Application of N-heterocyclic carbene-Cu(I) complexes as catalysts in organic synthesis: a review.

N-Heterocyclic carbenes (NHCs) are a special type of carbenes in which the carbene carbon atom is part of the nitrogen heterocyclic ring. Due to the simplicity of their synthesis and the modularity of their stereoelectronic properties, NHCs have unquestionably emerged as one of the most fascinating and well-known species in chemical science. The remarkable stability of NHCs can be attributed to both kinetic as well as thermodynamic effects caused by its structural features. NHCs constitute a well-established class of new ligands in organometallic chemistry. Although initially NHCs were regarded as pure σ-donor ligands, later experimental and theoretical studies established the presence of a significant back donation from the d-orbital of the metal to the π* orbital of the NHC. Over the last two decades, NHC-metal complexes have been extensively used as efficient catalysts in different types of organic reactions. Of these, NHC-Cu(I) complexes found prominence for various reasons, such as ease of preparation, possibility of structural diversity, low cost, and versatile applications. This article overviews applications of NHC-Cu(I) complexes as catalysts in organic synthesis over the last 12 years, which include hydrosilylation reactions, conjugate addition, [3 + 2] cycloaddition, A3 reaction, boration and hydroboration, N-H and C(sp2)-H carboxylation, C(sp2)-H alkenylation and allylation, C(sp2)-H arylation, C(sp2)-H amidation, and C(sp2)-H thiolation. Preceding the section of applications, a brief description of the structure of NHCs, nature of NHC-metal bond, and methods of preparation of NHC-Cu complexes is provided.

Enzymatic saccharification of pretreated rice straw by cellulases from Aspergillus niger BK01.

Alkali-assisted acid pretreated rice straw was saccharified using cellulase from Aspergillus niger BK01. The cellulase production by the fungus was enhanced by parametric optimization using solid-state fermentation conditions. Maximum cellulase production (12.0 U/gds of carboxymethyl cellulase, CMCase) was achieved in 96 h, using 6.0% substrate concentration, 7.5% inoculum concentration, 1:2 solid to liquid ratio, at pH 5.5, and temperature 28 °C, by supplementation of the fermentation medium with 0.1% carboxymethylcellulose and 0.1% ammonium nitrate. Characterization of crude cellulases showed that highest CMCase activity was observed at pH 4.8 and temperature 40 °C. The CMCase was stable from pH 4.8-5.5 and at a temperature range of 35-50 °C. The pretreated biomass was subjected to hydrolysis with the fungal cellulases. The saccharification optimization studies showed that 2% (v/v) enzyme concentration and hydrolysis time of 2.5 h were optimum for maximum yield, i.e, 23.78% sugars and 35.96% saccharification value.

Parametric Optimization of Cultural Conditions for Carboxymethyl Cellulase Production Using Pretreated Rice Straw by Bacillus sp. 313SI under Stationary and Shaking Conditions.

Carboxymethyl cellulase (CMCase) provides a key opportunity for achieving tremendous benefits of utilizing rice straw as cellulosic biomass. Out of total 80 microbial isolates from different ecological niches one bacterial strain, identified as Bacillus sp. 313SI, was selected for CMCase production under stationary as well as shaking conditions of growth. During two-stage pretreatment, rice straw was first treated with 0.5 M KOH to remove lignin followed by treatment with 0.1 N H2SO4 for removal of hemicellulose. The maximum carboxymethyl cellulase activity of 3.08 U/mL was obtained using 1% (w/v) pretreated rice straw with 1% (v/v) inoculum, pH 8.0 at 35°C after 60 h of growth under stationary conditions, while the same was obtained as 4.15 U/mL using 0.75% (w/v) pretreated substrate with 0.4% (v/v) inoculum, pH 8.0 at 30°C, under shaking conditions of growth for 48 h. For maximum titre of CMCase carboxymethyl cellulose was optimized as the best carbon source under both cultural conditions while ammonium sulphate and ammonium nitrate were optimized as the best nitrogen sources under stationary and shaking conditions, respectively. The present study provides the useful data about the optimized conditions for CMCase production by Bacillus sp. 313SI from pretreated rice straw.

Isolation and screening of polyhydroxyalkanoates producing bacteria from pulp, paper, and cardboard industry wastes.

Background. Polyhydroxyalkanoates (PHAs) are storage materials that accumulate by various bacteria as energy and carbon reserve materials. They are biodegradable, environmentally friendly, and also biocompatible bioplastics. Unlike petrochemical-based plastics that take several decades to fully degrade, PHAs can be completely degraded within a year by variety of microorganisms into CO2 and water. In the present study, we aim to utilize pulp, paper, and cardboard industry sludge and waste water for the isolation and screening of polyhydroxyalkanoates (PHAs) accumulating bacteria and production of cost-effective PHB using cardboard industry waste water. Results. A total of 42 isolates showed black-blue coloration when stained with Sudan black B, a preliminary screening agent for lipophilic compounds, and a total of 15 isolates showed positive result with Nile blue A staining, a more specific dye for PHA granules. The isolates NAP11 and NAC1 showed maximum PHA production 79.27% and 77.63% with polymer concentration of 5.236 g/L and 4.042 g/L with cardboard industry waste water. Both of the selected isolates, NAP11 and NAC1, were classified up to genus level by studying their morphological and biochemical characteristics and were found to be Enterococcus sp., Brevundimonas sp. and, respectively. Conclusion. The isolates Enterococcus sp. NAP11 and Brevundimonas sp. NAC1 can be considered as good candidates for industrial production of PHB from cardboard industry waste water. We are reporting for the first time the use of cardboard industry waste water as a cultivation medium for the PHB production.

Design, synthesis and antimicrobial evaluation of novel 1,3-oxazolidin-2- one derivatives.

A series of novel derivatives of 1,3-oxazolidin-2-one 12a-12n has been synthesized starting from 4-nitro-(L)- phenylalanine by involving five-step reaction sequence. All the compounds were screened for their in vitro antibacterial activity against four pathogenic bacterial strains namely, Staphylococcus aureus, Bacillus subtilis (Gram-positive), Escherichia coli, Pseudomonas aeruginosa (Gram-negative) and in vitro antifungal activity against two pathogenic fungal strains namely, Candida albicans and Saccharomyces cerevisiae. All the synthesized compounds showed activity against Gram-positive bacteria. Compounds 12c and 12l exhibited maximum antibacterial activity against Gram-positive bacteria. However, against Gram-negative bacteria only five of screened compounds were found to be active. Compounds 12c and 12i displayed best antifungal activity against the tested fungi. Docking studies were carried out in order to gain insight into the mechanism of action and the binding mode of these compounds. These studies were in agreement with the biological data.