On-line solid phase extraction LC-MS/MS analysis of pharmaceutical indicators in water: A green alternative to conventional methods

A method using automated on-line solid phase extraction (SPE) directly coupled to liquid chromatography/tandem mass spectrometry (LC-MS/MS) has been developed for the analysis of six pharmaceuticals by isotope dilution. These selected pharmaceuticals were chosen as representative indicator compounds and were used to evaluate the performance of the on-line SPE method in four distinct water matrices. Method reporting limits (MRLs) ranged from 10 to 25 ng/L, based on a 1 mL extraction volume. Matrix spike recoveries ranged from 88 to 118% for all matrices investigated, including finished drinking water, surface water, wastewater effluent and septic tank influent. Precision tests were performed at 50 and 1000 ng/L with relative standard deviations (RSDs) between 1.3 and 5.7%. A variety of samples were also extracted using a traditional off-line automated SPE method for comparison. Results for both extraction methods were in good agreement; however, on-line SPE used approximately 98% less solvent and less time. On-line SPE coupled to LC-MS/MS analysis for selected indicators offers an alternative, more environmentally friendly, method for pharmaceutical analysis in water by saving time and costs while reducing hazardous waste and potential environmental pollution as compared with off-line SPE methods.     

Classification of semiconducting polymeric mesophases to optimize device postprocessing

Semiconducting polymers form a variety of phases and mesophases that respond differently to postdeposition solvent or thermal treatments. Here it is shown that classification of these materials into their appropriate mesophases can be a useful tool to optimize their thermal postdeposition treatments. Calorimetry is used to quantify differences between materials having similar molecular structures, using a well‐established framework based on the kinetics and thermodynamics of phase changes. By way of example, this classification scheme is used to identify differences in three polymers, poly(3‐hexylthiophene‐2,5‐diyl) and two isomeric bithiophene–thienothiophene copolymers. It is demonstrated that poly(3‐hexylthiophene) is a “normal” polymer crystal and that the two bithiophene–thienothiophene copolymers have liquid crystalline phases. The different phase structure is notable in light of the molecular similarity of the three polymers and has an impact on the thermal postprocessing conditions that maximize field effect charge carrier mobility in thin film transistor devices. Strong superheating effects are demonstrated for the two bithiophene–thienothiophene copolymers and the impact on annealing is demonstrated using grazing incidence X‐ray diffraction. Some suggestions are also put forth for what post‐processing should be employed for each class of polymer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1641–1653     

Two-photon singlet oxygen microscopy: the challenges of working with single cells

A microscope is described in which singlet molecular oxygen, O2(a1deltag), is produced in a femtoliter focal volume via a nonlinear two-photon photosensitized process, and the 1270 nm phosphorescence from this population of O2(a1deltag) is detected in a photon counting experiment. Although two-photon excitation of a sensitizer is less efficient than excitation by a one-photon process, nonlinear excitation has several distinct advantages with respect to the spatial resolution accessible. Pertinent aspects of this two-photon O2(a1deltag) microscope were characterized using bulk solutions of photosensitizers. These data were compared to those obtained from a single biological cell upon linear one-photon excitation of a sensitizer incorporated in the cell. On the basis of the results obtained, we outline the challenges of using nonlinear optical techniques to create O2(aldeltag) at the single cell level and to then optically detect the O2(aldeltag) thus produced in a time-resolved experiment.     

C,O-dialkylation of Meldrum's acid: synthesis and reactivity of 1,3,7,7-tetramethyl-4H,10H-6,8,9-trioxa-2-thiabenz[f]azulen-5-one

Reaction of Meldrum's acid with 3,4-bis(chloromethyl)-2,5-dimethylthiophene (1) or 3,4-bis(bromomethyl)-2,5-dimethylthiophene (2) produces the kinetically favored C,O-dialkylation product, 1,3,7,7-tetramethyl-4H,10H-6,8,9-trioxa-2-thiabenz[f]azulen-5-one (4). Recrystallization of 4 from refluxing methanol results in the methanolysis product 5-(4-methoxymethyl-2,5-dimethylthiophen-3-ylmethyl)-2,2-dimethyl[1,3]dioxane-4,6-dione (5). Attempts to isomerize 4 to the thermodynamically favored C,C-dialkylation product, 1,3-dimethyl-5,6-dihydro-4H-cyclopenta[c]thiophene(2-spiro-5)2,2-dimethyl-4,6-dione (8), result in the formation of 1,3-dimethyl-7,8-dihydro-4H-thieno[3,4-c]oxepin-6-one (6). The transformation occurs via a retro-Diels-Alder elimination of acetone followed by hydrolysis and decarboxylation of the resulting ketene. The ketene is trapped by tert-butyl alcohol, furnishing 1,3-dimethyl-6-oxo-7,8-dihydro-4H,6H-thieno[3,4-c]oxepine-7-carboxylic acid tert-butyl ester (7). All compounds are characterized spectroscopically as well as by X-ray crystallography of products 4-7.     

The stochastic location model with risk pooling

In this paper, we present a stochastic version of the location model with risk pooling (LMRP) that optimizes location, inventory, and allocation decisions under random parameters described by discrete scenarios. The goal of our model (called the stochastic LMRP, or SLMRP) is to find solutions that minimize the expected total cost (including location, transportation, and inventory costs) of the system across all scenarios. The location model explicitly handles the economies of scale and risk-pooling effects that result from consolidating inventory sites. The SLMRP framework can also be used to solve multi-commodity and multi-period problems.     

Planar Harmonic Maps with Inner and Blaschke Dilatations

A univalent harmonic map of the unit disk :={zC:|z|<1} isa complex-valued function f(z) on that satisfies Laplace'sequation and is injective. The Jacobian of a univalent harmonic map can never vanish [18], and so we might as wellassume that J>0 throughout . Then |f_z|>0 and a short computationverifies that the analytic dilatation is indeed an analytic function, with ||<1 sinceJ>0. Clearly 0 when f is a conformal map, and in generalthe dilatation measures how far f is from being conformal.Also, if happens to be the square of an analytic function,then f ‘lifts’ to give an isothermal coordinatemap for a minimal surface, and in that case i/ equals the stereographicprojection of the Gauss map of the surface.     

Worst-case minimum rectilinear steiner trees in all dimensions

It is proved that the length of the longest possible minimum rectilinear Steiner tree ofn points in the unitd-cube is asymptotic toβ _dn^(d−1)/d , whereβ _d is a constant that depends on the dimensiond≥2. A method of Chung and Graham (1981) is generalized to dimensiond to show that 1≤β _d≤d4^(1−d)/d . In addition to replicating Chung and Graham's exact determination ofβ ₂=1, this generalization yields new bounds such as 1≤β ₃<1.191 and .     

Effect of oligonucleotide length on the assembly of DNA materials: molecular dynamics simulations of layer-by-layer DNA films

DNA strand length has been found to be an important factor in many DNA-based nanoscale systems. Here, we apply molecular dynamics simulations in a synergistic effort with layer-by-layer experimental data to understand the effect of DNA strand length on the assembly of DNA films. The results indicate that short (less than 10 bases) and long (more than 30 bases) single-stranded DNAs do not exhibit optimal film growth, and this can be associated with the limited accessibility of the bases on the surface due to formation of self-protected interactions that prevent efficient hybridization. Interestingly, the presence of a duplex attached to a single strand significantly alters the persistence length of the polyT strands. Our study suggests that restrained polyT, compared to labile suspensions of free polyT, are more capable of hybridization and hence DNA-based assembly.