Introducing variable cell shape methods in field theory simulations of polymers

We propose a new method for carrying out field-theoretic simulations of polymer systems under conditions of prescribed external stress, allowing for shape changes in the simulation box. A compact expression for the deviatoric stress tensor is derived in terms of the chain propagator, and it is used to monitor changes in the box shape according to a simple relaxation scheme. The method allows fully relaxed, stress free configurations to be obtained even in nontrivial morphologies, and it enables the study of morphology transitions induced by external stresses.     

Pump-probe differencing technique for cavity-enhanced, noise-canceling saturation laser spectroscopy

We present an experimental technique that permits mechanical-noise-free, cavity-enhanced frequency measurements of an atomic transition and its hyperfine structure. We employ the 532-nm frequency-doubled output from a Nd:YAG laser and an iodine vapor cell. The cell is placed in a folded ring cavity (FRC) with counterpropagating pump and probe beams. The FRC is locked with the Pound-Drever-Hall technique. Mechanical noise is rejected by differencing the pump and probe signals. In addition, this differenced error signal provides a sensitive measure of differential nonlinearity within the FRC.     

Microwave traps for cold polar molecules

We discuss the possibility of trapping polar molecules in the standing-wave electromagnetic field of a microwave resonant cavity. Such a trap has several novel features that make it very attractive for the development of ultracold molecule sources. Using commonly available technologies, microwave traps can be built with large depth (up to several Kelvin) and acceptance volume (up to several cm³), suitable for efficient loading with currently available sources of cold polar molecules. Unlike most previous traps for molecules, this technology can be used to confine the strong-field seeking absolute ground state of the molecule, in a free-space maximum of the microwave electric field. Such ground state molecules should be immune to inelastic collisional losses. We calculate elastic collision cross-sections for the trapped molecules, due to the electrical polarization of the molecules at the trap center, and find that they are extraordinarily large. Thus, molecules in a microwave trap should be very amenable to sympathetic and/or evaporative cooling. The combination of these properties seems to open a path to producing large samples of polar molecules at temperatures much lower than has been previously possible.Received: 30 June 2004, Published online: 23 November 2004PACS: 33.80.Ps Optical cooling of molecules; trapping - 34.50.-s Scattering of atoms and molecules - 33.80.-b Photon interactions with molecules - 33.55.Be Zeeman and Stark effects     

Isomerization of a peptidic fragment studied theoretically in vacuum and in explicit water solvent at finite temperature

The cis-trans isomerization of N-methylacetamide, a molecular model of the polypeptide chain, is examined via umbrella sampling Car-Parrinello MD and classical MD, in both gas and solution phases at 300 K. A new analysis of the C(O)-N bond interconversion and a full examination of the solvent shell structure are presented.     

Design of a Thin Film Infrared Barcode on a Flexible Substrate

We report the design, fabrication and characterization of an infrared barcode. This barcode is composed of a bilayer of titanium and amorphous silicon on a flexible Kapton substrate. Information encoded in the barcode shows high contrast when viewed with an infrared imaging system in the 8 to 12 m spectral region. The barcode information is concealed under visible viewing conditions, i.e., the barcode appears as an untreated, uniform metal sheet to a detector of visible radiation (400 to 700nm).     

Continuous polydispersity in a self-consistent field theory for diblock copolymers

An efficient algorithm is presented for numerically evaluating a self-consistent field theoretic (SCFT) model of an AB diblock copolymer that incorporates continuous polydispersity in one of the blocks. An interesting segregation effect is found in which chains of intermediate molecular weight are concentrated at domain interfaces. This model of continuous polydispersity is also implemented in the random phase approximation (RPA) to study the order-disorder transition and predicts that the stability of the disordered, homogeneous phase decreases as the polydispersity in one of the blocks increases. The RPA predictions are confirmed by SCFT calculations. Our approach and results are particularly relevant to block copolymers prepared by quasiliving synthesis techniques, where the polymerization of one block is much more controlled than the other block.     

Phosphoinositide signaling; from affinity probes to pharmaceutical targets

Lipid signaling by phosphoinositides (PIP(n)s) involves an array of proteins with lipid recognition, kinase, phosphatase, and phospholipase functions. Understanding PIP(n) pathway signaling requires identification and characterization of PIP(n)-interacting proteins. Moreover, spatiotemporal localization and physiological function of PIP(n)-protein complexes must be elucidated in cellular and organismal contexts. For protein discovery to functional elucidation, reporter-linked phosphoinositides or tethered PIP(n)s have been essential. The phosphoinositide 3-kinase (PI 3-K) signaling pathway has recently emerged as an important source of potential "druggable" therapeutic targets in human pathophysiology in both academic and pharmaceutical environments. This review summarizes the chemistry of PIP(n) affinity probes and their use in identifying macromolecular targets. The process of target validation will be described, i.e., the use of tethered PIP(n)s in determining PIP(n) selectivity in vitro and in establishing the function of PIP(n)-protein complexes in living cells.     

Biosynthesis of hydroxydiphenylacetylene by regiospecific monooxygenation

Bacterial monooxygenase enzymes catalyze a regiospecific single-step hydroxylation of diphenylacetylene to yield meta- and para-hydroxydiphenylacetylene.     

Catalytic construction and reconstruction of guanidines: Ti-mediated guanylation of amines and transamination of guanidines

Bis(guanidinate) titanium imido complexes [{(Me2N)C(NiPr)2}2TiNAr'] (Ar' = 2,6-Me2C6H3 (1a); C6F5 (1b)) are competent catalysts for the guanylation of a variety of arylamines with carbodiimide. The reversible [2 + 2] addition of iPrN=C=NiPr to 1b is demonstrated and is proposed to be part of the catalytic cycle. Compounds 1a and 1b are also effective precatalysts for the transamination of trialkylguanidines with arylamines to yield aryldialkylguanidines.     

Determination of Albuterol Enantiomers in Animal Tissue Matrices by LC–MS/MS: Application in Therapeutic Myoanabolic Studies

Albuterol (salbutamol) is a widely used medication in respiratory disease including asthma and chronic obstructive airways disease; however, like other beta2-agonists, it also exerts some extrapulmonary effects on muscle and fat. Surprisingly, there have been relatively few reports of albuterol tissue distribution, and the distribution of individual albuterol enantiomers into tissue has not been reported. The method presented here explores the use of an HPLC tandem mass spectrometry (LC–MS/MS) system (LTQ Orbitrap hybrid mass spectrometer) with deuterated standard and solid-phase extraction to determine low levels of albuterol enantiomers in tissue. The lower limit of quantification (LLOQ) was 0.156 ng g⁻¹, with a precision RSD <15% for both enantiomers. The assay was linear over the calibration range of LLOQ-10.0 ng g⁻¹ in muscle tissue (r ² > 0.98). The assay was successfully applied to pharmacokinetic studies in rats and mice. By utilizing a deuterated internal standard and LC–MS/MS detection, this assay can be used to measure albuterol enantiomers in muscle tissue. This assay has also identified that albuterol uptake appears to be stereoselective, and enantioselective assays are clearly warranted for myoanabolic studies involving administration of racemic-albuterol.