Asymmetric cross-aldol reaction of isatin and ketones catalyzed by crude earthworm extract as efficient biocatalyst

ABSTRACT

The asymmetric cross-aldol reaction of simple ketones (acetone, cyclohexanone) with isatin derivatives in the presence of crude extract from earthworms as green and effective biocatalyst proceeds easily in MeCN/H₂O (1:1) as solvent to afford 3-hydroxy-2-oxindoles derivatives. Ten compounds were synthesized in high yields (62–88%) and moderate ee (29–42%). Structure of the synthesized compounds has been characterized on the basis of NMR spectra and CHN analysis. The ee of the obtained compounds was determined by chiral phase HPLC analysis.     

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)₂) clusters based on coinage metals, [(PPh₃)₂AgO₂CFcCO₂Ag(PPh₃)₂]₂ ⋅ 7 CH₃OH (SC₁: super capacitor) and [(PPh₃)₃CuO₂CFcCO₂Cu(PPh₃)₃] ⋅ 3 CH₃OH (SC₂), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g⁻¹ and 210 F g⁻¹ specific capacitance at 1.5 A g⁻¹ in Na₂SO₄ electrolyte, respectively. The obtained results show that the presence of Cu^I instead of Ag^I improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC₂ ([(PPh₃)₂CuO₂CFcCO₂]_∞), a polymeric structure of SC₂, was synthesized and used as an energy storage electrode. PSC₂ displays high conductivity and gives 455 F g⁻¹ capacitance at 3 A g⁻¹. The PSC₂ as a supercapacitor electrode presents a high power density (2416 W kg⁻¹), high energy density (161 Wh kg⁻¹), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.     

Perlite–SO<Subscript>3</Subscript>H nanoparticles: very efficient and reusable catalyst for three-component synthesis of <Emphasis Type="Italic">N</Emphasis>-cyclohexyl-3-aryl-quinoxaline-2-amine derivatives under ultrasound irradiation

An efficient green approach for the synthesis of N-cyclohexyl-3-aryl-quinoxaline-2-amine derivatives, via a three-component one-pot condensation reaction of o-phenylenediamine, aromatic aldehydes and cyclohexyl isocyanide in the presence of perlite–SO₃H nanoparticles (diameter/thickness of platelets <?100 nm) under ultrasound irradiation has been demonstrated. The present method offers advantages such as shorter reaction time, easy work-up, excellent yields, recovery and reusability of catalyst. In addition, the methodology has been prosperous in getting the green chemistry purposes such as natural catalyst, using ultrasound irradiation instead of conventional heating and stirring, and a non-hazardous products in the thus combining the features of both economic and environmental advantages.     

Density functional investigation of the interaction of acetone with small gold clusters

The structural evolution of Au(n) (n=2, 3, 5, 7, 9, and 13) clusters and the adsorption of organic molecules such as acetone, acetaldehyde, and diethyl ketone on these clusters are studied using a density functional method. The detailed study of the adsorption of acetone on the Au(n) clusters reveals two main points. (1) The acetone molecule interacts with one gold atom of the gold clusters via the carbonyl oxygen. (2) This interaction is mediated through back donation mainly from the spd-hybridized orbitals of the interacting gold atom to the oxygen atom of the acetone molecule. In addition, a hydrogen bond is observed between a hydrogen atom of the methyl group and another gold atom (not involved in the bonding with carbonyl oxygen). Interestingly, the authors notice that the geometries of Au(9) and Au(13) undergo a significant flattening due to the adsorption of an acetone molecule. They have also investigated the role of the alkyl chain attached to the carbonyl group in the adsorption process by analyzing the interaction of Au(13) with acetaldehyde and diethyl ketone.     

Photodissociation of iodocyclohexane at 266 and 277 nm: Energy partitioning and curve crossing analysis

The photodissociation dynamics of iodocyclohexane (C₆H₁₁I) at 266 and 277 nm has been investigated by ion velocity imaging technique. The velocity distributions, angular distributions and relative quantum yields are obtained for I (²P_3/2) (denoted I) and I (²P_1/2) (denoted I*) fragments. The energy partitioning shows that about 70% of the available energy goes into the internal excitation of the photofragments for both dissociation channels. From the angular distributions, we found the value of the anisotropy parameter β for I* at the corresponding excitation wavelength was less than that for I. Based on the measured angular distributions and relative quantum yields, the relative fractions of each excited state to the products are determined. The curve crossing probabilities between the ³Q₀ and ¹Q₁ states are determined 0.503 at 266 nm and 0.443 at 277 nm.     

<Emphasis Type="Italic">N</Emphasis>=2 de Sitter Super-symmetry Algebra

It was shown that N=1 super-symmetry algebra can be constructed in de Sitter space (Pahlavan et al. in Phys Lett. B 627:217–223, 2005), through calculation of charge conjugation in the ambient space notation (Moradi et al. in Phys. Lett. B 613:74, 2005; Phys. Lett. B 658:284, 2008). Calculation of N=2 super-symmetry algebra constitutes the main frame of this paper. N=2 super-symmetry algebra was presented in Pilch et al. (Commun. Math. Phys. 98:105, 1985). In this paper, we obtain an alternative N=2 super-symmetry algebra.     

A novel three-component reaction of a secondary amine and a 2-hydroxybenzaldehyde derivative with an isocyanide in the presence of silica gel: an efficient one-pot synthesis of benzo[b]furan derivatives

Reaction of an isocyanide with an iminium ion intermediate, formed by reaction between an electron-poor 2-hydroxybenzaldehyde derivative and a secondary amine in the presence of silica gel proceeds smoothly at room temperature to afford benzo[b]furan derivatives in high yields.     

Mimicking DNA stretching with the Static Mode method: Shear stress versus transverse pulling stress

DNA sequencing using nanopores is closer than ever to become a reality, but further research and development still need to be done, especially to unravel the atomic-scale mechanisms of induced DNA stretching. At this level, molecular modeling and simulation are essential to investigate DNA conformational flexibility and its response to the forces involved. In this work, through a "Static Mode" approach, we present a directed exploration of the deformations of a 27-mer subjected to externally imposed forces, as it could be in a nanopore. We show how the DNA sugar-phosphate backbone undergoes the majority of the induced deformation, before the base pairing is affected, and to what extent unzipping initiation depends on the force direction.     

Chemoenzymatic Hydrogen Production from Methanol through the Interplay of Metal Complexes and Biocatalysts

Microbial methylotrophic organisms can serve as great inspiration in the development of biomimetic strategies for the dehydrogenative conversion of C₁ molecules under ambient conditions. In this Concept article, a concise personal perspective on the recent advancements in the field of biomimetic catalytic models for methanol and formaldehyde conversion, in the presence and absence of enzymes and co-factors, towards the formation of hydrogen under ambient conditions is given. In particular, formaldehyde dehydrogenase mimics have been introduced in stand-alone C₁-interconversion networks. Recently, coupled systems with alcohol oxidase and dehydrogenase enzymes have been also developed for in situ formation and decomposition of formaldehyde and/or reduced/oxidized nicotinamide adenine dinucleotide (NADH/ NAD⁺). Although C₁ molecules are already used in many industries for hydrogen production, these conceptual bioinspired low-temperature energy conversion processes may lead one day to more efficient energy storage systems enabling renewable and sustainable hydrogen generation for hydrogen fuel cells under ambient conditions using C₁ molecules as fuels for mobile and miniaturized energy storage solutions in which harsh conditions like those in industrial plants are not applicable.