Facile reduction of aromatic nitro/azido functionality on solid support employing Al/NiCl2·6H2O and Al/NH4Cl: synthesis of pyrrolo[2,1-c][1,4]benzodiazepines

An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl₂·6H₂O and Al/NH₄Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics.     

Redox reactions in nonaqueous media : Determination of organoisothiocyanates and organoisocyanates

A simple and accurate method has been developed for the determination of organoisothiocyanates and organoisocyanates based on their quantitative reaction with n-butylamine in dimethylformamide medium to form substituted thioureas and ureas, respectively. The solution is mixed with 6 to 7 times its volume of acetonitrile and an excess of carbon disulphide, which converts the residual amine quantitatively into the corresponding n-butylammonium n-butyl dithiocarbamate. The determination is completed by titrating the resulting dithiocarbamate with iodine monobromide solution in acetonitrile. The end point is detected visually by the yellow color imparted to the solution by the first drop of oxidant solution in excess. The dithiocarbamates are quantitatively oxidized to the corresponding thiuram disulphides.     

Spin crossover studies in cationic complexes of iron by using Mössbauer spectroscopy

The spin transitions in two new cationic complexes of iron, i. e., iron bipyridine formate, [Fe/bipy/₃]/HCOO/₂. 5/HCOOH/ and iron bipyridine tetrafluoro borate, [Fe/bipy/₃]/BF₄/₂. 2H₂O have been studied by using Mössbauer spectroscopy. From quadrupole splitting values, at different temperatures, it has been established that both the complexes show the coexistence of both the high spin state and the low spin state at 300 K while complete transformation to low spin state occurs at 77 K. Both compounds were prepared by electrochemical technique.     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.     

Non-aqueous cerimetric determination of thioureas

Ammonium hexanitratocerate (in acetonitrile) solution has been used as an oxidimetric reagent for the visual and potentiometric determination of thiourea and its alkyl derivatives in acetonitrile medium. The thioureas are oxidized to their corresponding disulphides. The method is simple, accurate, reliable and widely applicable.     

Supramolecular peptide helix from a novel double turn forming peptide containing a β-amino acid

A single-crystal X-ray diffraction study of the terminally protected tetrapeptide Boc-β-Ala-Aib-Leu-Aib-OMe 1 (Aib: α-aminoisobutyric acid; β-Ala: β-Alanine) reveals that it adopts a new type of double turn structure which self-associates to form a unique supramolecular helix through intermolecular hydrogen bonds. Scanning electron microscopic studies show that peptide 1 exhibits amyloid-like fibrillar morphology in the solid state.     

Use of a Water-in-Oil Microemulsion as Mobile Phase in Complexation TLC of Amino Acids on Silica Layers Impregnated with Metal Cations

JPC – Journal of Planar Chromatography – Modern TLC - A water-in-oil microemulsion has been used for the first time as a mobile phase in thin-layer chromatography of amino acids. A new...     

Physico-mechanical and free volume behaviour of guar gum filled polyurethane/polyacrylonitrile biodegradable composites

A series of different weight ratios of guar gum viz. 5, 10, 20 and 30 were incorporated into polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi interpenetrating polymer networks (SIPNs) using polyethylene glycol-400, 4,4′-diphenyl methane diisocyanate, acrylonitrile, benzoyl peroxide and new metallic catalyst. The obtained polymer composites were subjected to biodegradation studies using specific fungi Aspergillus niger. The composites are characterized for physico-mechanical properties like density and tensile behaviour of the specimens before and after biodegradation. The positron annihilation lifetime spectroscopy (PALS) was used to monitor the content of free volume before and after biodegradation. The extent of degradation was examined by change in tensile behaviour and surface morphology. The influences of fungi on mechanical and morphological behaviour of filled IPNs are found to be interesting. The free volume changes in the composite systems correlates well with the mechanical properties.     

Furan ring oxidation strategy for the synthesis of macrosphelides A and B

By using the convenient protocol for conversion of 2-substituted furans into 4-oxo-2-alkenoic acids ((i) NBS, (ii) NaClO(2)), macrosphelide B (2) was synthesized from furyl alcohol 5 (>98% ee) and acid 6 (99% ee). The protocol was first applied to the PMB ether of 5 to afford acid 13b. On the other hand, DCC condensation of acid 6 with 5 gave 16 after deprotection of the TBS group. Condensation was again carried out between 13b and 16 to furnish the key ketone 17, which upon reduction with Zn(BH(4))(2) afforded anti alcohol 18 stereoselectively (15:1). After protection/deprotection steps, the furan 18 was converted to seco acid 3 by using the furan oxidation protocol mentioned above, and lactonization of 3 with Cl(3)C(6)H(2)COCl, Et(3)N, and DMAP afforded 22 (MOM ether of 2), which upon deprotection with TFA produced 2. Transformation of 22 to macrosphelide A (1) was then investigated. Although the chelation-controlled reduction of 22 should afford the desired anti alcohol 24, Zn(BH(4))(2) at <-90 degrees C gave a 2 approximately 1:1 mixture of anti/syn alcohols. On the contrary, reduction with NaBH(4) in MeOH at -15 degrees C produced the syn isomer 23 with >10:1 diastereoselectivity. Mitsunobu inversion of the resulting C(14)-hydroxyl group and deprotection of the MOM group with TFA afforded 1. Similarly, reduction of 2 with NaBH(4) afforded the C(14)-epimer of 1 stereoselectively. The observed stereoselectivity in the reductions of 22 and 2 could be explained on the basis of computer-assisted calculation, which showed presence of the low-energy conformers responsible for the stereoselective reduction. In addition, conversion of 2 to 1 was established, for the first time.     

THE PHOTOREACTIVITY OF PYRIMIDINE-PURINE SEQUENCES IN SOME DEOXYDINUCLEOSIDE MONOPHOSPHATES AND ALTERNATING DNA COPOLYMERS

Abstract— A reversed-phase HPLC system has been developed which separates the common nucleo-bases from the 6-methylimidazo[4,5- b ]pyridin-5-one (6-MIP) produced on acid hydrolysis of a thymine-adenine photoadduct (TA*) that is formed between adjacent thymine and adenine bases in UV-irradiated polydeoxyribonucleotides. By measuring the relative amounts of adenine and 6-MIP in acid hydrolysates, this system has been used to investigate how polynucleotide conformation affects the yield of TA* in poly(dA-dT) irradiated at 254 nm. The photoreactivity of other pyrimidine-purine sequences has been examined with the deoxydinucleoside monophosphates d(TpI) and d(m⁵CpA) and with the alternating DNA copolymers poly(dA-dU), poly(dI-dC), poly(dG-dC) and poly(dA-dC).poly(dG-dT). Samples were irradiated at 254 nm in aqueous solution and in ice, and at wavelengths >290 nm with acetone as photosensitizer. A photoproduct resembling TA*, and giving 6-MIP on acid hydrolysis, was isolated from d(TpI) irradiated at 254 nm in solution or in ice; d(m⁵CpA) was comparatively unreactive. Acid hydrolysates of the irradiated DNA copolymers were screened by HPLC and by TLC and paper electrophoresis, for the presence of imidazo[4,5- b ]pyridin-5-one, 6-MIP, or other species attributable to specific photoproduct formation. By this criterion, however, none of the copolymers showed evidence of significant photoreactivity in either their single- or double-stranded conformational states. The formation of mixed pyrimidine-purine photoadducts in DNA is therefore probably restricted to T-A doublets.