New environmentally friendly catalysts containing Pd-interstitial carbon made from Pd-glucose precursors for ultraselective hydrogenations in the liquid phase

We report a novel preparation of a Pd nanocatalyst modified with subsurface C via blending a glucose precursor at the molecular level: the catalyst is demonstrated for the first time to be stereoselective in the hydrogenation of alkynes to cis-alkenes in the liquid phase.     

Perfect state transfer in cubelike graphs

Suppose C is a subset of non-zero vectors from the vector space . The cubelike graphX(C) has as its vertex set, and two elements of are adjacent if their difference is in C. If M is the d×|C| matrix with the elements of C as its columns, we call the row space of M the code of X. We use this code to study perfect state transfer on cubelike graphs. Bernasconi et al. have shown that perfect state transfer occurs on X(C) at time π/2 if and only if the sum of the elements of C is not zero. Here we consider what happens when this sum is zero. We prove that if perfect state transfer occurs on a cubelike graph, then it must take place at time τ=π/2D, where D is the greatest common divisor of the weights of the code words. We show that perfect state transfer occurs at time π/4 if and only if D=2 and the code is self-orthogonal.     

A facile synthesis of pyrazoles with multi-point structural diversity by 1,3-dipolar cycloaddition

We describe the synthesis of diverse pyrazoles by 1,3-dipolar cycloaddition of ethyl diazoacetate with various acetylenes in refluxing toluene. The product pyrazoles are useful starting points for preparing a diverse collection of trisubstituted pyrazole carboxamides. For aryl and heteroaryl alkynes a single product is obtained while alkyl alkynes afford a ca. 6:1 mixture of regioisomers. The observed regioselectivity for the cycloaddition step and the ease of reaction are consistent with predictions derived from computing the HOMO-LUMO energies of the reactants.     

Minimizing weighted tardiness of job-shop scheduling using a hybrid genetic algorithm

Relative to job-shop scheduling problems that optimize makespan or flow time, due-date-related problems are usually much more computationally complex and are classified as strongly NP-hard. In this paper, a hybrid framework integrating a heuristic and a genetic algorithm (GA) is utilized for job-shop scheduling to minimize weighted tardiness. For each new generation of schedules, the GA determines the first operation of each machine, and the heuristic determines the assignment of the remaining operations. Schedules with inferior tardiness are discarded before the next round of evolution. Extensive numerical experiments were conducted for different levels of due-date tightness. The results show that the hybrid framework performs significantly better than does either a heuristic or GA alone. It is also found to be superior to a well-recognized heuristic improvement procedure (lead-time iterations). Specifically, the combination of the R&M heuristic and a GA outperforms a number of heuristics commonly used to minimize total tardiness and weighted total tardiness; this combination is, however, outperformed by the heuristic of Kreipl [Kreipl, S., 2000. A large step random walk for minimizing total weighted tardiness in a job shop. Journal of Scheduling 3, 125–138]. We also develop a generalized hybrid framework that can adapt to different job-shop problems—with or without sequence-dependent setups and with different objectives (e.g., makespan, tardiness, flow time). The new framework allows the interaction of parallel evolutions, extending the GA-heuristic environment to the solving of multi-objective scheduling problems.     

Ruthenium complexes with a terminal hydrazido ligand. Synthesis, spectroscopy, and X-ray crystal structure

Bis(1,1-diphenylhydrazido(1-))ruthenium(IV) porphyrins, [Ru(IV)(Por)(NHNPh2)2] (Por = TPP, TTP, 4-Cl-TPP, 4-MeO-TPP), were prepared in approximately 60% yields through the reaction of dioxoruthenium(VI) porphyrins, [Ru(VI)(Por)O2], with 1,1-diphenylhydrazine in ethanol. This new type of ruthenium complex has been characterized by 1H NMR, IR, UV-vis, and FABMS with elemental analysis. The crystal structure of [Ru(IV)(TTP)(NHNPh2)2], which reveals an eta1-coordination mode for both hydrazido axial ligands, has been determined. The average Ru-NHNPh2 distance and Ru-N-N angle were found to be 1.911(3) A and 141.1(3) degrees, respectively. The porphyrin ring exhibits a ruffling distortion that is unprecedentedly large for ruthenium complexes with simple porphyrinato ligands (such as TTP). This is probably due to the steric effect of the axial hydrazido(1-) ligands.     

