A three-component protocol for the enantiodifferentiation of amines using triphenyl borate and BINOL: is it an ion pair or an amine-coordinated complex?

The structure of the borate complex responsible for the enantiodifferentiation of amines using a previously reported three-component protocol has been established. The choice between an ion pair and an amine-coordinated complex with the N atom of the amine coordinated to the B atom is favored for the former structure based on the DFT-calculated B-11 NMR chemical shifts. In contrast to expectations, the anisotropies of the quadrupolar B-11 nucleus for the two structures were calculated to be indistinguishable with regard to their effect on the linewidth of the NMR signal. (C) 2014 Elsevier Ltd. All rights reserved.

The Structure of 9b-Methyl- 3afl,3b~,5 a~t,9a0h9bfl, 11 afl-perhydrophenanthro-[2,l-b]furan-7-one

C17H2602, M, = 262, triclinic, PI, a = 8.513(2), b = 8.970(2), c = 11.741(3)A, a = 120.51 (5), fl = 93.30(4), y = 68.43(4) ° , V = 708.9,/k 3, Z = 2, D O = 1.213, D e = 1.227 Mg m -a, g(Mo Ka, 2 = 0.7107 ,&) = 0.084 mm -1, F(000) = 288. The structure, solved by direct methods, has been refined to an R value of 5.9% using 1361 intensity measurements. The ring junctions, in sequence from either end of the polycycle, are cis, trans and cis.

Asymmetric synthesis of steroidal Tröger's base analogues. X-Ray molecular structure of methyl 3?,12?-{6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-bisacetoxy}-5?-cholan-24-oate

Cyclization of compound 5c in trifluoroacetic acid/hexamethylenetetramine produces Tröger's base analogue 6c in 75% yield with 70% diastereoselectivity.

Enantiospecific total synthesis of ent-10, 11-thapsan-10-ol

First enantiospecific total synthesis of optical antipode of the sesquiterpene 10,11-epoxythapsan-10-ol has been described. (R)-Carvone has been employed as the chiral starting material and a combination of intramolecular alkylation and Criegee fragmentation are employed for intramolecular stereospecific transfer of the chirality. An intramolecular diazoketone cyclopropanation and regioselective cyclopropane ring cleavage reactions have been employed for the creation of the three requisite contiguous quaternary carbon atoms.

Critical Cation Balance In B-]Z Transition - Role Of Li+

The sodium salt of poly(dG-dC) is known to exhibit a B + Z transition in the presence of various cations and 60% alcohol. We here show that the lithium salt of poly(dG-dC) does not undergo B 4 Z transition in the presence of 60% alcohol since Li’ with its large hydration shell cannot stabilize the Z-form. On the other hand, high concentrations of Mg2* or micromolar concentrations of the cobalt hexamine complex which are known to stabilize the Z-form can compete with Li+ for charge neutraIization and hence bring about a B--t Z transition in the same polymer. From the model building studies the mode of action of the cobalt-hexamine complex in stabilizing the Z-form is postulated.

Sequence dependence and role of 5'-phosphate in the B to Z transition

Spectroscopic studies on pd(CG)3 and pd(GC)3 have been carried out to elucidate the sequence dependence and effect of free 5'-phosphate on the B to Z transition. Unlike d(CG)3, pd(CG)3 fails to undergo salt-induced B to Z transition at ambient temperature. Model building studies have been carried out to determine the inhibitory role of the 5'-phosphate group, but have been unsuccessful.

X-Ray Studies On Crystalline Complexes Involving Amino-Acids And Peptides .11. Peptide Aggregation And Water-Structure In The Crystals Of A Hydrated 1-1 Complex Between L-Histidyl-L-Serine And Glycyl-L-Glutamic Acid

The hexahydrate of a 1:1 complex between L-histidyl-L-serine and glycyl-L-glutamic acid crystallizes in space group P1 with a = 4.706(1), b= 8.578(2), c= 16.521(3) ÅA; α= 85.9(1), β= 89.7(1)°, = 77.4(1). The crystal structure, solved by direct methods, has been refined to an R value of 0.046 for 2150 observed reflections. The two peptide molecules in the structure have somewhat extended conformations. The unlike molecules aggregate into separate alternating layers. Each layer is stabilized by hydrogen bonded head-to-tail sequences as well as sequences of hydrogen bonds involving peptide groups. The arrangement of molecules in each layer is similar to one of the plausible idealized arrangements of L-alanyl-L-alanine worked out from simple geometrical considerations. Adjacent layers in the structure are held together by interactions involving side chains as well as water molecules. The water structure observed in the complex provides a good model, at atomic resolution, for that in protein crystals. An interesting feature of the crystal structure is the existence of two water channels in the interfaces between adjacent peptide layers.

