An electronic structure investigation of the BNO-BON-NBO system

The potential energy hypersurface of the ground triplet states of the BNO-BON-NBO system has been investigated using traditional ab initio electronic structure theory. The molecules studied have the molecular formula BON and include three linear and three angular species, and two transition states for the isomerization of an angular N-B-O to an angular B-O-N and a linear B-NO, respectively. All stationary points on the BNO-BON-NBO isomerization potential energy surface have been characterized employing UMP2, UMP4, and Gaussian-2 (G2) theory with the 6-311G(d), 6-311G(2d), and TZ2P basis sets. The isomerization for an angular N-BO to the linear B-NO has a lower energy barrier than that of the former to an angular B-ON. Energetics are presented with G2 energies. Two sets of resonance structures for both bent B-NO (boron nitrosyl) and B-ON (boron isonitrosyl) were proposed and the bonding in the two species was analyzed. For the purpose of comparison, the density functional theory based hybrid methods B3LYP/6-311G(d) and B3LYP/TZ2P have also been applied to both geometry optimization and single-point calculations. It is found that the B3LYP prediction of the nature of the linear B-O is contradictory to that made by all MPn(n = 2 and 4) calculations. The cause for this contradiction is discussed.     

Preparation of 103Pd seeds Part II. “Molecular Plating” of 103Pd onto copper rod

A method for ¹⁰³Pd molecular plating onto the surface of the copper rod is reported. The optimal composition of the plating bath was: palladium chloride 2 g/l, ammonium hydroxide (28%) 150 ml/l, sodium hypophosphite 12 g/l, and ammonium chloride 37 g/l. The whole procedure of ¹⁰³Pd molecular plating will last 50 minutes at 40 °C. This article provides valuable experience for the preparation of ¹⁰³Pd seeds.     

Molecular dynamics simulations of the mononuclear zinc-beta-lactamase from Bacillus cereus complexed with benzylpenicillin and a quantum chemical study of the reaction mechanism

Herein, we present results from MD simulations of the Michaelis complex formed between the B. cereus zinc-beta-lactamase enzyme and benzylpenicillin. The structural and dynamical effects induced by substrate-binding, the specific role of the conserved residues, and the near attack conformers of the Michaelis complex are discussed. Quantum chemical methods (HF/6-31G* and B3LYP/6-31G*) are also applied to study the hydrolysis reaction of N-methylazetidinone catalyzed by a monozinc system consisting of the side chains of the histidine residues (His86, His88, and His149) complexed with Zn-OH and the side chains of Asp90 and His210. From this model system, we built molecular-mechanics representations of the prereactive complex and transition state configurations docked into the active site. Linear-scaling semiempirical calculations coupled with a continuum solvent model were then performed on these static models. We propose that the experimental rate data for the B. cereus enzyme is compatible with a one-step mechanism for the hydrolysis of beta-lactam substrates in which His210 acts as a proton donor.     

Radiation patterns of electric dipole antenna in the presence of a biisotropic sphere

Analytic expressions of the dyadic Green's function of an arbitrary electric current source embedded in a general biisotropic sphere are presented at first, and the radiation characteristics of an electric dipole antenna placed on the surface of a biisotropic sphere lens are examined. The effects of the electric-and the magnetic-coefficients ( _e and _m ) of biisotropic medium on the radiation patterns of electric dipole antenna are investigated in detail.     

Theoretical study of addition reactions of heavy carbenes to carbon and boron nitride nanotubes

In an effort to gain insight into the activation energies and reaction enthalpies of the chemical functionalization of carbon and boron nitride nanotubes, calculations using density functional theory have been carried out for the cycloaddition of a heavy carbene to a single-walled carbon (SWCNT; C(130)H(20)) and a boron nitride (SWBNNT; B(65)N(65)H(20)) nanotube. The (CH(3))(2)X + SWCNT and (CH(3))(2)X + SWBNNT (X = C, Si, Ge, Sn, and Pb) reactions are the subject of the present study. All the stationary points were determined at the B3LYP/LANL2DZ level of theory. The major conclusions that can be drawn from this work are as follows: (i) Considering both the activation barrier and reaction enthalpy based on the model calculations presented here, it is found that the order of (CH(3))(2)X reactivity is X = C > Si > Ge > Sn > Pb, irrespective of whether cycloaddition is to a SWCNT or a SWBNNT sidewall. That is to say, (CH(3))(2)C and (CH(3))(2)Si can readily add to the sidewalls of SWCNT and SWBNNT, whereas (CH(3))(2)Ge, (CH(3))(2)Sn, and (CH(3))(2)Pb are unreactive. (ii) Since the chemical reactivities of SWCNT and SWBNNT sidewalls closely resemble those of the small C(16)H(10) and B(8)N(8)H(10) molecules, at least in a qualitative sense, the use of the above small molecules as models is sufficient to provide qualitatively correct results. (iii) Our theoretical observations indicate that all the (5,5) SWCNT and SWBNNT cycloadducts favor opened rather than closed three-membered ring structures. (iv) The theoretical investigations demonstrate that the singlet-triplet splitting of the carbene species (R(2)X) as well as that of the small model molecules can be used as a diagnostic tool to predict the addition reactivities of carbene analogues and sidewalls of various nanotubes, respectively. Moreover, the results obtained in this work allow a number of predictions to be made.     

Determination of hexamethylene-based isocyanates in spray-painting operations. Part 1. Evaluation of a polyurethane foam sponge sampler

A polyurethane foam (PUF) sponge was mounted in a cassette sampler and evaluated as a sorbent for the collection of hexamethylene diisocyanate (HDI) monomer and HDI-based oligomers. Recovery studies indicated 112 +/- 34% average recovery of HDI monomer and 92 +/- 9% and 97 +/- 25% average recovery of HDI-based oligomers when using impregnated PUF sponges. The PUF sponge was also evaluated during actual spray-painting operations. In a series of side-by-side sampling events, an impinger filled with 1-(2-methoxyphenyl)piperazine (MOP) in toluene was compared directly with a cassette sampler containing a PUF sponge impregnated with MOP or 1-(9-anthracenylmethyl)piperazine (MAP) in dimethyl sulfoxide (DMSO). For the analysis of HDI-based oligomer, there is no significant difference (p < 0.05, n = 7) in the air concentration when sampling with either the PUF sponge cassette or the impinger. The results are significant because they indicate that a PUF sponge, which is more convenient than an impinger, may be used for the collection of HDI-based oligomer generated during spray-painting operations.     

A practical synthetic route to 4′-alkylaristeromycin derivatives: 4′-methylaristeromycin

(−)-(1S,4R)-4-Hydroxy-2-cyclopenten-1-yl acetate provided a convenient entry point for a 16-step chiral preparation of 4′-methylaristeromycin. This procedure is adaptable to a number of carbocyclic nucleosides with a diversity of substitution at C-4′ and C-5′ and a variety of heterocyclic bases.     

The compensation effect revisited

It is generally accepted that the compensation effect arises when a linear relation between InA andE is detected for a simple reaction taking place over different catalysts or for different reactions over one catalyst. For a perfect linear relation between InA andE representation of the reaction rate constant in an Arrhenius plot results in a series of straight lines which intersect in a single point. The importance is stressed of defining unambiguously what is meant by the compensation effect, and it is shown how the scatter in the values of InA is translated into Arrhenius plots.