase and serum creatinine were determined and connected to histological conventional findings. Urinary d ‐lactate was analyzed using column‐switching high‐performance liquid chromatography with fluorescence detection. The results showed a remarkable increase of urinary markers, including of urinary proteins and N‐acetyl‐β‐d ‐glucosaminidase, and the histological examination confirmed a diagnosis of acute tubule necrosis. The ratio of d ‐lactate to creatinine in the urine of aristolochic acid‐treated mice was approximately 36 times greater than that of the mice in the control group (p < 0.05). The ratios for the two groups of mice were 311.00 ± 71.70 and 8.60 ± 1.80 µmol/mmol creatinine, respectively. These data confirm in vivo that urinary d ‐lactate reflects renal injury conditions in aristolochic acid‐treated mice and may be a marker for the assessment of nephropathy. Copyright © 2013 John Wiley & Sons, Ltd.     

Mesogenic and optical properties of α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes

Liquid crystalline α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes (bi‐ and ter‐thiophene) have been synthesized and their mesogenic behaviour and optical properties investigated. They all exhibited a nematic mesophase, and compounds with long alkoxy chains also showed lamellar phases. Increasing the number of thiophene units increased both the transition temperatures and the mesophase ranges. As for their optical properties, incorporating more thiophene units results in red‐shifted absorption and emission spectra, slightly enhanced quantum efficiency, and a larger Stoke's shift. Most importantly, in terms of the absorption and emission maxima, the incorporation of one 4‐alkoxyphenylethynyl moiety was found to be equivalent to adding one thiophene ring.     

Reactive Polymers and Oligomers from Cyclic Ethers and Cyclic Sulfides

(2-Bromoethyl)oxirane is converted in 39% yield to poly-[(2-bromoethyl)oxirane] of inherent viscosity 1.99 dL/g. The AlEt₃/H₂O/AcAc system is a very effective initiator for the polymerization of (2-bromoethyl)oxirane. Poly[(2-bromoethyl)-oxirane] is a white elastomer, soluble in CHCl₃ and insoluble in CH₃OH. Polyether-urethane hydrogels are prepared by the room temperature crosslinking of poly[(3-hydroxypropyl)oxirane] with aliphatic or aromatic diisocyanates. These networks absorb 100–200% of their weights in water, and can be prepared in transparent form with potential application as biomaterials or contact lenses.     

THEN FILM CELLS BASED ON CuInSe2

Abstract

Using thin film devices of the form CdS(n)/CuInSe₂(p) fabricated on electrodeposited CuInSe₂, electrical and optical measurements have been made. From temperature-dependent I-V measurements, it was observed that the recombination current became progressively more important as the temperature was decreased. Results of dark C-V measurements indicated that CuInSe₂ films with carrier concentrations in the range from 10¹⁵ to 10¹⁷ cm^?3 can be easily prepared using the electrodeposition method. Photoresponse of the devices was also measured, giving an essentially flat region in the range from 0.6 to 1.0 micron. At wavelengths beyond 1 micron, the quantum efficiency decreased continuously with the increase in the wavelength. This continuous decrease in the quantum efficiency could be due to the presence of interface states as suggested by the photo capacitance measurements.