A comparative kinetic and mechanistic study of glutamic acid oxidation by acid permanganate in the absence and presence of sodium dodecyl sulphate

The kinetics and mechanism of glutamic acid (GCO₂H) oxidation by acid permanganate has been carried out in the absence and presence of sodium dodecyl sulphate (SDS). The surfactant enhances the reaction rate without changing the reaction mechanism. The overall rate expression for the reduction of Mn^VII may be written:

Microwave-assisted cleavage of Weinreb amide for carboxylate protection in the synthesis of a (R)-3-hydroxyalkanoic acid

A versatile route for the modular synthesis of (R)-3-hydroxyalkanoic acids, constituents of the naturally biodegradable poly(3-hydroxyalkanoate) polymers, and its application to the synthesis of (R)-3-hydroxydecanoic acid is described. Key steps include a microwave-assisted catalytic transfer hydrogenation and a facile microwave-assisted hydrolysis of an N-methoxy-N-methyl (Weinreb) amide, which enhances the practicality of this protecting group for carboxylic acids.     

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2

The oxidation of transition metals such as manganese and copper by dioxygen (O₂) is of great interest to chemists and biochemists for fundamental and practical reasons. In this report, the O₂ reactivities of 1:1 and 1:2 mixtures of [(TPP)Mn^II] (1; TPP: Tetraphenylporphyrin) and [(tmpa)Cu^I(MeCN)]⁺ (2; TMPA: Tris(2-pyridylmethyl)amine) in 2-methyltetrahydrofuran (MeTHF) are described. Variable-temperature (−110 °C to room temperature) absorption spectroscopic measurements support that, at low temperature, oxygenation of the (TPP)Mn/Cu mixtures leads to rapid formation of a cupric superoxo intermediate, [(tmpa)Cu^II(O₂^•–)]⁺ (3), independent of the presence of the manganese porphyrin complex (1). Complex 3 subsequently reacts with 1 to form a heterobinuclear μ-peroxo species, [(tmpa)Cu^II–(O₂^2–)–Mn^III(TPP)]⁺ (4; λ_max = 443 nm), which thermally converts to a μ-oxo complex, [(tmpa)Cu^II–O–Mn^III(TPP)]⁺ (5; λ_max = 434 and 466 nm), confirmed by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy. In the 1:2 (TPP)Mn/Cu mixture, 4 is subsequently attacked by a second equivalent of 3, giving a bis-μ-peroxo species, i.e., [(tmpa)Cu^II−(O₂²⁻)−Mn^IV(TPP)−(O₂²⁻)−Cu^II(tmpa)]²⁺ (7; λ_max = 420 nm and δ_pyrrolic = −44.90 ppm). The final decomposition product of the (TPP)Mn/Cu/O₂ chemistry in MeTHF is [(TPP)Mn^III(MeTHF)₂]⁺ (6), whose X-ray structure is also presented and compared to literature analogs.     

Kinetics and mechanism of the oxidation of N-methylformamide and N,N-dimethylformamide by silver (II) in aqueous perchlorate media and comparison with oxidation by CoIII and MnIII

Detailed measurements on the kinetics and stoichiometry of the oxidation of N-methylformamide and N,N-dimethylformamide by aquosilver (II) ions are reported. Four Ag ions are consumed for each amide, and the reaction is first order in [Ag] and first order in [amide]. The reaction is inversely dependent on acidity in the range of 1.5–5.0M HClO₄. The oxidation rate is independent of [Ag^I] and ionic strength. The proposed reaction mechanism and activation parameters are compared with those found for the oxidation of amides by other oxidants such as cobalt(III) and manganese(III).     

Efficient remainder rule

Understanding the solution of a problem may require the reader to have background knowledge on the subject. For instance, finding an integer which, when divided by a nonzero integer leaves a remainder; but when divided by another nonzero integer may leave a different remainder. To find a smallest positive integer or a set of integers following the given conditions, one may need to understand the concept of modulo arithmetic in number theory. The Chinese Remainder Theorem is a known method to solve these types of problems using modulo arithmetic. In this paper, an efficient remainder rule has been proposed based on basic mathematical concepts. These core concepts are as follows: basic remainder rules of divisions, linear equation in slope intercept form, arithmetic progression and the use of a graphing calculator. These are easily understood by students who have taken prealgebra or intermediate algebra.     

