Reduction of chromano–piperidine-fused isoxazolidines: Tandem intramolecular rearrangements leading to 2-(methylamino)-4-oxo-N-phenyl-N-propyl-4H-chromene-3-carboxamide

Reductive ring opening of isoxazolidine moiety of chromano–piperidine-fused isoxazolidines (3a–c) with HCOONH₄ and 10% Pd/C in a mixture of solvents (THF/MeOH) at ambient temperature, affords novel 2-(methylamino)-4-oxo-N-phenyl-N-propyl-4H-chromene-3-carboxamide (4), which is apparently derived from reductive NO bond cleavage followed by tandem intramolecular rearrangements. Plausible mechanistic rationale for the formation of compound 4 is proffered.     

Phonon Dispersion in Polyadenylic Acid

A study of the normal modes of vibration and their dispersion in polyadenylic acid based on the Urey–Bradley force field is reported. It gives a better interpretation of FTIR spectra as compared with the valence force field. Characteristic features of dispersion curves such as regions of high density‐of‐states, repulsion, and character mixing of dispersive modes are discussed. Predictive valuzes of heat capacity as a function of temperature are reported.     

EFFECT OF TEMPERATURE AND pH ON THE QUENCHING OF TRIPLET LUMIFLAVIN IN THE PRESENCE AND ABSENCE OF FERRI- AND FERROCYANIDE

Abstract— –Flash photolysis at 450 nm over the temperature range 0.8–60°C was used to determine Arrhenius parameters for the first and second order disappearance of triplet lumiflavin (1.66 µ .M ) at a flash energy of 2 kj in deaerated phosphate buffer at varying pH:
³Lf → Lf₀
³Lf +³Lf → Lf₀+ Lf₀
Arrhenius parameters were also determined for the pseudo first-order quenching of triplet lumiflavin by 10 µ M ferri- and ferrocyanide ions,
³Lf + Fe³⁺→ Fe³⁺→ Lf₀+ Fe³⁺ (energy transfer)
³Lf + Fe²⁺→ Lf^-+ Fe³⁺ (electron transfer)
and for disappearance of the semireduced lumiflavin in the presence of ferrocyanide at pH 6.8, by the second-order reaction
Lf^-+Lf ^-→ Lf₀+ Lf⁼.     

Structure of Copper Chelate of 2-Hydroxy-4-methylthiobutanoic Acid as Trace Mineral Additive in Animal Feeding

The chelate complex of Cu2+ with 2-hydroxy-(4-methylthio)butanoate(MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA) is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure(C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158(4), b = 4.9733(12), c = 9.159(2) ?, β = 104.786(4)°) exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.     

ENERGY CONVERSION IN THE DECAY OF TRIPLET LUMIFLAVIN IN THE PRESENCE OF FERRI- AND FERROCYANIDE

Abstract— Flash photolysis at 450 nm has been used to study the quenching of the excited triplet state of lumiflavin and the transient species formed in subsequent reactions in deaerated phosphate buffer (pH 6.9).
The effect of the presence of ferricyanide on the life time of triplet lumiflavin has been studied. The results suggest an energy transfer reaction without concurrent electron transfer reactions. The rate constant for the process was 2.8 times 10⁹ M ^-1 s^-1. The analogous reaction with ferrocyanide could not be observed because of the efficient electron transfer reaction (δG = -20.6 kcal mol^-1) leading to the formation of the semireduced lumiflavin and ferricyanide. The rate constant for this reaction was 3.3 times 10⁹ M ^-1 s^-1. The semireduced lumiflavin radical was found to disappear in a second order reaction with a rate constant of 1.7 times 10⁹ M ^-1 s^-1. It was found to react with ferricyanide with a rate constant of 0.7 times 10⁹ M ^-1 s^-1.
A model for the various photochemical and photophysical processes involved in the decay and quenching of the lumiflavin triplet state is suggested and discussed.     

