C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: solvent-free synthesis of alpha-aminonitriles and beta-nitroamines under aerobic condition

A solvent-free synthesis of alpha-aminonitriles and beta-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(VI) acetylacetonoate was found to catalyze cyanation of tertiary amines to form alpha-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish beta-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.

Molybdenum trioxide catalyzed oxidative cross-dehydrogenative coupling of benzylic sp(3) C-H bonds: synthesis of alpha-aminophosphonates under aerobic conditions

Molybdenum trioxide (MoO3) catalyzed efficient oxidative cross-dehydrogenative-coupling (CDC) method for C-H functionalization of N-aryl tetrahydroisoquinolines has been explored. This user-friendly method of synthesizing alpha-aminophosphonates employs 1.1 equiv of dialkyl-H-phosphonate under aerobic condition. Formation of new C-P bonds from unfunctionalized starting materials under environmentally benign conditions provides an excellent avenue for the synthesis of biologically active alpha-aminophosphonates. (C) 2012 Elsevier Ltd. All rights reserved.

Combining adiabatic and Hartmann-Hahn cross-polarization for sensitivity enhancement in solid state separated local field 2D-NMR experiments of partially ordered systems

In this Letter, we examine magnetization in double- and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and describe their role in determining the sensitivity of a class of separated local field NMR experiments based on Hartmann-Hahn cross-polarization. We observe that for the liquid crystal system studied, a large dilute spin-polarization, obtained initially by the use of adiabatic cross-polarization, can enhance the sensitivity of the above experiment. The signal enhancement factors, however, are found to vary and depend on the local dynamics. The experimental results have been utilized to obtain the local order-parameters of the system. (C) 2012 Elsevier B. V. All rights reserved.

Cross-Guided Clustering: Transfer of Relevant Supervision across Tasks

Lack of supervision in clustering algorithms often leads to clusters that are not useful or interesting to human reviewers. We investigate if supervision can be automatically transferred for clustering a target task, by providing a relevant supervised partitioning of a dataset from a different source task. The target clustering is made more meaningful for the human user by trading-off intrinsic clustering goodness on the target task for alignment with relevant supervised partitions in the source task, wherever possible. We propose a cross-guided clustering algorithm that builds on traditional k-means by aligning the target clusters with source partitions. The alignment process makes use of a cross-task similarity measure that discovers hidden relationships across tasks. When the source and target tasks correspond to different domains with potentially different vocabularies, we propose a projection approach using pivot vocabularies for the cross-domain similarity measure. Using multiple real-world and synthetic datasets, we show that our approach improves clustering accuracy significantly over traditional k-means and state-of-the-art semi-supervised clustering baselines, over a wide range of data characteristics and parameter settings.

Surrogate based design optimisation of composite aerofoil cross-section for helicopter vibration reduction

Design optimisation of a helicopter rotor blade is performed. The objective is to reduce helicopter vibration and constraints are put on frequencies and aeroelastic stability. The ply angles of the D-spar and skin of the composite rotor blade with NACA 0015 aerofoil section are considered as design variables. Polynomial response surfaces and space filling experimental designs are used to generate surrogate models of the objective function with respect to cross-section properties. The stacking sequence corresponding to the optimal cross-section is found using a real-coded genetic algorithm. Ply angle discretisation of 1 degrees, 15 degrees, 30 degrees and 45 degrees are used. The mean value of the objective function is used to find the optimal blade designs and the resulting designs are tested for variance. The optimal designs show a vibration reduction of 26% to 33% from the baseline design. A substantial reduction in vibration and an aeroelastically stable blade is obtained even after accounting for composite material uncertainty.

NMR Analysis of Cross Strand Aromatic Interactions in an 8 Residue Hairpin and a 14 Residue Three Stranded beta-Sheet Peptide

Cross strand aromatic interactions between a facing pair of phenylalanine residues in antiparallel beta-sheet structures have been probed using two structurally defined model peptides. The octapeptide Boc-(LFVPPLFV)-P-D-P-L-OMe (peptide 1) favors the beta-hairpin conformation nucleated by the type II' beta-turn formed by the (D)Pro-(L)Pro segment, placing Phe2 and Phe7 side chains in proximity. Two centrally positioned (D)Pro-(L)Pro segments facilitate the three stranded beta-sheet formation in the 14 residue peptide Boc-LFV(D)P(L)PLFVA(D)P(L)PLFV-OMe (peptide 2) in which the Phe2/Phe7 orientations are similar to that in the octapeptide. The anticipated folded conformations of peptides 1 and 2 are established by the delineation of intramolecularly hydrogen bonded NH groups and by the observation of specific cross strand NOEs. The observation of ring current shifted aromatic protons is a diagnostic of close approach of the Phe2 and Phe7 side chains. Specific assignment of aromatic proton resonances using HSQC and HSQC-TOCSY methods allow an analysis of interproton NOEs between the spatially proximate aromatic rings. This approach facilitates specific assignments in systems containing multiple aromatic rings in spectra at natural abundance. Evidence is presented for a dynamic process which invokes a correlated conformational change about the C-alpha-C-beta(chi(1)) bond for the pair of interacting Phe residues. NMR results suggest that aromatic ring orientations observed in crystals are maintained in solution. Anomalous temperature dependence of ring current induced proton chemical shifts suggests that solvophobic effects may facilitate aromatic ring clustering in apolar solvents.

