Milling Bifurcations from Structural Asymmetry and Nonlinear Regeneration

This paper investigates multiple modeling choices for analyzing the rich and complex dynamics of high-speed milling processes. Various models are introduced to capture the effects of asymmetric structural modes and the influence of nonlinear regeneration in a discontinuous cutting force model. Stability is determined from the development of a dynamic map for the resulting variational system. The general case of asymmetric structural elements is investigated with a fixed frame and rotating frame model to show differences in the predicted unstable regions due to parametric excitation. Analytical and numerical investigations are confirmed through a series of experimental cutting tests. The principal results are additional unstable regions, hysteresis in the bifurcation diagrams, and the presence of coexisting periodic and quasiperiodic attractors which is confirmed through experimentation.     

Metabolite identification by liquid chromatography-mass spectrometry

Metabolite identification (Met ID) is important during the early stages of drug discovery and development, as the metabolic products may be pharmacologically active or toxic in nature. Liquid chromatography-mass spectrometry (LC-MS) has a towering role in metabolism research.This review discusses current approaches and recent advances in using LC-MS for Met ID. We critically assess and compare various mass spectrometers, highlighting their strengths and limitations. Citing appropriate examples, we cover recent LC and ion sources, isotopic-pattern matching, hydrogen/deuterium-exchange MS, data dependent analyses, MS^E, mass defect filter, 2D and 3D approaches for the elucidation of molecular formula, polarity switching, and background-subtraction and noise-reduction algorithms. A flow chart outlines a comprehensive strategy for Met ID, including a focus on reactive metabolites.     

Total synthesis of (-)-N-methylwelwitindolinone C isothiocyanate

We report the first total synthesis of (-)-N-methylwelwitindolinone C isothiocyanate. Our route features a number of key transformations, including an indolyne cyclization to assemble the [4.3.1]-bicyclic scaffold, as well as a late-stage intramolecular nitrene insertion to functionalize the C11 bridgehead carbon en route to the natural product.     

A fungal nonribosomal peptide synthetase module that can synthesize thiopyrazines

A nonribosomal peptide synthetase-like enzyme (NRPS325) from Aspergillus terreus was reconstituted in vitro and was shown to synthesize thiopyrazines using an unprecedented mechanism. Substrate promiscuity of NRPS325 toward different amino acids and free thiols was explored to produce >60 different thiopyrazine compounds.     

Production of lantipeptides in Escherichia coli

Lantipeptides are ribosomally synthesized and posttranslationally modified peptides containing thioether cross-links. We describe the preparation of seven different lantipeptides in Escherichia coli and demonstrate that this methodology can be used to incorporate nonproteinogenic amino acids.     

Synthesis and antibacterial activity of some 5-hydroxy-5-trifluoromethyl-4,5-dihydropyrazol-1-thiocarboxamides, 3-trifluoromethylpyrazol-1-thiocarboxamides and 4-aryl-2-(5(3)-trifluoromethyl-1-pyrazolyl)thiazoles

5-Hydroxy-5-trifluoromethyl-4,5-dihydropyrazol-1-thiocarboxamides 3 and 3-trifluoromethylpyrazol-1-thiocarboxamides 4, regioselectively obtained by the condensation of trifluoromethyl-β-diketones with thiosemicarbazide under neutral and acidic conditions, on further reaction with phenacyl bromides 5 afforded 4-aryl-(5-trifluoromethyl-pyrazol-1-yl)thiazoles 6 and 4-aryl-(3-trifluoromethyl-pyrazol-1-yl)thiazoles 7, respectively. Five 4,5-dihydropyrazoles (3a–e) and two pyrazolylthiazoles (6a and 6c) were tested against one Gram-positive and one Gram-negative bacteria to assess their in vitro antibacterial activity. Compounds 3a, 3b and 3e showed moderate antibacterial activity against Gram-positive bacterium, Bacillus pumilus.     

Syntheses and photophysical properties of luminescent mono-cyclometalated gold(III) cis-dialkynyl complexes

A series of novel luminescent neutral cyclometalated gold(III) complexes of the type cis-[(N^C)Au(C≡CR)(2)] (R = aryl, silyl groups) having different cyclometalating cores (N^C) have been synthesized by CuI promoted halide to alkynyl metathesis with NEt(3) as in situ deprotonating agent. Along with spectroscopic characterizations (nuclear magnetic resonance and infrared spectroscopies and electrospray ionization mass spectrometry) and elemental analysis, the molecular structures of some of the complexes have been established by single-crystal X-ray diffraction studies. Photophysical studies reveal that the complexes exhibit room-temperature phosphorescence (RTP). Experimental observations and density functional theory calculations qualitatively suggest limited participation of the metal and alkynyl ligands in the lowest energy emitting state. The nature of the emission is mainly governed by metal-perturbed (3)IL(π-π*) transitions originating from the cyclometalate part of the molecule, and its variation readily leads to the tuning of the emission wavelengths. Cyclic voltammetry measurements of selected complexes showed irreversible redox behavior with near-equivalent cathodic peak potential (E(p,c)) assigned to the C^N core.     

Finite p-groups with non-cyclic center have a non-inner automorphism of order p

Archiv der Mathematik - Let G be a finite non-abelian p-group and let $$W(G)/Z(G)=\Omega _1(Z_2(G)/Z(G))$$ . A longstanding conjecture asserts that G admits a non-inner automorphism of order p. We...     

Low-temperature magnetization relaxation in magnetic molecular solids

The low temperature relaxation of the magnetization in molecular magnetic solids such as Fe₈ is studied using Monte Carlo simulations. A set of rate equations is then developed to understand the simulations, and the results are compared. The simulations show that the magnetization of an initially saturated sample deviates as a square-root in time at short times, as observed experimentally, and this law is derived from the rate equations analytically.     

An optimal protection and restoration scheme (OPARS) for optical networks

Protection and restoration are critical network design issues for optical networks since even a single failure for a short duration may result in huge data loss due to the large capacity of optical fibers. However, few studies have been done on these issues for optical burst switching (OBS) networks. Protection and restoration are essential mechanisms for guaranteeing more reliable traffic delivery services. But it is not easy to apply existing mechanisms to optical burst switching (OBS) networks due to its one-way reservation signaling and the statistical burst multiplexing. Thus, to achieve the high transmission performance and reliability simultaneously, unique properties of OBS must be considered in the design of protection scheme. In this paper, an optimal protection and restoration scheme (OPARS) has been introduced that not only optimizes the number of provisioned protection wavelengths adaptively based on the traffic load as well as the quality of service (QoS) requirements of bursts in high speed networks but also minimizes burst loss rates. In addition, the proposed scheme has been used as an efficient contention resolution technique. The simulation results verify that the proposed scheme improve the network resource and channel utilization while guaranteeing the targeted protection reliability and QoS requirements of bursts.