The use of symmetry in direct Møller-Plesset second-order calculations

Summary An algorithm for utilising abelian point group symmetry in direct MP2 energy calculations is presented. This is based upon the direct MP2 method of Head-Gordon, Pople and Frisch. The method uses the petite atomic orbital integral list as in conventional transformations coupled with a symmetry adaption of the three quarter transformed integrals. Representative calculations for ethylene and benzene are presented which demonstrate the potential of the method.     

Supramolecular chemistry under mechanochemical conditions: a small molecule template generated and integrated into a molecular-to-supramolecular and back-to-molecular cascade reaction

We describe the integration of a small-molecule hydrogen-bond-donor template into a cascade reaction that is comprised of a combination of molecular and supramolecular events. The cascade is performed mechanochemically and in the presence of μL amounts of water. The small-molecule template is generated (molecular) using water-assisted vortex grinding and is then used to assemble an alkene (supramolecular) to undergo an intermolecular [2 + 2] photodimerization reaction (molecular). The chemical cascade results in a cyclobutane photoproduct that we show serves as a building block of a hydrogen-bonded network with a topology that conforms to T-silica. Remarkably, the molecular–supramolecular–molecular chemical cascade occurs stepwise and entirely regioselectively within the continuous mechanochemical conditions employed.

Mechanochemistry is applied to molecular and supramolecular chemistry to support a template-directed photochemical reaction.     

Correlation of free radical yields with strand break yields produced in plasmid DNA by the direct effect of ionizing radiation

The purpose of this study was to determine how free radical formation (fr) correlates with single strand break (ssb) and double strand break (dsb) formation in DNA exposed to the direct effects of ionizing radiation. Chemical yields have been determined of (i) total radicals trapped on DNA at 4 K, G(Sigmafr), (ii) radicals trapped on the DNA sugar, Gsugar(fr), (iii) prompt single strand breaks, Gprompt(ssb), (iv) total single strand breaks, Gtotal(ssb), and (v) double strand breaks, G(dsb). These measurements make it possible, for the first time, to quantitatively test the premise that free radicals are the primary precursors to strand breaks. G(fr) were measured by EPR applied to films of pEC (10,810 bp) and pUC18 (2686 bp) plasmids hydrated to Gamma = 22 mol of water/nucleotide and X-irradiated at 4 K. Using these same samples warmed to room temperature, strand breaks were measured by gel electrophoresis. The respective values for pEC and pUC18 were G(fr) = 0.71 +/- 0.02 and 0.61 +/- 0.01 micromol/J, Gtotal(ssb) = 0.09 +/- 0.01 and 0.14 +/- 0.01 micromol/J, G(dsb) = 0.010 +/- 0.001 and 0.006 +/- 0.001 micromol/J, and Gtota)(ssb)/G(dsb) approximately 9 and approximately 20. Surprisingly, Gsugar(fr) approximately 0.06 mumol/J for pUC18 films, less than half of Gtotal(ssb). This indicates that a significant fraction of strand breaks are derived from precursors other than trapped DNA radicals. To explain this disparity, various mechanisms were considered, including one that entails two one-electron oxidations of a single deoxyribose carbon.     

New Methods and Synthetic Applications of Asymmetric Nitrogen Transfer

Structure/reactivity relationships of N-alkoxycarbonyl- and N-carboxamidooxaziridines are explored, and conditions are discovered for the efficient amination of sulfides and primary amines. Reactions of these oxaziridines with alkenes are also examined, and lead to interesting new heteroatom transfer reaction products. Finally, the aminative rearrangement of 2-alkoxydihydropyrans leads to a useful stereocontrolled synthesis of pyrrolidines which can undergo synthetic manipulations to give [2.2.1]- and [3.2.1]-azabicycles.     

