A zeolitic organo-metallophosphate hybrid material with bimodal porosity

The first metal carboxylatophosphate, NTHU-2, contains inorganic ZnHPO4 layers linked by BDC units (BDC = 1,4-benzene dicarboxylate or terephthalic anion); the three-dimensional anionic framework has large pores with the smallest diameter being 1.36 nm; N2 sorption isotherms reveal both micro- and mesoporosity; the new material is photoluminescent and disassembles in water wherein the discharged organic fragments form mixed crystals.     

Iron and copper complexes of tetraphenyl-m-benziporphyrin: reactivity of the internal C-H bond

Iron and copper complexes of tetraphenyl-m-benziporphyrin (TPmBPH)H have been prepared and structurally characterized. The iron system, (TPmBPH)Fe(II)Br, contains a high-spin Fe(II) center. In the solid state the complex forms dimeric units linked by weak CH.Br hydrogen bonds. The Cu complex contains a tetrameric copper cluster with a Cu(2)Cl(4)(2)(-) unit bridging two [(TPmBPCl)Cu(II)](+) fragments. The formation of (TPmBPCl)H represents an example of copper-catalyzed chlorination on the internal carbon atom of (TPmBPH)H.     

Technique for incorporating the density functional Hessian into the geometry optimization of biomolecules, solvated molecules, and large floppy molecules

Traditional geometry optimization methods require the gradient of the potential surface, together with a Hessian which is often approximated. Approximation of the Hessian causes difficulties for large, floppy molecules, increasing the number of steps required to reach the minimum. In this article, the costly evaluation of the exact Hessian is avoided by expanding the density functional to second order in both the nuclear and electronic variables, and then searching for the minimum of the quadratic functional. The quadratic search involves the simultaneous determination of both the geometry step and the associated change in the electron density matrix. Trial calculations on Taxol indicate that the cost of the quadratic search is comparable to the cost of the density functional energy plus gradient. While this procedure circumvents the bottleneck coupled-perturbed step in the evaluation of the full Hessian, the second derivatives of the electron-repulsion integrals are still required for atomic-orbital-based calculations, and they are presently more expensive than the energy plus gradient. Hence, we anticipate that the quadratic optimizer will initially find application in fields in which existing optimizers breakdown or are inefficient, particularly biochemistry and solvation chemistry.     

Impulse response techniques to measure binary diffusion coefficients under supercritical conditions

This review describes impulse response techniques with a curve-fitting method to measure thermodynamic properties, such as binary diffusion coefficient, retention factor, and partial molar volume, under supercritical conditions. Theoretical background, parameter sensitivity, sources of experimental error, noise elimination technique, and the correction of apparent binary diffusion coefficients due to column coiling are discussed based on recent studies, together with data sources and predictive correlations for binary diffusion coefficients.     

Chromatographic impulse response technique with curve fitting to measure binary diffusion coefficients and retention factors using polymer-coated capillary columns

The theoretical basis of a Gaussian-like approximate solution was applied to a chromatographic impulse response technique with curve fitting for measuring binary diffusion coefficients and retention factors using a polymer-coated capillary column. The formulae were derived for evaluating both the accuracy of the approximate solution and the sensitivity of the parameters. The validity of the solution also was confirmed experimentally for pulse injection of phenol in acetone into supercritical carbon dioxide flowing at 313.15 K and 11.6-28.6 MPa. Potential sources for experimental errors of the method are discussed.     

Stereochemical control of the Passerini reaction

A catalytic asymmetric Passerini reaction using tridentate indan (pybox) Cu(II) Lewis acid complex 4 with substrates capable of bidentate coordination has been achieved. The reaction occurs via ligand-accelerated catalysis.     

Anionic O --> alpha- and beta-vinyl carbamoyl translocation of 2-(O-carbamoyl) stilbenes

[reaction: see text] New anionic oxygen to alpha- and beta-vinyl carbamoyl migration reactions, 17a and 26a-c --> 18 and 30a-c, proceed under LDA-mediated conditions leading stereoselectively to highly substituted stilbenes bearing electron-donating and -withdrawing substituents. Compounds 17a and 26a-c are prepared by combination of efficient, directed ortho metalation, Sonogashira, and Suzuki-Miyaura cross-coupling procedures.     

Routes to control of H2 Coulomb explosion in few-cycle laser pulses

We have measured coincident ion pairs produced in the Coulomb explosion of H2 by 8-30 fs laser pulses at different laser intensities. We show how the Coulomb explosion of H2 can be experimentally controlled by tuning the appropriate pulse duration and laser intensity. For laser pulses less than 15 fs, we found that the rescattering-induced Coulomb explosion is dominated by first-return recollisions, while for longer pulses and at the proper laser intensity, the third return can be made to be the major one. Additionally, by choosing suitable pulse duration and laser intensity, we show H2 Coulomb explosion proceeding through three distinct processes that are simultaneously observable, each exhibiting different characteristics and revealing distinctive time information about the H2 evolution in the laser pulse.     

Measurement of nonrandom event-by-event fluctuations of average transverse momentum in square root of (sNN)=200 GeV Au+Au and p+p collisions

Event-by-event fluctuations of the average transverse momentum of produced particles near midrapidity have been measured by the PHENIX Collaboration in square root of (sNN)=200 GeV Au+Au, and p+p collisions at the Relativistic Heavy Ion Collider. The fluctuations are observed to be in excess of the expectation for statistically independent particle emission for all centralities. The excess fluctuations exhibit a dependence on both the centrality of the collision and on the pT range over which the average is calculated. Both the centrality and pT dependence can be well reproduced by a simulation of random particle production with the addition of contributions from hard-scattering processes.