Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy

Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.     

A new approach to constructing exponentially many nonisomorphic nonorientable triangular embeddings of complete graphs

We prove a theorem that for an integer s?0, if 12s+7 is a prime number, then the number of nonisomorphic face 3-colorable nonorientable triangular embeddings of K_n, where n=(12s+7)(6s+7), is at least . By some number-theoretic arguments there are an infinite number of integers s satisfying the hypothesis of the theorem. The theorem is the first known example of constructing at least 2^αn?+o(n?), ?>1, nonisomorphic nonorientable triangular embeddings of K_n for n=6t+1, . To prove the theorem, we use a new approach to constructing nonisomorphic triangular embeddings of complete graphs. The approach combines a cut-and-paste technique and the index one current graph technique. A new connection between Steiner triple systems and constructing triangular embeddings of complete graphs is given.     

A Property Satisfying Reducedness over Centers

This article concerns a ring property called pseudo-reduced-over-center that is satisfied by free algebras over commutative reduced rings.The properties of radicals of pseudo-reduced-over-center rings are investigated,especially related to polynomial rings.It is proved that for pseudo-reduced-over-center rings of nonzero characteristic,the centers and the pseudo-reduced-over-center property are preserved through factor rings modulo nil ideals.For a locally finite ring R,it is proved that if R is pseudo-reduced-over-center,then R is commutative and R/J(R) is a commutative regular ring with J(R) nil,where J(R) is the Jacobson radical of R.     

Dopamine Detection Using the Selective and Spontaneous Formation of Electrocatalytic Poly(dopamine) Films on Indium?Tin Oxide Electrodes

In this study, we report the simple and sensitive electrochemical detection of dopamine in the presence of excess ascorbic acid. The detection is based on the spontaneous formation of electrocatalytic poly(dopamine) films on bare indium? tin oxide (ITO) electrodes. The poly(dopamine) films are formed by immersing ITO electrodes in a solution of dopamine and ascorbic acid for 10 min. Afterwards, the electrocatalytic oxidation of hydrazine is measured using modified electrodes. The electrooxidation current of hydrazine increases with increasing dopamine concentration. This method allows a detection limit of 1 nM for dopamine in the presence of 100 µM of ascorbic acid.     

Optically active, lyotropic liquid crystalline poly(diphenylacetylene) derivative: hierarchical chiral ordering from isotropic solution to anisotropic solid films

The side chain chirality of a poly(diphenylacetylene) derivative was transferred and amplified spontaneously from solution to a bulk film due to lyotropic liquid crystallinity.     

Structural and spectroscopic properties of the peroxodiferric intermediate of Ricinus communis soluble Δ9 desaturase

Large-scale quantum and molecular mechanical methods (QM/MM) and QM calculations were carried out on the soluble Δ(9) desaturase (Δ(9)D) to investigate various structural models of the spectroscopically defined peroxodiferric (P) intermediate. This allowed us to formulate a consistent mechanistic picture for the initial stages of the reaction mechanism of Δ(9)D, an important diferrous nonheme iron enzyme that cleaves the C-H bonds in alkane chains resulting in the highly specific insertion of double bonds. The methods (density functional theory (DFT), time-dependent DFT (TD-DFT), QM(DFT)/MM, and TD-DFT with electrostatic embedding) were benchmarked by demonstrating that the known spectroscopic effects and structural perturbation caused by substrate binding to diferrous Δ(9)D can be qualitatively reproduced. We show that structural models whose spectroscopic (absorption, circular dichroism (CD), vibrational and M?ssbauer) characteristics correlate best with experimental data for the P intermediate correspond to the μ-1,2-O(2)(2-) binding mode. Coordination of Glu196 to one of the iron centers (Fe(B)) is demonstrated to be flexible, with the monodentate binding providing better agreement with spectroscopic data, and the bidentate structure being slightly favored energetically (1-10 kJ mol(-1)). Further possible structures, containing an additional proton or water molecule are also evaluated in connection with the possible activation of the P intermediate. Specifically, we suggest that protonation of the peroxide moiety, possibly preceded by water binding in the Fe(A) coordination sphere, could be responsible for the conversion of the P intermediate in Δ(9)D into a form capable of hydrogen abstraction. Finally, results are compared with recent findings on the related ribonucleotide reductase and toluene/methane monooxygenase enzymes.     