Simultaneous quantification of mycophenolic acid and its glucuronide metabolites in human plasma by an UPLC–MS/MS assay

The aim of this study was to develop a reliable UPLC–MS/MS assay for accurate quantification of mycophenolic acid (MPA) and its glucuronide conjugates in human plasma. Plasma proteins were precipitated with acetonitrile and the chromatographic separation was achieved on a C₁₈ column with a gradient elution. The detection was performed by a triple quadrupole mass spectrometer in the positive electrospray ionization and multiple reaction monitoring mode. Linearity of the assay was demonstrated over the range of 20–10,000 ng/mL for MPA and MPA glucuronide (MPAG), and 2–1000 ng/mL for acyl MPA glucuronide in human plasma. The assay was precise and accurate with coefficient of variation and bias <15%. MPA and MPAG were stable at 25 °C up to 1 day in both heparin‐ and EDTA‐treated blood. In heparin‐ and EDTA‐plasma, MPA and MPAG were stable for at least 1 week at 25 and 4 °C, and 1 month at ?20 °C. However, 99% acyl MPA glucuronide degraded in both heparin‐ and EDTA‐blood as well as plasma when stored at room temperature for 1 day. All the analytes remained stable for at least 3 months in acidified EDTA‐plasma at ?80 °C. The assay was successfully applied on patients post hematopoietic stem cell transplantation. Copyright © 2016 John Wiley & Sons, Ltd.     

Completely positive semidefinite rank

Mathematical Programming - An $$n\times n$$ matrix X is called completely positive semidefinite (cpsd) if there exist $$d\times d$$ Hermitian positive semidefinite matrices $$\{P_i\}_{i=1}^n$$ (for...     

Synthesis of the dysiherbaine tetrahydropyran core employing a tethered aminohydroxylation reaction

A stereocontrolled and scalable synthesis of an advanced intermediate of the dysiherbaine tetrahydropyran core has been achieved in 11 steps and 27% overall yield. The key feature of this synthetic approach is the application of the Donohoe tethered aminohydroxylation reaction to install the amino diol and establish the four contiguous syn stereocenters on the tetrahydropyran ring.     

Partnering a Three-Coordinate Gallium Cation with a Hydroborate Counter-Ion for the Catalytic Hydrosilylation of CO2

A novel β-diketiminate stabilized gallium hydride, (^DippL)Ga(Ad)H (where ( ^Dipp L)={HC(MeCDippN)₂}, Dipp=2,6-diisopropylphenyl and Ad=1-adamantyl), has been synthesized and shown to undergo insertion of carbon dioxide into the Ga−H bond under mild conditions. In this case, treatment of the resulting κ¹-formate complex with triethylsilane does not lead to regeneration of the hydride precursor. However, when combined with B(C₆F₅)₃, (^DippL)Ga(Ad)H catalyses the reductive hydrosilylation of CO₂. Under stoichiometric conditions, the addition of one equivalent of B(C₆F₅)₃ to (^DippL)Ga(Ad)H leads to the formation of a 3-coordinate cationic gallane complex, partnered with a hydroborate anion, [(^DippL)Ga(Ad)][HB(C₆F₅)₃]. This complex rapidly hydrometallates carbon dioxide and catalyses the selective reduction of CO₂ to the formaldehyde oxidation level at 60 °C in the presence of Et₃SiH (yielding H₂C(OSiEt₃)₂). When catalysis is undertaken in the presence of excess B(C₆F₅)₃, appreciable enhancement of activity is observed, with a corresponding reduction in selectivity: the product distribution includes H₂C(OSiEt₃)₂, CH₄ and O(SiEt₃)₂. While this system represents proof-of-concept in CO₂ hydrosilylation by a gallium hydride system, the TOF values obtained are relatively modest (max. 10 h⁻¹). This is attributed to the strength of binding of the formatoborate anion to the gallium centre in the catalytic intermediate (^DippL)Ga(Ad){OC(H)OB(C₆F₅)₃}, and the correspondingly slow rate of the turnover-limiting hydrosilylation step. In turn, this strength of binding can be related to the relatively high Lewis acidity measured for the [(^DippL)Ga(Ad)]⁺ cation (AN=69.8).