Surface modification of semiconductor photoelectrodes for better photoelectrochemical performance

The present paper describes the modification and solar hydrogen production studies employing a new semiconductor-septum (SC-SEP) photoelectrode ns-TiO₂/In₂O₃ based photoelectrochemical solar cell. The current-voltage characteristics of the above SC-SEP cell revealed that an enhancement in short-circuit current (I_SC) up to three times (5 ～ 14.6 mA cm^?2). The optimum hydrogen production rate was found to be 11.8 lh^?1 m^?2 for 5M H₂SO₄ and with a further increase in H₂SO₄ concentration, the hydrogen production rate was found to be invariant. In yet another part of our study instead of using new SC-SEP solar cell design, we used another new oxide material form such as ns-TiO₂/WO₃. The ns-TiO₂/WO₃ exhibited a high photocurrent and photo-voltage of 15.6 mA cm^?2, 960 mV, respectively. The ns-TiO₂/WO₃ electrode exhibited a higher hydrogen gas evolution rate of 13.8 lh^?1 m^?2. Evidences and arguments are put forward to show that, whereas for the bare ns-TiO₂ electrode, the improvement in the performance of this photo-electrode compared with its original form was due to the higher quantum yield. In the case of ns-TiO₂/In₂O₃ and ns-TiO₂/WO₃ photo-electrodes, the improvement is due to the improved spectral response resulting from decrease of energy band gap.     

New parasite inhibitors encompassing novel conformationally-locked 5'-acyl sulfamoyl adenosines

We describe the design, synthesis and biological evaluation of conformationally-locked 5'-acyl sulfamoyl adenosine derivatives as new parasitic inhibitors against Trypanosoma and Leishmania. The conformationally-locked (3'-endo, North-type) nucleosides have been synthesized by covalently attaching a 4'-CH(2)-O-2' bridge () across C2'-C4' of adenosine in order to reduce the conformational flexibility of the pentose ring. This is designed to decrease the entropic penalty for complex formation with the target protein, which may improve free-energy of stabilization of the complex leading to improved potency. Conformationally-locked 5'-acyl sulfamoyl adenosine derivatives (16-22) were tested against parasitic protozoans for the first time in this work, and showed potent inhibition of Trypanosoma cruzi, Trypanosoma brucei, Trypanosoma rhodesiense and Leishmania infantum with IC(50) = 0.25-0.51 μM. In particular, the potent 5'-pentanyl acyl sulfamoyl adenosine derivative 17 (IC(50) = 0.25 μM) against intracellular L. infantum amastigotes and Trypanosoma subspecies is interesting in view of its almost insignificant cytotoxicity in murine macrophage host cells (CC(50) >4 μM) and in diploid human fibroblasts MRC-5 cell lines (CC(50) 4 μM). This work also suggests that variable alkyl chain length of the acyl group on the acylsulfamoyl side chain at 5' can modulate the toxicity of 5'-O-sulfamoylnucleoside analogues. This conformationally-locked sulfamoyl adenosine scaffold presents some interesting possibilities for further drug design and lead optimization.     

Synthesis and Characterization of Amphiphilic Block Copolymer by Block Copolymerization of Butadiene and Acrylamide using Macroazoinitiator

Abstract

Macroazoinitiator (MAI) was prepared from hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐azobis‐4‐cyanopentanoic acid by direct polycondensation in the presence of 1‐methyl‐2‐chloropyridinium iodide at room temperature. This MAI used for block copolymerization of AAm at 60°C gave the best results in chloroform but the formation of a crosslinked product could not be ruled out in dioxane. It was inferred that for production of a linear block copolymer, homogeneous reaction mixture was required.

The resulting products were characterized by spectral studies IR and NMR, viscosity measurements. Distinct phase segregation of hydrophobic and hydrophilic blocks was evident through DSC analysis.     

SYNTHESIS AND SPECTROSCOPIC STUDIES OF SOME FUNGITOXIC ORGANOLEAD(IV) COMPLEXES OF SULFUR AND NITROGEN DONOR LIGANDS

Abstract

Some organolead(IV) complexes derived from biologically active sulfur and nitrogen donor ligands have been synthesized and characterized by elemental analyses, molecular weight determinations and conductivity measurements. The trigonal bipyramidal and octahedral geometries for these complexes have been proposed on the basis of electronic, infrared and NMR (¹H and ¹³C) spectral evidences. The antifungal activity of some of the ligands and their complexes have also been evaluated against Fursarium oxysporum SCW. ex Frics f. sp. Ciceri (Pedwick) subram.     