Formulation development and evaluation of lamivudine controlled release tablets using cross-linked sago starch

Objectives: Modified starches based polymeric substances find utmost applicability in pharmaceutical formulation development. Cross-linked starches showed very promising results in drug delivery application. The present investigation concerns with the development of controlled release tablets of lamivudine using cross-linked sago starch. Methods: The cross-linked derivative was synthesized with phosphorous oxychloride and native sago starch in basic pH medium. The cross-linked sago starch was tested for acute toxicity and drug-excipient compatibility study. The formulated tablets were evaluated for various physical characteristics, in vitro dissolution release study and in vivo pharmacokinetic study in rabbit model. Results: In vitro release study showed that the optimized formulation exhibited highest correlation (R) in case of zero order kinetic model and the release mechanism followed a combination of diffusion and erosion process. There was a significant difference in the pharmacokinetic parameters (T-max, C-max, AUC, V-d, T-1/2, and MDT) of the optimized formulation as compared to the marketed conventional tablet Lamivir (R). Conclusion: The cross-linked starch showed promising results in terms of controlling the release behavior of the active drug from the matrix. The hydrophilic matrix synthesized by cross-linking could be used with a variety of active pharmaceutical ingredients for making their controlled/sustained release formulations.

Biocides - resistance, cross-resistance mechanisms and assessment

Importance of the field: Antibiotic resistance in bacterial pathogens has increased worldwide leading to treatment failures. Concerns have been raised about the use of biocides as a contributing factor to the risk of antimicrobial resistance (AMR) development. In vitro studies demonstrating increase in resistance have often been cited as evidence for increased risks. It is therefore important to understand the mechanisms of resistance employed by bacteria toward biocides used in consumer products and their potential to impart cross-resistance to therapeutic antibiotics. Areas covered: In this review, the mechanisms of resistance and cross-resistance reported in the literature toward biocides commonly used in consumer products are summarized. The physiological and molecular techniques used in describing and examining these mechanisms are reviewed and application of these techniques for systematic assessment of biocides for their potential to develop resistance and/or cross-resistance is discussed. Expert opinion: The guidelines in the usage of biocides in household or industrial purpose should be monitored and regulated to avoid the emergence of any MDR strains. The genetic and molecular methods to monitor the resistance development to biocides should be developed and included in preclinical and clinical studies.

Border basis detection is NP-complete

Border basis detection (BBD) is described as follows: given a set of generators of an ideal, decide whether that set of generators is a border basis of the ideal with respect to some order ideal. The motivation for this problem comes from a similar problem related to Grobner bases termed as Grobner basis detection (GBD) which was proposed by Gritzmann and Sturmfels (1993). GBD was shown to be NP-hard by Sturmfels and Wiegelmann (1996). In this paper, we investigate the computational complexity of BBD and show that it is NP-complete.

QCD mini-jets contribution to the total cross-section for pions and protons and expectations at LHC

We describe our kt-resummation model for total cross-sections and show its application to pp and ¯pp scattering. The model uses mini-jets to drive the rise of the cross-section and soft gluon resummation in the infrared region to transform the violent rise of the mini-jet cross-section into a logarithmic behaviour in agreement with the Froissart bound.

A practical approach for cross-functional vehicle body weight optimization

The goal of optimization in vehicle design is often blurred by the myriads of requirements belonging to attributes that may not be quite related. If solutions are sought by optimizing attribute performance-related objectives separately starting with a common baseline design configuration as in a traditional design environment, it becomes an arduous task to integrate the potentially conflicting solutions into one satisfactory design. It may be thus more desirable to carry out a combined multi-disciplinary design optimization (MDO) with vehicle weight as an objective function and cross-functional attribute performance targets as constraints. For the particular case of vehicle body structure design, the initial design is likely to be arrived at taking into account styling, packaging and market-driven requirements. The problem with performing a combined cross-functional optimization is the time associated with running such CAE algorithms that can provide a single optimal solution for heterogeneous areas such as NVH and crash safety. In the present paper, a practical MDO methodology is suggested that can be applied to weight optimization of automotive body structures by specifying constraints on frequency and crash performance. Because of the reduced number of cases to be analyzed for crash safety in comparison with other MDO approaches, the present methodology can generate a single size-optimized solution without having to take recourse to empirical techniques such as response surface-based prediction of crash performance and associated successive response surface updating for convergence. An example of weight optimization of spaceframe-based BIW of an aluminum-intensive vehicle is given to illustrate the steps involved in the current optimization process.

