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.     

First observation of the decay B --> J/psistraight phiK

We present the first observation of the decay B-->J/psistraight phiK. Using 9.6x10(6) B&Bmacr; meson pairs collected with the CLEO detector, we have observed ten fully reconstructed B-->J/psistraight phiK candidates, whereas the estimated background is 0.5+/-0.2 event. We obtain a branching fraction of B(B-->J/psistraight phiK) = (8. 8(+3.5)(-3.0)[stat]+/-1.3[syst])x10(-5). This is the first observed B meson decay requiring the creation of an additional s&smacr; quark pair.     

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.

     

On the ruin time distribution for a Sparre Andersen process with exponential claim sizes

We derive a closed-form (infinite series) representation for the distribution of the ruin time for the Sparre Andersen model with exponentially distributed claims. This extends a recent result of Dickson et al. [Dickson, D.C.M., Hughes, B.D., Zhang, L., 2005. The density of the time to ruin for a Sparre Andersen process with Erlang arrivals and exponential claims. Scand. Actuar. J., 358–376] for such processes with Erlang inter-claim times. The derivation is based on transforming the original boundary crossing problem to an equivalent one on linear lower boundary crossing by a spectrally positive Lévy process. We illustrate our result in the cases of gamma, mixed exponential and inverse Gaussian inter-claim time distributions.     

Differential transport and dispersion of colloids relative to solutes in single fractures

This work employed numerical experiments simulating colloid and solute transport in single parallel-plate fractures, using the random walk particle tracking method, to demonstrate that (1) there exists an aspect ratio of the colloid radius to half the fracture aperture, δ_o, where the average velocities of colloids and solutes are similar. When δ > δ_o, the velocity distribution assumption is satisfied, and the fact that the ratio of the colloid transport velocity to the solute transport velocity, τ_p, decreases as δ increases is well documented in the literature. However, when δ < δ_o, the velocity distribution assumption is violated, and τ_p increases as δ increases and (2) the Taylor dispersion coefficient and its extension by James and Chrysikopoulos [S.C. James, C. V. Chrysikopoulos, J. Colloid Interface Sci. 263 (2003) 288] will overestimate the colloid dispersion coefficient significantly. Additionally, numerical experiments simulating colloid and solute transport in variable-aperture fractures demonstrated that τ_p and D_L,coll/D_L,solute decrease with increasing CoV, and the anisotropy ratio only plays a minor role compared to the CoV. These observations have important implications towards the interpretation of colloid transport in both porous and fractured media.