Non-covalent monolayer-piercing anchoring of lipophilic nucleic acids: preparation, characterization, and sensing applications

Functional interfaces of biomolecules and inorganic substrates like semiconductor materials are of utmost importance for the development of highly sensitive biosensors and microarray technology. However, there is still a lot of room for improving the techniques for immobilization of biomolecules, in particular nucleic acids and proteins. Conventional anchoring strategies rely on attaching biomacromolecules via complementary functional groups, appropriate bifunctional linker molecules, or non-covalent immobilization via electrostatic interactions. In this work, we demonstrate a facile, new, and general method for the reversible non-covalent attachment of amphiphilic DNA probes containing hydrophobic units attached to the nucleobases (lipid-DNA) onto SAM-modified gold electrodes, silicon semiconductor surfaces, and glass substrates. We show the anchoring of well-defined amounts of lipid-DNA onto the surface by insertion of their lipid tails into the hydrophobic monolayer structure. The surface coverage of DNA molecules can be conveniently controlled by modulating the initial concentration and incubation time. Further control over the DNA layer is afforded by the additional external stimulus of temperature. Heating the DNA-modified surfaces at temperatures >80 °C leads to the release of the lipid-DNA structures from the surface without harming the integrity of the hydrophobic SAMs. These supramolecular DNA layers can be further tuned by anchoring onto a mixed SAM containing hydrophobic molecules of different lengths, rather than a homogeneous SAM. Immobilization of lipid-DNA on such SAMs has revealed that the surface density of DNA probes is highly dependent on the composition of the surface layer and the structure of the lipid-DNA. The formation of the lipid-DNA sensing layers was monitored and characterized by numerous techniques including X-ray photoelectron spectroscopy, quartz crystal microbalance, ellipsometry, contact angle measurements, atomic force microscopy, and confocal fluorescence imaging. Finally, this new DNA modification strategy was applied for the sensing of target DNAs using silicon-nanowire field-effect transistor device arrays, showing a high degree of specificity toward the complementary DNA target, as well as single-base mismatch selectivity.     

Positive‐/Negative‐, Erasable‐/Immobilized‐, Mono‐/Multi‐Color Fluorescence Image Patterning of Molecular‐Scale Porous Polymer Film via a Microcontact Printing Method Using Various Chemical Inks

Fluorescent image patterns of a substituted acetylene polymer film with a large FFV were successfully obtained by a µCP method using several kinds of chemical ink compounds. PO and SCA generated positive‐type fluorescent image patterns. On the other hand, an ethanolic solution of DNT generated a negative‐type fluorescent image pattern due to a significant quenching effect. An NMP solution of NR gave a two‐color image pattern due to an intermolecular energy transfer from PTMSDPA to NR.

     

Dynamic changes of gangliosides expression during the differentiation of embryonic and mesenchymal stem cells into neural cells

Stem cells are used for the investigation of developmental processes at both cellular and organism levels and offer tremendous potentials for clinical applications as an unlimited source for transplantation. Gangliosides, sialic acid-conjugated glycosphingolipids, play important regulatory roles in cell proliferation and differentiation. However, their expression patterns in stem cells and during neuronal differentiation are not known. Here, we investigated expression of gangliosides during the growth of mouse embryonic stem cells (mESCs), mesenchymal stem cells (MSCs) and differentiated neuronal cells by using high-performance thin-layer chromatography (HPTLC). Monosialoganglioside 1 (GM1) was expressed in mESCs and MSCs, while GM3 and GD3 were expressed in embryonic bodies. In the 9-day old differentiated neuronal cells from mESCs cells and MSCs, GM1 and GT1b were expressed. Results from immunostaining were consistent with those observed by HPTLC assay. These suggest that gangliosides are specifically expressed according to differentiation of mESCs and MSCs into neuronal cells and expressional difference of gangliosides may be a useful marker to identify differentiation of mESCs and MSCs into neuronal cells.     

Effect of barium loading on the desulfation of Pt-BaO/Al2O3 studied by H2 TPRX, TEM, sulfur K-edge XANES, and in situ TR-XRD

Desulfation processes were investigated over sulfated Pt-BaO/Al2O3 with different barium loading (8 and 20 wt %) by using H2 temperature programmed reaction (TPRX), transmission electron microscope (TEM) with energy dispersive spectroscopy (EDS), sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and in situ time-resolved X-ray diffraction (TR-XRD) techniques. Both sulfated samples (8 and 20 wt %) form sulfate species (primarily BaSO4) as evidenced by S K-edge XANES and in situ TR-XRD. However, the desulfation behavior is strongly dependent on the barium loading. Sulfated Pt-BaO8/Al2O3, consisting predominantly of surface BaO/BaCO3 species, displays more facile desulfation by H2 at lower temperatures than sulfated Pt-BaO20/Al2O3, a material containing primarily bulk BaO/BaCO3 species. Therefore, after desulfation with H2 up to 1073 K, the amount of the remaining sulfur species on the former, mostly as BaS, is much less than that on the latter. This suggests that the initial morphology differences between the two samples play a crucial role in determining the extent of desulfation and the temperature at which it occurs. It is concluded that the removal of sulfur is significantly easier at lower barium loading. This finding can potentially be important in developing more sulfur resistant LNT catalyst systems.