A numerical bifurcation study of friction effects in a slip-controlled torque converter clutch

Friction plays a key role in the efficiency and stability of the slip-controlled torque converter clutches. The effects of friction on the dynamics and stability of a slip-controlled torque converter clutch system using a bifurcation-analysis-based approach is presented in this paper. A three degree-of-freedom nonlinear driveline model with integral feedback action to control the clutch slip speed has been utilized for this study. The clutch interface friction is dependent on the slip speed and is a function of the static friction constant, μ ₀, the low velocity friction constant μ ₁, and the low velocity exponential rate, γ. Using one-parameter numerical continuation, local Hopf bifurcations of the subcritical type are observed as the friction parameters μ ₁ and γ were varied at low slip speeds. The continuation results are verified using simulations of the full nonlinear model. Stick-slip and undesirable oscillations of the model inertia elements are observed for certain parameter values. As the slip speed is increased, the bifurcation instability occurs at an increasingly higher value of μ ₁ signifying an improved tolerance of negative friction gradient at higher slip speeds. Smaller exponential rates γ are tolerated at higher slip speeds before the bifurcation instability occurs. For the range of parameter values considered, no bifurcations occur for a slip speeds higher than 3.4 and 4.5 rad/s with μ ₁ and γ as the continuation parameters, respectively. These values of slip speeds are much lower than the system’s first mode of torsional vibration of 16 Hz (≈100 rad/s).     

One-step synthesis of labeled sugar nucleotides for protein O-GlcNAc modification studies by chemical function analysis of an archaeal protein

Herein we present the chemical function analysis of a recombinant sugar nucleotidyltransferase from the hyperthermophile Pyrococcus furiosus and its use in the one-pot synthesis of chloroacetyl- and alkyne-tagged analogues of uridinediphospho-N-acetylglucosamine (UDP-GlcNAc). The gene was originally annotated as a glucose-1-phosphate deoxythymidylyltransferase; however, kinetic analysis of a panel of sugar-1-phosphates with the protein shows that it is better described as a bifunctional protein that synthesizes UDP-GlcNAc from glucosamine-1-phosphate and acetyl coenzyme A (CoA). A new mass-spectrometry-based assay for the rapid analysis of the acyltransferase activity demonstrates that the enzyme can also accept cheaper truncated N-acetylcysteamine thioester substrates in place of the natural acetyl CoA. The enzyme can tolerate alkyne or chloride substitutions in the acyl moiety, thereby allowing the facile synthesis of tagged sugar nucleotides for future use in protein O-GlcNAc modification studies.     

White-light-induced fragmentation of methane

We experimentally probe molecular ionization and dissociation of methane molecules in the gas phase upon their irradiation by intense pulses of white light that spans the wavelength range 500-850 nm. White light pulses are generated upon irradiation of BK7 glass by 36-fs-long pulses of intense 820 nm laser light. Comparison is made of the molecular fragmentation patterns obtained using white light that is depolarized with those obtained using single-color (820 nm) light that is highly chirped. On the basis of such comparison, we make hitherto-unavailable estimates of the in situ intensity of white light pulses. Results obtained using white light also indicate that resonances apparently do not play any role in the ionization dynamics that ensue upon irradiation by intense, broadband light; neither are the dynamics affected by the polarization properties of the 820 nm light that is used to generate the white light.     

3 β ‐Acetoxy‐5 α ‐cholestan‐6‐one: A Steroid

The crystal and molecular structure of 3 β ‐Acetoxy‐5 α ‐cholestan‐6‐one has been determined by X‐ray crystallographic techniques. The compound crystallizes in the space group P2₁ with cell parameters : a = 13.060(3), b=6.299(2), c=17.152(6)Å; β =96.47(3)o, V = 1402.02ų, Z = 2, R = 0.072 for 1921 observed reflections. The six‐membered rings (A, B and C) exist in the chair conformations while the five‐membered ring‐d assumes half‐chair. All rings of the steroid skeleton are trans connected.     

Preparation and evaluation of novel stationary phases for improved chromatographic purification of pneumocandin B0

Preparation and evaluation of a number of stationary phases for improved chromatographic purification of pneumocandin B0, a key intermediate in the synthesis of the antifungal agent, Cancidas, has led to the identification of several materials with potential for improved performance.