The Mycobacterial MsDps2 Protein Is a Nucleoid-Forming DNA Binding Protein Regulated by Sigma Factors sigma(A) and sigma(B)

The Dps (DNA-binding protein from starved cells) proteins from Mycobacterium smegmatis MsDps1 and MsDps2 are both DNA-binding proteins with some differences. While MsDps1 has two oligomeric states, with one of them responsible for DNA binding, MsDps2 has only one DNA-binding oligomeric state. Both the proteins however, show iron-binding activity. The MsDps1 protein has been shown previously to be induced under conditions of starvation and osmotic stress and is regulated by the extra cellular sigma factors sigma(H) and sigma(F). We show here, that the second Dps homologue in M. smegmatis, namely MsDps2, is purified in a DNA-bound form and exhibits nucleoid-like structures under the atomic force microscope. It appears that the N-terminal sequence of Dps2 plays a role in nucleoid formation. MsDps2, unlike MsDps1, does not show elevated expression in nutritionally starved or stationary phase conditions; rather its promoter is recognized by RNA polymerase containing sigma(A) or sigma(B), under in vitro conditions. We propose that due to the nucleoid-condensing ability, the expression of MsDps2 is tightly regulated inside the cells.

Non-linear couette flow with heat transfer using the B-G-K model

In recent years a large number of investigators have devoted their efforts to the study of flow and heat transfer in rarefied gases, using the BGK [1] model or the Boltzmann kinetic equation. The velocity moment method which is based on an expansion of the distribution function as a series of orthogonal polynomials in velocity space, has been applied to the linearized problem of shear flow and heat transfer by Mott-Smith [2] and Wang Chang and Uhlenbeck [3]. Gross, Jackson and Ziering [4] have improved greatly upon this technique by expressing the distribution function in terms of half-range functions and it is this feature which leads to the rapid convergence of the method. The full-range moments method [4] has been modified by Bhatnagar [5] and then applied to plane Couette flow using the B-G-K model. Bhatnagar and Srivastava [6] have also studied the heat transfer in plane Couette flow using the linearized B-G-K equation. On the other hand, the half-range moments method has been applied by Gross and Ziering [7] to heat transfer between parallel plates using Boltzmann equation for hard sphere molecules and by Ziering [83 to shear and heat flow using Maxwell molecular model. Along different lines, a moment method has been applied by Lees and Liu [9] to heat transfer in Couette flow using Maxwell's transfer equation rather than the Boltzmann equation for distribution function. An iteration method has been developed by Willis [10] to apply it to non-linear heat transfer problems using the B-G-K model, with the zeroth iteration being taken as the solution of the collisionless kinetic equation. Krook [11] has also used the moment method to formulate the equivalent continuum equations and has pointed out that if the effects of molecular collisions are described by the B-G-K model, exact numerical solutions of many rarefied gas-dynamic problems can be obtained. Recently, these numerical solutions have been obtained by Anderson [12] for the non-linear heat transfer in Couette flow,

Japanese Encephalitis Virus Utilizes the Canonical Pathway To Activate NF-kappa B but It Utilizes the Type I Interferon Pathway To Induce Major Histocompatibility Complex Class I Expression in Mouse Embryonic Fibroblasts

Flaviviruses have been shown to induce cell surface expression of major histocompatibility complex class I (MHC-I) through the activation of NF-kappa B. Using IKK1(-/-), IKK2(-/-), NEMO-/-, and IKK1-/- IKK2-/- double mutant as well as p50(-/-) RelA(-/-) cRel(-/-) triple mutant mouse embryonic fibroblasts infected with Japanese encephalitis virus (JEV), we show that this flavivirus utilizes the canonical pathway to activate NF-kappa B in an IKK2- and NEMO-, but not IKK1-, dependent manner. NF-kappa B DNA binding activity induced upon virus infection was shown to be composed of RelA: p50 dimers in these fibroblasts. Type I interferon (IFN) production was significantly decreased but not completely abolished upon virus infection in cells defective in NF-kappa B activation. In contrast, induction of classical MHC-I (class 1a) genes and their cell surface expression remained unaffected in these NF-kappa B-defective cells. However, MHC-I induction was impaired in IFNAR(-/-) cells that lack the alpha/beta IFN receptor, indicating a dominant role of type I IFNs but not NF-kappa B for the induction of MHC-I molecules by Japanese encephalitis virus. Our further analysis revealed that the residual type I IFN signaling in NF-kappa B-deficient cells is sufficient to drive MHC-I gene expression upon virus infection in mouse embryonic fibroblasts. However, NF-kappa B could indirectly regulate MHC-I expression, since JEV-induced type I IFN expression was found to be critically dependent on it.

Enantiospecific total synthesis of ent-5-senceioyloxy-10,11-epoxythapsan-10-ol

Enantiospecific total synthesis of optical antipode of the sesquiterpene 5-senecioyloxy-10,11-epoxythapsan-10-ol has been described. (R)-Carvone has been employed as the chiral starting material and a combination of intramolecular alkyation and Criegee fragmentation are employed for intramolecular stereospecific transfer of the chirality. An intramolecular diazoketone cyclopropanation and regioselective cyclopropane ring cleavage reactions have been employed or the creation of the three requisite contiguous quaternary carbon atoms.

