Total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide γ-butyrolactones

The first total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide was achieved in a convergent pathway. The salient features of our synthesis include Ohira–Bestmann reaction, regioselective alkyne addition to terminal epoxide, TEMPO/BAIB mediated oxidative lactonization, and partial hydrogenation.     

Total synthesis of two γ-butyrolactone containing compounds (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide

The first total synthesis of (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide was accomplished using Jacobsen hydrolytic kinetic resolution, Ohira–Bestmann reaction, regioselective alkyne addition to terminal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated oxidative lactonization and partial hydrogenation as the key steps.     

Langmuir Analysis of Nanoparticle Polyvalency in DNA‐Mediated Adsorption

Many nanoparticle adsorption processes are dictated by the collective interactions of surface‐bound ligands. These adsorption processes define how nanoparticles interact with biological systems and enable the assembly of nanoparticle‐based materials and devices. Herein, we present an approach for quantifying nanoparticle adsorption thermodynamics in a manner that satisfies the assumptions of the Langmuir model. Using this approach, we study the DNA‐mediated adsorption of polyvalent anisotropic nanoparticles on surfaces and explore how deviations from model assumptions influence adsorption thermodynamics. Importantly, when combined with a solution‐based van’t Hoff analysis, we find that polyvalency plays a more important role as the individual interactions become weaker. Furthermore, we find that the free energy of anisotropic nanoparticle adsorption is consistent across multiple shapes and sizes of nanoparticles based on the surface area of the interacting facet.     

N-donor stabilized complexes of nickel(II) diphenyldithiophosphates: single-crystal X-ray,HSA and computational analysis

Transition Metal Chemistry - Nickel(II) complexes with octahedral coordination stabilized by N-donor ligands corresponds to [{(ArO)2PS2}2Ni·L2] [Ar = 4-(C2H5)C6H4 (3), and...     

Sensitivity enhancement and matrix effect evaluation during summation of multiple transition pairs—case studies of clopidogrel and ramiprilat

Sensitivity enhancement via summation of multiple MRM transition pairs is gaining popularity in tandem mass spectrometric assays. Numerous validation experiments describing the assays for two model substrates, clopidogrel and ramiprilat, were performed. The quantitation of clopidogrel was achieved by the summation of transition pairs m/z 322.2 to m/z 212.0 and m/z 322.2 to m/z 184.0, while that of ramiprilat was achieved by the summation of transition pairs m/z 389.2 to m/z 206.1 and m/z 389.2 to m/z156.1. The use of summation approach achieved sensitivities of >2 fold for both compounds as compared with the reported single MRM transition pair assays. The validation experiments addressed some important assay development issues, such as: (a) lack of impact of matrix effect; (b) unequivocal verification of the percentage contribution of each MRM transition pair towards sensitivity; (c) sensitivity enhancement factor achieved by summation approach of MRM transition pairs; and (d) accurate prediction of quality control samples using summation approach vs a single MRM transition pair. In summary, the appropriateness of using two MRM transition pairs for quantitation was demonstrated for both clopidogrel and ramiprilat. Additionally, pharmacokinetic application of the MRM transition pair assays using a summation approach was established for the two compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of nonuniform illumination on implosion asymmetry in direct-drive inertial confinement fusion

Target areal density (rhoR) asymmetries in OMEGA direct-drive spherical implosions are studied. The rms variation / for low-mode-number structure is approximately proportional to the rms variation of on-target laser intensity / with an amplification factor of approximately 1/2(C(r)-1), where C(r) is the capsule convergence ratio. This result has critical implications for future work on the National Ignition Facility as well as OMEGA.     

Progress in direct-drive inertial confinement fusion research at the laboratory for laser energetics

Direct-drive inertial confinement fusion (ICF) is expected to demonstrate high gain on the National Ignition Facility (NIF) in the next decade and is a leading candidate for inertial fusion energy production. The demonstration of high areal densities in hydrodynamically scaled cryogenic DT or D₂ implosions with neutron yields that are a significant fraction of the “clean” 1-D predictions will validate the ignition-equivalent direct-drive target performance on the OMEGA laser at the Laboratory for Laser Energetics (LLE). This paper highlights the recent experimental and theoretical progress leading toward achieving this validation in the next few years. The NIF will initially be configured for X-ray drive and with no beams placed at the target equator to provide a symmetric irradiation of a direct-drive capsule. LLE is developing the “polar-direct-drive” (PDD) approach that repoints beams toward the target equator. Initial 2-D simulations have shown ignition. A unique “Saturn-like” plastic ring around the equator refracts the laser light incident near the equator toward the target, improving the drive uniformity. LLE is currently constructing the multibeam, 2.6-kJ/beam, petawatt laser system OMEGA EP. Integrated fast-ignition experiments, combining the OMEGA EP and OMEGA Laser Systems, will begin in FY08.     

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

Apolar aprotic solvents are particularly advantageous for investigating the intrinsic metasubstituent effect free from complications of specific solvent effects. A kinetic study for toluene‐phase proton transfers between meta‐Me, F, Cl, Br, I, OMe, OPh, COPh, CF₃, CN, NO₂, H benzoic acids and Crystal Violet carbinol base has shown the forward rate constant (log k₁) the most appropriate reactivity parameter in toluene. log k₁ (toluene) as compared to other reported reactivity parameters in benzene or toluene have been found more sensitive to the metasubstituent effect. The regression results of the correlation of log k₁ (toluene) of the acids according to the four dual substituent parameter models are statistically significant, and the best result has been obtained using Taft's model. The overall analysis reveals that metasubstituent's effect is exerted by a 65:35 pattern of its field and second‐order resonance effects. The results further demonstrate that a metasubstituent's resonance effect is virtually a relayed universal field/inductive effect. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 303–311, 2011     

Green Approaches to Field Nitrate Analysis: An Electroanalytical Perspective

The different approaches that have been taken in the development of analytical methods for the determination of nitrate within the field are reviewed. The emphasis has been placed on providing a critical appraisal of the chemistry that underpins current commercial systems and the need to remove the dependence on heavy metal and concentrated acid components. The search for more environmentally acceptable and user friendly systems has long been pursued and the present communication seeks to explore the recent development in portable testing technologies and how they might evolve in the future. In particular, the role of electrochemical techniques in the latter are investigated and their potential application compared and contrasted with the more traditional wet chemical detection strategies.