Mixed-Isotope Labeling with LC-IMS-MS for Characterization of Protein–Protein Interactions by Chemical Cross-Linking

Chemical cross-linking of proteins followed by proteolysis and mass spectrometric analysis of the resulting cross-linked peptides provides powerful insight into the quaternary structure of protein complexes. Mixed-isotope cross-linking (a method for distinguishing intermolecular cross-links) was coupled with liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS) to provide an additional separation dimension to the traditional cross-linking approach. This method produced multiplet m/z peaks that are aligned in the IMS drift time dimension and serve as signatures of intermolecular cross-linked peptides. We developed an informatics tool to use the amino acid sequence information inherent in the multiplet spacing for accurate identification of the cross-linked peptides. Because of the separation of cross-linked and non-cross-linked peptides in drift time, our LC-IMS-MS approach was able to confidently detect more intermolecular cross-linked peptides than LC-MS alone.      

Aryl Nitro Reduction with Iron Powder or Stannous Chloride under Ultrasonic Irradiation

The selective reduction of aryl nitro compounds in the presence of sensitive functionalities, including halide, carbonyl, nitrile, and ester substituents, under ultrasonic irradiation at 35 kHz is reported in yields of 39–98%. Iron powder proved superior to stannous chloride with high tolerance of sensitive functional groups and high yields of the desired aryl amines in relatively short reaction times. Simple experimental procedure and purification also make the iron reduction of aryl nitro compounds advantageous over other methods of reduction.     

Development of a general approach to the synthesis of a library of isoflavonoid derivatives

Isoflavonoids are a class of organic compounds that act primarily as antioxidants. They are produced almost exclusively by various members of the bean family including soybeans, tofu, peanuts, chick peas, and alfalfa. The antioxidant characteristics that isoflavonoids exhibit help hinder the progression of certain cancers, primarily breast, prostate, and colon cancer. We have developed a three-five step synthesis for obtaining a suite of isoflavonoid derivatives. The synthesis involves an enamine formation, a ring closure and halogenation, a Suzuki coupling, and finally a global deprotection to obtain the respective isoflavonoid derivatives.     

Efficient Copper-Catalyzed Highly Stereoselective Synthesis of Unprotected C-Acyl Manno-, Rhamno- and Lyxopyranosides

Due to their high stability towards enzymatic hydrolysis C-acyl glycosidic compounds are useful synthetic intermediates for potential candidates in drug discovery. Syntheses for C-acyl mannosides have remained scarce and usually employ donors obtained from lengthy syntheses. Furthermore, syntheses of unprotected C-acyl mannosides have not been reported so far, due to the incapability of the C-acyl mannoside motif with deprotection conditions for protective groups commonly used in carbohydrate chemistry. Herein, we report an efficient and highly α-selective four-step one-pot method for the synthesis of C-acyl α-d -manno-, l -rhamno- and d -lyxopyranosides from easily accessible persilylated monosaccharides and dithianes requiring only trace amounts of a copper source as catalyst and explain the crucial role of the catalyst by mechanistic studies. Furthermore, the C-acyl α-glycosides were easily isomerized to give rapid access to their β-anomers.     

An ignition-temperature model with two free interfaces in premixed flames†

In this paper we consider an ignition-temperature zero-order reaction model of thermo-diffusive combustion. This model describes the dynamics of thick flames, which have recently received considerable attention in the physical and engineering literature. The model admits a unique (up to translations) planar travelling wave solution. This travelling wave solution is quite different from those usually studied in combustion theory. The main qualitative feature of this travelling wave is that it has two interfaces: the ignition interface where the ignition temperature is attained and the trailing interface where the concentration of deficient reactants reaches zero. We give a new mathematical framework for studying the cellular instability of such travelling front solutions. Our approach allows the analysis of a free boundary problem to be converted into the analysis of a boundary value problem having a fully nonlinear system of parabolic equations. The latter is very suitable for both mathematical and numerical analysis. We prove the existence of a critical Lewis number such that the travelling wave solution is stable for values of Lewis number below the critical one and is unstable for Lewis numbers that exceed this critical value. Finally, we discuss the results of numerical simulations of a fully nonlinear system that describes the perturbation dynamics of planar fronts. These simulations reveal, in particular, some very interesting ‘two-cell’ steady patterns of curved combustion fronts.     

Fermi surface of CeIn3 above the Néel critical field

We report measurements of the de Haas-van Alphen effect in CeIn(3) in magnetic fields extending to approximately 90 T, well above the Néel critical field of mu(0)H(c) approximately 61 T. The unreconstructed Fermi surface a sheet is observed in the high magnetic field polarized paramagnetic limit, but with its effective mass and Fermi surface volume strongly reduced in size compared to that observed in the low magnetic field paramagnetic regime under pressure. The spheroidal topology of this sheet provides an ideal realization of the transformation from a "large Fermi surface" accommodating f electrons to a "small Fermi surface" when the f-electron moments become polarized.