Novel applications of photobiocatalysts in chemical transformations.

Photocatalysis has proven to be an effective approach for the production of reactive intermediates under moderate reaction conditions. The possibility for the green synthesis of high-value compounds using the synergy of photocatalysis and biocatalysis, benefiting from the selectivity of enzymes and the reactivity of photocatalysts, has drawn growing interest. Mechanistic investigations, substrate analyses, and photobiocatalytic chemical transformations will all be incorporated in this review. We seek to shed light on upcoming synthetic opportunities in the field by precisely describing mechanistically unique techniques in photobiocatalytic chemistry.

Metal-free visible light mediated direct C-H amination of benzoxazole with secondary amines.

An efficient visible light mediated, eosin Y catalyzed direct C-H oxidative amination of benzoxazoles with secondary amines has been developed, which providing a straightforward, green, and environmentally benign access to a wide variety of substituted benzoxazole-2-amines under mild reaction conditions. The biological studies such as drug-likeness and molecular docking are also carried out on the molecule.

Visible light-induced photoredox catalyzed C-N coupling of amides with alcohols.

A visible-light-mediated method for the construction of N-monoalkylated products from easily available benzamides and benzyl alcohol in the presence of eosin Y has been developed. The reaction proceeded smoothly, for a wide range of derivatives of benzamides and benzyl alcohols, to give the desired products in good to excellent yields. Biological studies, such as those on drug-likeness and molecular docking, are carried out on the molecules.

Molecular Epidemiology and Polymorphism Analysis in Drug-Resistant Genes in M. tuberculosis Clinical Isolates from Western and Northern India.

Introduction: The mechanistic details of first line drug (FLD) resistance have been thoroughly explored but the genetic resistance mechanisms of second line injectables, which form the backbone of the combinatorial drug resistant tuberculosis therapy, are partially identified. This study aims to highlight the genetic and spoligotypic differences in the second line drug (SLD) resistant and sensitive Mycobacterium tuberculosis (Mtb) clinical isolates from Mumbai (Western India) and Lucknow (Northern India). Methods: The rrs, eis, whiB7, tlyA, gyrA and gyrB target loci were screened in 126 isolates and spoligotyped. Results: The novel mutations were observed in whiB7 loci (A43T, C44A, C47A, G48T, G59A and T152G in 5'-UTR; A42C, C253T and T270G in gene), tlyA (+CG200, G165A, C415G, and +G543) and gyrB (+G1359 and +A1429). Altogether, the rrs, eis, and whiB7 loci harbored mutations in ~86% and ~47% kanamycin resistant isolates from Mumbai and Lucknow, respectively. Mumbai strains displayed higher prevalence of mutations in gyrA (~85%) and gyrB loci (~13%) as compared to those from Lucknow (~69% and ~3.0%, respectively). Further, spoligotyping revealed that Beijing lineage is distributed equally amongst the drug resistant strains of Mumbai and Lucknow, but EAI-5 is existed at a higher level only in Mumbai. The lineages Manu2, CAS1-Delhi and T1 are more prevalent in Lucknow. Conclusion: Besides identifying novel mutations in whiB7, tlyA and gyrB target loci, our analyses unveiled a potential polymorphic and phylogeographical demarcation among two distinct regions.

Recent applications of Rose Bengal catalysis in N-heterocycles: a short review.

The visible light harnessing ability of Rose Bengal, an organic dye, has been extensively employed in organic chemistry over the last few years. In visible light mediated reactions, this photoredox catalyst operates through multiple pathways and has the ability to provide distinctly different and valuable results. The most significant of these results are bond creation, bond functionalization, particularly for C-H and C-heteroatom bonds, and cross couplings. It is crucial to study these cases whenever these bond formations and couplings lead to the formation of heterocyclic compounds or their functionalization. The diverse biological activity and medicinal applications of heterocyclic compounds is an extensively explored area. This review primarily attempts to demonstrate the synthetic potential of Rose Bengal for synthesis and site selective functionalization of nitrogen containing heterocycles.

Recent application of visible-light induced radicals in C-S bond formation.

The sulphur centered radicals, produced from various organic compounds, in high efficiency by single-electron-transfer (SET) oxidation. These radicals are highly reactive intermediates having various applications in the construction of organosulphur compounds in the field of synthetic organic chemistry. These S-centred radical-mediated organic transformations have been achieved using photoredox catalysts, including organic dyes and transition metal catalysts, as well as in the absence of any catalyst. Compared with previous methods, photoredox catalysis is inexpensive and features the advantages of being environmentally benign, highly efficient and easy to use. This review focuses on recent developments in the photocatalyzed carbon-sulphur bond formation.

Limited Scope of Shorter Drug Regimen for MDR TB Caused by High Resistance to Fluoroquinolone.

Resistance to second-line tuberculosis drugs for patients with multidrug-resistant tuberculosis has emerged globally and is a potential risk factor for unfavorable outcomes of shorter duration drug regimens. We assessed the proportion of patients eligible for a shorter drug regimen in Uttar Pradesh, India, which had the highest rate of multidrug-resistant tuberculosis in India.

Synthesis and fungicidal activity of novel 3-(substituted/unsubstituted phenylselenonyl)-1-ribosyl/deoxyribosyl-1H-1,2,4-triazole.