Effect of temperature,particle size and percentage deacetylation on the adsorption of acid dyes on chitosan

The adsorption of five acidic dyes on chitosan—a by-product from waste crustacean shell—has been studied. The equilibrium data have been studied using Langmuir, Freundlich and Redlich-Peterson equations. The best correlations are obtained using the Langmuir isotherm suggesting the mechanism involves one process step of dyes complexing with the free amino group. The effect of chitosan particle size was investigated and showed an increase in adsorption capacity with decreasing particle size indicating that the available external surface was an important factor. Increasing solution temperature resulted in an increase in adsorption capacity indicating an exothermic process with a negative ΔH. Finally, the effect of varying the percentage degree of deacetylation showed that from 52% to 97% resulted in decrease in the dye adsorption capacity suggesting that more amorphisation may cause changes in the internal structure of chitosan and reduce the capacity.     

Simultaneous determination of ascorbic acid, caffeine and paracetamol in drug formulations by differential-pulse voltammetry using a glassy carbon electrode

A simple, rapid and accurate method for the simultaneous determination of ascorbic acid, caffeine and paracetamol in drug formulations has been developed. Peak currents were measured with a glassy carbon electrode at +0.350, +0.618 and +1.425 V versus a saturated calomel electrode for ascorbic acid, paracetamol and caffeine, respectively. Perchloric acid (0.1 M) - methanol (1 + 1) was used both as a solvent and supporting electrolyte. The optimum modulation amplitude, pulse repeat time and scan rate of the polarographic analyser were found to be 50 mV, 0.5 s and 5 mV s-1, respectively and the linear calibration ranges for ascorbic acid, caffeine and paracetamol were 0-35, 0-50, and 0-55 micrograms ml-1, respectively. The relative standard deviations for 9.30 micrograms ml-1 of ascorbic acid, 8.50 micrograms ml-1 of caffeine and 7.30 micrograms ml-1 of paracetamol were 1.3, 2.5 and 0.7%, respectively. Results are reported for several commercially available drugs.     

Light activates reduction of methotrexate by NADPH in the ternary complex with Escherichia coli dihydrofolate reductase

Methotrexate (MTX), a strong inhibitor of dihydrofolate reductase (DHFR), has been widely used for chemotherapy for many types of cancer as well as for juvenile rheumatoid arthritis. It mimics folate substrates and binds tightly to the active site of DHFR, perhaps in a conformation close to the transition state of the folate catalyzed reaction. Absorption, fluorescence and ultrasensitive Raman difference spectroscopies show that light-activated MTX reacts with NADPH in the enzyme active site, producing 5,8-dihydromethotrexate (5,8-dihydro-MTX) and NADP+. The reaction, which proceeds with a hydride transfer between C4 (pro-R side) of the nicotinamide ring and N5 of the pteridine ring, is similar to that between folate and NADPH except that the hydride is transferred to C6 in this case. Hence, MTX is catalytically competent in its excited state. Most experiments were performed on the Escherichia coli enzyme, but preliminary studies show that the reaction also occurs with human DHFR.     

Hyperfine interactions at 57Fe in octaethylhaemin

Mössbauer measurements on octaethylhaemin have been made between 4.2 and 300 K, and (at the lower temperature) in applied magnetic fields of up to 50 kG. From a spin hamiltonian treatment the saturation value of the hyperfine field at the ⁵⁷Fe nucleus is found to be 495 kG, and the splitting parameter for the ferric ion levels by the axial ligand field is D = 8.0 cm^?1. The electric field gradient 1/2e²qQ = +0.93 mm s^?1.     

Chiral C1-symmetric 2,2′:6′,2′′-terpyridine ligands: Synthesis,characterization, complexation with copper(II), rhodium(III) and ruthenium(II) ions and use of the complexes in catalytic cyclopropanation of styrene

Three new optically pure C₁-terpyridine ligands (L1–3) were prepared and the copper(II) complexes, of formula [Cu(L)Cl₂], the rhodium(III) complexes, of formula [Rh(L)Cl₃], and the ruthenium(II) complexes, of formula cis- or trans-[Ru(L)(X)Cl₂] (X = DMSO or CO), were synthesized. Structures of a chiral C₁-ligand, a copper complex, a rhodium complex and a ruthenium DMSO complex were analysed using X-ray crystal structure analysis. The copper, rhodium and ruthenium complexes were shown to be precursors of catalysts for cyclopropanation. Reaction of [Cu(L)Cl₂], [Rh(L)Cl₃] or cis- or trans-[Ru(L)(X)Cl₂] with AgOTf converted the complex to catalyst, which in the case of trans-[Ru(L)(CO)Cl₂] gave enantioselectivities of up to 67% ee for the cis-isomers of styrene cyclopropanes with t-butyl diazoacetate. Comparisons with C₂-analog of copper, rhodium and ruthenium catalysts were made.