Effects of different modes of hot cross-rolling in 7010 aluminum alloy: part I. evolution of microstructure and texture

The current study describes the evolution of microstructure and texture in an Al-Zn-Mg-Cu-Zr-based 7010 aluminum alloy during different modes of hot cross-rolling. Processing of materials involves three different types of cross-rolling. The development of texture in the one-step cross-rolled specimen can be described by a typical beta-fiber having the maximum intensity near Copper (Cu) component. However, for the multi-step cross-rolled specimens, the as-rolled texture is mainly characterized by a strong rotated-Brass (Bs) component and a very weak rotated-cube component. Subsequent heat treatment leads to sharpening of the major texture component (i.e., rotated-Bs). Furthermore, the main texture components in all the specimens appear to be significantly rotated in a complex manner away from their ideal positions because of non-symmetric deformations in the two rolling directions. Detailed microstructural study indicates that dynamic recovery is the dominant restoration mechanism operating during the hot rolling. During subsequent heat treatment, static recovery dominates, while a combination of particle-stimulated nucleation (PSN) and strain-induced grain boundary migration (SIBM) causes partial recrystallization of the grain structure. The aforementioned restoration mechanisms play an important role in the development of texture components. The textural development in the current study could be attributed to the combined effects of (a) cross-rolling and inter-pass annealing that reduce the intensity of Cu component after each successive pass, (b) recrystallization resistance of Bs-oriented grains, (c) stability of Bs texture under cross-rolling, and (d) Zener pinning by Al3Zr dispersoids.

Effects of different modes of hot cross-rolling in 7010 aluminum alloy: part II. mechanical properties anisotropy

The influence of microstructure and texture developed by different modes of hot cross-rolling on in-plane anisotropy (A (IP)) of yield strength, work hardening behavior, and anisotropy of Knoop hardness (KHN) yield locus has been investigated. The A (IP) and work hardening behavior are evaluated by tensile testing at 0 deg, 45 deg, and 90 deg to the rolling direction, while yield loci have been generated by directional KHN measurements. It has been observed that specimens especially in the peak-aged temper, in spite of having a strong, rotated Brass texture, show low A (IP). The results are discussed on the basis of Schmid factor analyses in conjunction with microstructural features, namely grain morphology and precipitation effects. For the specimen having a single-component texture, the yield strength variation as a function of orientation can be rationalized by the Schmid factor analysis of a perfectly textured material behaving as a quasi-single crystal. The work hardening behavior is significantly affected by the presence of solute in the matrix and the state of precipitation rather than texture, while yield loci derived from KHN measurements reiterate the low anisotropy of the materials. Theoretic yield loci calculated from the texture data using the visco-plastic self-consistent model and Hill's anisotropic equation are compared with that obtained experimentally.

Tensile flow and work hardening behavior of hot cross-rolled AA7010 aluminum alloy sheets

The present work describes the tensile flow and work hardening behavior of a high strength 7010 aluminum alloy by constitutive relations. The alloy has been hot rolled by three different cross-rolling schedules. Room temperature tensile properties have been evaluated as a function of tensile axis orientation in the as-hot rolled as well as peak aged conditions. It is found that both the Ludwigson and a generalized Voce-Bergstrom relation adequately describe the tensile flow behavior of the present alloy in all conditions compared to the Hollomon relation. The variation in the Ludwigson fitting parameter could be correlated well with the microstructural features and anisotropic contribution of strengthening precipitates in the as-rolled and peak aged conditions, respectively. The hardening rate and the saturation stress of the first Voce-Bergstrom parameter, on the other hand, depend mainly on the crystallographic texture of the specimens. It is further shown that for the peak aged specimens the uniform elongation (epsilon(u)) derived from the Ludwigson relation matches well with the measured epsilon(u) irrespective of processing and loading directions. However, the Ludwigson fit overestimates the epsilon(u) in case of the as-rolled specimens. The Hollomon fit, on the other hand, predicts well the measured epsilon(u), of the as-rolled specimens but severely underestimates the epsilon(u), for the peak aged specimens. Contrarily, both the relations significantly overestimate the UTS of the as-rolled and the peak aged specimens. The Voce-Bergstrom parameters define the slope of e Theta-sigma plots in the stage-III regime when the specimens show a classical linear decrease in hardening rate in stage-III. Further analysis of work hardening behavior throws some light on the effect of texture on the dislocation storage and dynamic recovery.

Unprecedented formation of a 14-membered dihydropyran macrocycle via sequential olefin cross metathesis-intramolecular hetero Diels-Alder reaction

Formation of a 2,3-dihydro-4H-pyran containing 14-membered macrocycle by sequential olefin cross metathesis and a highly regiospecific hetero Diels-Alder reaction was observed in the reaction of a hydroxydienone derived from tartaric acid with Grubbs' second generation catalyst. It was found that the free alcohol in the hydroxyenone led to the macrocycle formation, while protection of the hydroxy group formed the ring closing metathesis product. (C) 2013 Elsevier Ltd. All rights reserved.