Discovery of Novel Epoxyketone Peptides as Lipase Inhibitors

Obesity is the most common nutritional disorder in the developed world and is associated with important comorbidities. Pancreatic lipase (PL) inhibitors play a key role in the metabolism of human fat. A series of novel epoxyketones peptide derivatives were investigated for their pancreatic lipase inhibitory activity. The epoxyketone moiety is a well-known reactive electrophile group that has been used as part of proteasome inhibitors in cancer therapy, and it is widely believed that these are very selective for targeting the proteasome active site. Here we investigated various peptide derivatives with an epoxide warhead for their anti-lipase activity. The assessment of these novel epoxyketones was performed by an in-house method that we developed for rapid screening and identification of lipase inhibitors using GC-FID. Herein, we present a novel anti-lipase pharmacophore based on epoxyketone peptide derivatives that showed potent anti-lipase activity. Many of these derivatives had comparable or more potent activity than the clinically used lipase inhibitors such as orlistat. In addition, the lipase appears to be inhibited by a wide range of epoxyketone analogues regardless of the configuration of the epoxide in the epoxyketone moiety. The presented data in this study shows the first example of the use of epoxyketone peptides as novel lipase inhibitors.     

Photodecomposition of molybdenum(II) and tungsten(II) carbonyl complexes with triazole, benz-imidazole, and oxadiazole acetylinic derivatives

Photodecomposition of 10 different molybdenum and tungsten mixed carbonyl complexes, [M(CO)₃(B)(A)]I₂ where B=o-phenanthroline or bipyridyl, A=3-(2-propynyl)thio-4,5-diphenyl-4H-1,2,4-triazole (TRZA) or S-propynyl-2-thio benz-imidazole (BIMDA) and 2(2-propynyl-thio(5-phenyl)-1,3,4-oxadiazole (OXA). M(CO)₃(TRZA)I₂, [M(CO)₂(PPh₃)_X(TRZA)I_Y]I_Z where M=Mo, X, Y and Z=1 and M=W, X and Z=2, Y=0, have been performed at 365 nm in oxygen saturated chloroform at 25 °C. The absorbance spectrum of these complexes have been recorded with the time of irradiation in order to examine the kinetics of photodecay.

The apparent rate constant (K_d) for the first-order reaction have been calculated and found to be (3.32–4.79)×10⁻⁵ s⁻¹. The primary quantum yields (Φ) has also been calculated and were in the range (8.33–12.1)×10⁻⁴. The mechanism of the photodecomposition has been suggested according to the kinetic, and photoproduct analysis data, and is similar to reaction of photo-oxidative degradation of polluted molecules in the water.     

Adaptive regularization with cubics on manifolds

Mathematical Programming - Adaptive regularization with cubics (ARC) is an algorithm for unconstrained, non-convex optimization. Akin to the trust-region method, its iterations can be thought of as...     

Analysis of the stress singularity for a bi-material V-notch by the boundary element method

A new algorithm coupling the boundary element technique with the characteristic expansion method is proposed for the computation of the singular stress field in the V-notched bi-material structure. After the stress asymptotic expansions are introduced into the linear elasticity equilibrium equations, the governing equations at the small sector dug out from the bi-material V-notch tip region are transformed into the ordinary differential eigen-equations. All the parameters in the asymptotic expansions except the combination coefficients can be achieved by solving the established eigen-equations with the interpolating matrix method. Furthermore, the conventional boundary element method is applied to modeling the remaining structure without the notch tip region. The combination coefficients in the asymptotic expansion forms can be computed by the discretized boundary integral equations. Thus, the singular stress field at the V-notch tip and the generalized stress intensity factors of the bi-material notch are successfully calculated. The accurate singular stress field obtained here is very useful in the evaluation of the fracture property and the fatigue life of the V-notched bi-material structure.     

Evaluation of the stress singularities of plane V-notches in bonded dissimilar materials

According to the linear theory of elasticity, there exists a combination of different orders of stress singularity at a V-notch tip of bonded dissimilar materials. The singularity reflects a strong stress concentration near the sharp V-notches. In this paper, a new way is proposed in order to determine the orders of singularity for two-dimensional V-notch problems. Firstly, on the basis of an asymptotic stress field in terms of radial coordinates at the V-notch tip, the governing equations of the elastic theory are transformed into an eigenvalue problem of ordinary differential equations (ODEs) with respect to the circumferential coordinate θ around the notch tip. Then the interpolating matrix method established by the first author is further developed to solve the general eigenvalue problem. Hence, the singularity orders of the V-notch problem are determined through solving the corresponding ODEs by means of the interpolating matrix method. Meanwhile, the associated eigenvectors of the displacement and stress fields near the V-notches are also obtained. These functions are essential in calculating the amplitude of the stress field described as generalized stress intensity factors of the V-notches. The present method is also available to deal with the plane V-notch problems in bonded orthotropic multi-material. Finally, numerical examples are presented to illustrate the accuracy and the effectiveness of the method.