Polymer-DNA hybrids as electrochemical probes for the detection of DNA

The syntheses of several norbornene block copolymers containing oligonucleotide and ferrocenyl side chains and their use in the electrochemical detection of DNA are described. Two kinds of DNA-containing block copolymers with either ferrocenyl or dibromoferrocenyl groups were prepared via ring-opening metathesis polymerization (ROMP). Based on these two distinct ferrocene derivatives, a triblock copolymer labeling strategy was developed. With this strategy, the identity of DNA target can be determined by the E1/2s of the ferrocenyl moieties and the ratio of peak currents. These polymers exhibit predictable and tailorable electrochemical properties, high DNA duplex stability, and unusually sharp melting transitions, which are highly desirable characteristics for DNA detection applications. Significantly, single-base mismatches could be easily detected using two distinct block copolymers as dual-channel detection probes in an electrochemical DNA detection format.     

Preparation and phase relationships in systems of the type CdSMIMIIIS2 where MI = Ag,Cu and MIII = Al,Ga, In

Systems of the type M^IM^IIIS₂ (chalcopyrite)-CdS (wurtzite) where M^I = Ag, Cu and M^III = Al, Ga, In were investigated to determine the regions of mutual solid solubility. It was found that the chalcopyrite structure could not tolerate extensive CdS substitution. When M^III was Al or Ga the solubility of M^IM^IIIS₂ in CdS was also very limited. However, when M^III = In (r_In³⁺ ? r_Ga³⁺ > r_Al³⁺), the solubility of M^IInS₂ in CdS was quite extensive (～50%). These results are consistent with a prior study on systems of the type M^IM^IIIS₂ZnS which indicated that in sulfides, larger cations tend to result in the formation of new quaternary, wurtzite phases.     

Surface-localized release of nitric oxide via sol-gel chemistry

The release of nitric oxide (NO) from polymers has proven to be highly effective at inhibiting platelet adhesion and thus enhancing the blood compatibility of medical implants. Micropatterning techniques were used to design surfaces that release NO while preserving the underlying substrate for other applications (e.g., sensors). Micropatterned NO-releasing substrates based on aminosilane-containing methyltrimethoxysilane sol-gels were prepared and characterized in terms of stability, NO surface flux, and resistance to in vitro platelet adhesion. We have found that surface-localized NO release from substrates modified with sol-gel micropatterns exhibit enhanced blood compatibility relative to controls.     

Consistent concepts of self‐organization and self‐assembly

We critically review concepts of self‐organization and self‐assembly, and extract from this analysis consistent and workable definitions of both concepts that are applicable across many scientific disciplines. In essence, we distinguish self‐organization from self‐assembly on a thermodynamic basis, where self‐organization implies a nonequilibrium process and self‐assembly is reserved for spontaneous processes tending toward equilibrium. This discrimination is consistent with early uses of both terms. © 2008 Wiley Periodicals, Inc. Complexity, 2008.     

A stochastic programming model for scheduling call centers with global Service Level Agreements

We consider the issue of call center scheduling in an environment where arrivals rates are highly variable, aggregate volumes are uncertain, and the call center is subject to a global service level constraint. This paper is motivated by work with a provider of outsourced technical support services where call volumes exhibit significant variability and uncertainty. The outsourcing contract specifies a Service Level Agreement that must be satisfied over an extended period of a week or month. We formulate the problem as a mixed-integer stochastic program. Our model has two distinctive features. Firstly, we combine the server sizing and staff scheduling steps into a single optimization program. Secondly, we explicitly recognize the uncertainty in period-by-period arrival rates. We show that the stochastic formulation, in general, calculates a higher cost optimal schedule than a model which ignores variability, but that the expected cost of this schedule is lower. We conduct extensive experimentation to compare the solutions of the stochastic program with the deterministic programs, based on mean valued arrivals. We find that, in general, the stochastic model provides a significant reduction in the expected cost of operation. The stochastic model also allows the manager to make informed risk management decisions by evaluating the probability that the Service Level Agreement will be achieved.     

A facile and efficient direct aldol addition of simple thioesters

[reaction: see text] Simple thioesters undergo direct aldol addition to aldehydes in the presence of MgBr(2).OEt(2) and i-Pr(2)NEt using untreated, reagent-grade CH(2)Cl(2) under atmospheric conditions. The reactions proceed extremely rapidly and in excellent yield.     

TANGENT UNIT-VECTOR FIELDS:NONABELIAN HOMOTOPY INVARIANTS AND THE DIRICHLET ENERGY

Let O be a closed geodesic polygon in S~2 . Maps from O into S~2 are said to satisfy tangent boundary conditions if the edges of O are mapped into the geodesics which contain them. Taking O to be an octant of S 2,we compute the infimum Dirichlet energy E(H) for continuous maps satisfying tangent boundary conditions of arbitrary homotopy type H . The expression for E (H ) involves a topological invariant - the spelling length - associated with the (non-abelian) fundamental group of the n-times punctured two-sphere, π 1 (S 2 ? {s 1 , ··· , s n }, ?). The lower bound for E(H) is obtained from combinatorial group theory arguments, while the upper bound is obtained by constructing explicit representa- tives which, on all but an arbitrarily small subset of O, are alternatively locally conformal or anticonformal. For conformal and anticonformal classes (classes containing wholly con- formal and anticonformal representatives respectively), the expression for E (H ) reduces to a previous result involving the degrees of a set of regular values s 1 , ··· , s n in the target S 2 space. These degrees may be viewed as invariants associated with the abelianization of π 1 (S 2 ? {s 1 , ··· , s n }, *). For nonconformal classes, however, E(H) may be strictly greater than the abelian bound. This stems from the fact that, for nonconformal maps, the number of preimages of certain regular values may necessarily be strictly greater than the absolute value of their degrees.This work is motivated by the theoretical modelling of nematic liquid crystals in confined polyhedral geometries. The results imply new lower and upper bounds for the Dirichlet energy (one-constant Oseen-Frank energy) of reflection-symmetric tangent unit- vector fields in a rectangular prism.     

Tandem facial amphiphiles for membrane protein stabilization

We describe a new type of synthetic amphiphile that is intended to support biochemical characterization of intrinsic membrane proteins. Members of this new family displayed favorable behavior with four of five membrane proteins tested, and these amphiphiles formed relatively small micelles.