Peptide models for b-turns.A circular dichroism study

The circular dichroism spectra of four 0-turn model peptides, Z-Aib-Pro-Aib-Pro- OMe (l), Piv-Pro-Aib-NHMe (2), Piv-Pro-D-Ala-NHMe (3) and Piv-Pro-Val-NHMe (4) have been examined under a wide range of solvent conditions, using methanol, hexafluoroisopropanol and cyclohexane. Type I and Type I1 0-turns have been observed for peptides 1 and 2 respectively, in the solid state, while the Pro-D-Ala sequence adopts a Type I1 Sturn in a related peptide crystal structure. A class C spectrum is observed for 1 in various solvents, suggesting a variant of a Type I(II1) structure. The Type I1 f3-turn is characterized by a CD spectrum having two positive CD bands at - 230 nm and - 202 nm, a feature observed in Piv-Pro- D-Ala-NHMe in cyclohexane and methanol and for Piv-Pro-Aib-NHMe in methanol. Peptide 2 exhibits solvent dependent CD spectra, which may be rationalized by considering Type 11, I11 and V reverse turn structures. Piv-Pro- Val-NHMe adopts nonaturn structures in polar solvents, but exhibits a class B spectrum in cyclohexane suggesting a population of Type I &turns.

High-Temperature (1023 K to 1273 K 750 degrees C to 1000 degrees C]) Plastic Deformation Behavior of B-Modified Ti-6Al-4V Alloys: Temperature and Strain Rate Effects

A minor addition of B to the Ti-6Al-4V alloy, by similar to 0.1 wt pct, reduces its as-cast prior beta grain size by an order of magnitude, whereas higher B content leads to the presence of in situ formed TiB needles in significant amounts. An experimental investigation into the role played by these microstructural modifications on the high-temperature deformation behavior of Ti-6Al-4V-xB alloys, with x varying between 0 wt pct and 0.55 wt pct, was conducted. Uniaxial compression tests were performed in the temperature range of 1023 K to 1273 K (750 degrees C to 1000 degrees C) and in the strain rate range of 10(-3) to 10(+1) s(-1). True stress-true strain responses of all alloys exhibit flow softening at lower strain rates and oscillations at higher strain rates. The flow softening is aided by the occurrence of dynamic recrystallization through lath globularization in high temperature (1173 K to 1273 K 900 degrees C to 1000 degrees C]) and a lower strain rate (10(-2) to 10(-3) s(-1)) regime. The grain size refinement with the B addition to Ti64, despite being marked, had no significant effect on this. Oscillations in the flow curve at a higher strain rate (10(0) to 10(+1) s(-1)), however, are associated with microstructural instabilities such as bending of laths, breaking of lath boundaries, generation of cavities, and breakage of TiB needles. The presence of TiB needles affected the instability regime. Microstructural evidence suggests that the matrix cavitation is aided by the easy fracture of TiB needles.

Src Homology 3-interacting Domain of Rv1917c of Mycobacterium tuberculosis Induces Selective Maturation of Human Dendritic Cells by Regulating PI3K-MAPK-NF-kappa B Signaling and Drives Th2 Immune Responses

Mycobacterium tuberculosis, an etiological agent of pulmonary tuberculosis, causes significant morbidity and mortality worldwide. Pathogenic mycobacteria survive in the host by subverting host innate immunity. Dendritic cells (DCs) are professional antigen-presenting cells that are vital for eliciting immune responses to infectious agents, including pathogenic mycobacteria. DCs orchestrate distinct Th responses based on the signals they receive. In this perspective, deciphering the interactions of the proline-glutamic acid/proline-proline-glutamic acid (PE/PPE) family of proteins of M. tuberculosis with DCs assumes significant pathophysiological attributes. In this study, we demonstrate that Rv1917c (PPE34), a representative member of the proline-proline-glutamic-major polymorphic tandem repeat family, interacts with TLR2 and triggers functional maturation of human DCs. Signaling perturbations implicated a critical role for integrated cross-talk among PI3K-MAPK and NF-kappa B signaling cascades in Rv1917c-induced maturation of DCs. However, this maturation of DCs was associated with a secretion of high amounts of anti-inflammatory cytokine IL-10, whereas Th1-polarizing cytokine IL-12 was not induced. Consistent with these results, Rv1917c-matured DCs favored secretion of IL-4, IL-5, and IL-10 from CD4(+) T cells and contributed to Th2-skewed cytokine balance ex vivo in healthy individuals and in patients with pulmonary tuberculosis. Interestingly, the Rv1917c-skewed Th2 immune response involved induced expression of cyclooxygenase-2 (COX-2) in DCs. Taken together, these results indicate that Rv1917c facilitates a shift in the ensuing immunity toward the Th2 phenotype and could aid in immune evasion by mycobacteria.