Reaction of potassium 1H-1,2,4-triazole-3-selenolate (I) with acetylated ribose/deoxyribose (IIa,b) in the presence of montmorillonite K 10 as a solid adsorbent furnished potassium 1-acetylated ribosyl/deoxyribosyl-1H-1,2,4-triazole-3-selenolate (IIIa,b) with excellent yield under microwave irradiation in solvent-free conditions. This eliminates a series of complex isolation procedures and often minimizes the use of a large amount of expensive, toxic, and hazardous solvents after each step. This procedure reduces reaction time and cost and enhances yield. Reaction of compound (IIIa,b) with substituted/unsubstituted aryl diazonium chloride (IVa-e) at 0-5 °C gave pure 3-(substituted/unsubstituted phenyl selanyl)-1-acetylribosyl/deoxyribosyl-1H-1,2,4-triazole (Va-j). Oxidation of compound (Va-j) with oxone followed by alkaline hydrolysis furnished quantitatively and analytically pure 3-(substituted/unsubstituted phenylselenonyl)-1-ribosyl/deoxyribosyl-1H-1,2,4-triazole (VIIa-j). Compounds VIa-j and VIIa-j were evaluated in vitro for their fungitoxicities against Fusarium oxysporum and Penicillium citrinum. All the compounds were found to be antifungal active. Some of the compounds displayed activities comparable with that of the commercial fungicide Dithane M-45 and griseofulvin. Structure-activity relationships for the screened compounds were discussed. The fact that both of these fungi have developed resistance to several fungicide groups made them optimal candidates as target organisms for ongoing research about the potential application of 1,2,4-triazole and analogue compounds as reduced-risk fungicides.

Decentralization of health services in India: barriers and facilitating factors.

BACKGROUND: In India, the process of decentralization of health services started taking shape in the mid-1990s. Systemic reforms envisaged delegation of administrative and financial responsibilities at district level for management of health-care institutions in 23 states of India in 1999. Subsequently, some of these reforms became part of the National Rural Health Mission (NRHM) launched in 2005. This study aims to document the process of decentralization in health services with special reference to the barriers and facilitating factors encountered during formulation and implementation of reform policies. METHODS: Secondary data were reviewed, health facilities were observed, and semi-structured interviews of the key actors involved in decentralization were carried out in Haryana (India). RESULTS: Political and bureaucratic commitment to reforms was found to be the most important facilitating factor. Orientation training on decentralized administrative structures and performance-based resource distribution were the other important facilitators. Structural changes in administrative procedures led to improvement in the financial management system. Significant improvement in the public health infrastructure was observed. From 2004 to 2008, the state government increased the budget of health sector by nearly 60%. Frequent changes in the top administration at the state level hampered the decentralization process. Districts having a dynamic administrative leadership implemented decentralization more effectively than the rest. CONCLUSIONS: Decentralization of financial resources has improved the functioning of health services to some extent. Major policy decisions on decentralization of human resource management, increase in financial allocation, and greater involvement of community in decision-making are required.

Mineral supported facile synthesis of novel 4-hydroxybenzoxazin-2-thione N-nucleosides.

One-pot montmorillonite K-10 clay-supported reactions of substituted/unsubstituted salicylaldehyde and ribosyl/deoxyribosyl thioureas expeditiously yielded novel N-nucleosides, 4-hydroxy-3,4-dihydro-3-(beta-D-ribofuranosyl or beta-D-2'-deoxyribofuranosyl)-2''-benz[e]-1,3-oxazin-2-thione via cycloisomerization of aldehyde intermediate under solvent-free microwave irradiation conditions.

Synthesis and fungicidal activity of novel 4,4'-bis(2' '-aryl-5' '-methyl/unsubstituted-4' '-oxo-thiazolidin-3' '-yl) bibenzyl.

Reduction followed by nitration of benzil I yielded 4,4'-dinitrobibenzyl (III) which by reduction furnished quantitatively and analytically pure 4,4'-diaminobibenzyl (IV) which on condensation with different carbonyl compounds gave 4,4'-bis (benzylideneamino) bibenzyls (Va-f). Compounds (Va-f) on cycloaddition with mercaptoacetic acid/2-mercaptopropionic acid yielded the corresponding 4-oxothiazolidin-3-yl bibenzyls (VIa-l). The compounds VIg-l have two chiral centers in each thiazolidinone moiety so two diastereomers are possible, but on crystallization and repeated chromatography, one diastereomer was obtained. The absolute configuration of the diastereomer was tentatively assigned on the basis of (1)H NMR spectra. (1)H NMR spectra of the product showed a distinct doublet at delta 1.22 for C(5)-CH(3) of thiazolidinone ring (22, 23) and a distinct quartet at delta 4.20 for the C(5)-H proton. Similarly, the C(2) proton showed an independent singlet at delta 5.95, so the diastereomers obtained were assigned trans configuration. Compounds Va-f and VIa-l were evaluated in vitro for their fungitoxicities against Fusarium oxysporium and Penicillium citrinum. All the compounds were found to be antifungal active. Some of the compounds displayed activities comparable with that of the commercial fungicide Dithane M-45. Structure-activity relationships for the screened compounds are discussed.