Synthesis and Characterization of Some Heteroaromatic Derivatives of 3‐But‐2‐enoyl‐chromen‐2‐one and Their Potential as Anti‐inflammatory Agents

A novel series of chromen‐2‐ones containing pyrazole, isoxazole, oxazine, and thiazine substitutions have been synthesized by reacting 3‐[3‐(4‐chloro‐phenyl)‐acryloyl]‐chromen‐2‐one and 3‐[3‐(3‐methoxy‐phenyl)‐acryloyl]‐chromen‐2‐one with various cyclizing agents such as hydrazine, phenylhydrazine, urea, and thiourea. The structures of all the synthesized compounds were confirmed by the use of IR, ¹H‐NMR, mass spectroscopy, and elemental analysis data. All the newly synthesized compounds were evaluated for their anti‐inflammatory activity at a dose of 100 mg/kg body weight in carrageenan‐induced rat paw edema model. The entire series of the compounds exhibited moderate to good anti‐inflammatory activity, with the percentage inhibition of edema formation ranging from 39.99 to 63.15 against the reference drug ibuprofen (100 mg/kg) that showed 78.96% inhibition at the third hour. Compounds 3a , 3c , and 3d showed good inhibitory activity, whereas compounds 3b , 3e , 3f , and 3j showed moderate inhibitory activity at the third hour.     

An efficient synthesis of 4,5-dihydronaphtho[2,1-b]furan through a novel ring transformation of 2H-pyran-2-one

An innovative route for the synthesis of substituted naphtho[2,1-b]furan has been delineated through a ring transformation reaction of suitably functionalized 2H-pyran-2-ones by reaction with 6,7-dihydro-5H-benzofuran-4-one, in good yield.     

Quantum yields for product formation in the 120-133 nm photodissociation of O2

The photodissociation of O(2) in the region from 120-133 nm has been investigated using product imaging. The spectrum in this region is dominated by transitions from the ground state to the first three vibrational levels of the E (3)Sigma(u) (-) state. The O((1)D)+O((3)P) channel is the only product channel observed by product imaging for dissociation at either 124.4 nm or 120.4 nm. The O((1)D(2)) product is aligned in the molecular frame in such a way that its J vector is perpendicular to the relative velocity vector between the O((1)D) and the O((3)P). The variation in the anisotropy of dissociation is approximately predicted by considering transitions on individual lines and then taking into account the coherent excitation of overlapping resonances. At 132.7 nm, both the O((1)D)+O((3)P) and the O((3)P)+O((3)P) channels are observed with branching ratios of 0.40+/-0.08 and 0.60+/-0.09, respectively. At 130.2 nm, the quantum yield for production of O((1)D) is 0.76+/-0.28.     

Do N-heterocyclic aromatic rings prefer π-stacking?

The IR-UV double resonance spectroscopy of phenylacetylene complexes with triazine, pyrazine and pyridine in the acetylene C-H group of phenylacetylene was investigated. These spectra indicate that in the complexes of triazine, pyrazine and pyridine the acetylenic group is minimally perturbed and the predominant interaction is with the π electron density of the phenyl ring of phenylacetylene. Geometries of the complexes optimized at M06-2X/aug-cc-pVDZ and MP2/aug-cc-pVDZ levels, combined with highly accurate energy calculations at the complete basis set (CBS) limit of CCSD(T), indicate the formation of π-stacked complexes in all the three cases. Additionally, a C-H...N hydrogen-bonded complex between pyridine and phenylacetylene was also observed. The present results indicate that N-heterocyclic aromatic rings favor formation of π-stacked complexes.     

Synthesis and antimicrobial activities of sulfonohydrazide‐substituted 8‐hydroxyquinoline derivative and its oxinates

Looking at the pharmacological importance of 8‐hydroxyquinolines and sulfonamides, in the present study, a novel bi‐dentate ligand 4‐amino‐N′‐[(8‐hydroxyquinoline‐5‐yl)methyl] benzenesulfonohydrazide (AHQMBSH) having above both moieties within a single molecular framework was synthesized by the reaction of N‐acetamidobenzene sulfonohydrazide with 5‐chloromethyl‐8‐hydroxyquinoline hydrochloride. Its metal(II) oxinates were also prepared with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) salts. All the above compounds were investigated by physicochemical analyses, thermogravimetric analysis and spectroscopic techniques. Antimicrobial activities for the above prepared compounds were carried out using the agar‐plate method against various strains of bacteria (Staphylococcus aureus, Bacillus subtillis, Pseudomonas aerugionsa, Escherichia coli) and fungi (Aspergillus niger and Aspergillus flavous). The results show a significant increase in antimicrobial and antifungal activities of AHQMBSH compared with the parent 8‐hydroxyquinoline and sulfonamides. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthetic approaches to 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines

The preparation of 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines, exemplified by 5-[3-(benzyloxy)phenyl]-7-cyclobutylimidazo[5,1-f][1,2,4]triazin-4-amine, was developed through a linear and three convergent synthetic strategies, with the latter providing the greatest flexibility for diversification at the 5-position at the last step of the synthesis.