Decarboxylative Trifluoromethylating Reagent [Cu(O2CCF3)(phen)] and Difluorocarbene Precursor [Cu(phen)2][O2CCF2Cl]

This article describes the new economic decarboxylative trifluoromethylating reagent [Cu(phen)(O₂CCF₃)] ( 1 ; phen=1,10‐phenanthroline) and the efficient difluorocarbene precursor [Cu(phen)₂][O₂CCF₂Cl] ( 2 ). Treatment of copper tert‐butoxide with phen and subsequent addition of trifluoroacetic acid or chlorodifluoroacetic acid afforded air‐stable complexes 1 and 2 , respectively, which were characterized by X‐ray crystallography. The copper(I) ion in 1 is coordinated by a bidentate phen ligand, a monodentate trifluoroacetate group, and a molecule of CH₃CN in a distorted tetrahedral coordination geometry. The molecular structure of 2 adopts an ionic form that consists of a [Cu(phen)₂]⁺ cation and a chlorodifluoroacetate anion. Complex 1 reacted with a variety of aryl and heteroaryl halides to form trifluoromethyl (hetero)arenes in good yields. The corresponding Hammett plot exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest‐to‐excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper‐mediated formation of difluorocarbene and subsequent concerted addition of difluorocarbene to the phenol to form a three‐center transition state.     

Finite groups with <Emphasis Type="Italic">SS</Emphasis>-supplement

Let G be a finite group. A subgroup H of G is said to be SS-quasinormal in G if there is a subgroup K such that \(G=HK\) and \(HS=SH\), for all \(S\in \) Syl(K), where Syl(K) denotes the collection of all Sylow subgroups of K. A subgroup H of G is said to be SS-supplemented in G if there is a subgroup K such that \(G=HK\) and \(H\cap K\) is SS-quasinormal in G. In this paper, we investigate the SS-supplemented subgroups and strengthen a result of Skiba which gives a positive answer to an open question of Shemetkov.     

Crystallization and stability of different protein crystal modifications: A case study of lysozyme

The crystallization, including both the phase diagram and the phase transition of hen egg white lysozyme (HEWL) was investigated. A tetragonal modification and a needle modification were obtained during crystallization. The phase diagram and stability of two modifications in both acid and basic pH solutions (pH 4.5, 8.0 and 9.0) were determined. Besides in acid solutions, the well‐known tetragonal crystals can also be obtained in basic solutions at low temperature (7 °C) while the needle like modification can only crystallize in a basic solution. Based on the phase diagram, phase transfer behavior was found to exist between the two modifications. In basic solutions, tetragonal modification can transfer to needle shaped crystals. This process can be affected by a changing of pH and temperature. While in acid buffer, the needle shaped crystals dissolve and tetragonal crystals crystallize and remain in solution.     

A lipase-based electrochemical biosensor for target DNA

A lipase-based electrochemical biosensor has been fabricated for the quantitative determination of target DNA. It is based on a stem-loop nucleic acid probe labeled with ferrocene containing a butanoate ester that is hydrolyzed by lipase. The other end of the probe DNA is linked, via carboxy groups, to magnetic nanoparticles. The binding of target DNA transforms the hairpin structure of the probe DNA and causes the exposure of ester bonds. This results in the release of electro-active ferrocene after hydrolysis of the ester bonds, and in an observable electrochemical response. The quantity of target DNA in the concentration range between 1?×?10^?12 mol·L^?1 and 1?×?10^?8 mol·L^?1 can be determined by measuring the electrochemical current. The method can detect target DNA with rapid response (30 min) and low interference.

Defining and using microbial spectral databases

This work shows how fingerprints of mass spectral patterns from microbial isolates are affected by variations in instrumental condition, by sample environment, and by sample handling factors. It describes a novel method by which pattern distortions can be mathematically corrected for variations in factors not amenable to experimental control. One uncontrollable variable is "between-batch" differences in culture media. Another, relevant for determination of noncultured extracts, is differences between the cells' environmental experience (e.g., starved environmental extracts versus cultured standards). The method suggests that, after a single growth cycle on a solid medium (perhaps, a selective one), pyrolysis MS spectra of microbial isolates can be algorithmically compensated and an unknown isolate identified using a spectral database defined by culture on a different (perhaps, nonselective) medium. This reduces identification time to as few as 24 h from sample collection. The concept also proposes a possible way to compensate certain noncultured, nonisolated samples (e.g., cells concentrated from urine or impacted from aerosol or semi-selectively extracted by immunoaffinity methods from heavily contaminated matrices) for identification within half an hour. Using the method, microbial mass spectra from different labs can be assembled into coherent databases similar to those routinely used to identify pure compounds. This type of data treatment is applicable for rapid detection in biowarfare and bioterror events as well as in forensic, research, and clinical laboratory contexts.     

Sm–Co and Nd–Fe–B thin films with perpendicular anisotropy for high-density magnetic recording media

Sm–Co and Nd–Fe-B thin films have been prepared by sputtering. Particular efforts are concentrated on the perpendicular texture growth of the films. The Sm–Co and Nd–Fe–B thin films with perpendicular magnetic anisotropy can be prepared on Cu and W underlayer, respectively. Those underlayers play an important role to prevent oxidation and improve crystal lattice orientation. Perpendicular coercivity and remanent squareness ratio are higher than 10 kOe and almost 1.0, respectively, in both films prepared under optimum conditions.     

Self-assembled L10 FePt thin films for high-density magnetic recording

A new technique, which utilizes the interlayer diffusion, for preparation of self-assembled nanodot magnetic structures has been proposed. L1₀-phase Pt/FeCu and Pt/FeAg films have been successfully synthesized by this technique. Both the coercivity of Pt/FeCu and Pt/FeAg films exhibited, respectively 4.1 and 8.0 kOe in perpendicular direction. Pt/Fe and Pt/FeAg films show positive values, while Pt/FeCu shows negative value in δm plot. The results indicate that the exchange coupling between the grains has been decoupled in the self-assembled nanodot structure in Pt/FeCu film.     

The effect of In doping on optical properties of Fe:LiNBO3 crystals

Fe:LiNbO₃ and In:Fe:LiNbO₃ crystals were grown by Czochralski method. The absorption spectra were measured to investigate their defect structure. The photo damage resistance and photorefractive properties were measured. The photo damage resistance of the In:Fe:LiNbO₃ crystal in which the In concentration is above the threshold value is one order of magnitude higher than that of the Fe:LiNbO₃ crystal. The mechanisms of the violet shift of the absorption edge and the enhancement of the photorefractive effect of In:Fe:LiNbO₃ crystals were investigated.     

Dinitrogen Activation and Addition to Unsaturated C−E (E=C,N, O,S) Bonds Mediated by Transition Metal Complexes

Dinitrogen (N₂) activation and functionalization is of fundamental interest and practical importance. This review focuses on N₂ activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N−C bond formation products. Emphases are placed on the reaction modes and mechanisms. We hope that this work would stimulate further explorations in this challenging field.