Probing the protic ionic liquid surface using X-ray reflectivity

The structure of the free liquid surface of three protic ionic liquids, ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and ethylammonium formate (EAF), has been elucidated using X-ray reflectivity. The results show all three liquids have an extended interfacial region, spanning at least five ion pairs, which can be divided into two parts. Adjacent to the gas phase are aggregates consisting of multiple cations and anions. Below this are layers oriented parallel to the macroscopic surface that are alternately enriched and depleted in cation alkyl chains and polar domains of cation ammonium groups and their anions, gradually decaying to the isotropic sponge-like bulk structure. The most pronounced layering is observed for PAN, driven by strong solvophobic interactions, while reduced hydrogen bonding in EAF results in the least structured and least extensive interfacial region.     

Discovery of kibdelomycin, a potent new class of bacterial type II topoisomerase inhibitor by chemical-genetic profiling in Staphylococcus aureus

Bacterial resistance to known therapeutics has led to an urgent need for new chemical classes of antibacterial agents. To address this we have applied?a Staphylococcus aureus fitness test strategy to natural products screening. Here we report the discovery of kibdelomycin, a novel class of antibiotics produced by a new member of the genus Kibdelosporangium. Kibdelomycin exhibits broad-spectrum, gram-positive antibacterial activity and is a potent inhibitor of DNA synthesis. We demonstrate through chemical genetic fitness test profiling and biochemical enzyme assays that kibdelomycin is a structurally new class of bacterial type II topoisomerase inhibitor preferentially inhibiting the ATPase activity of DNA gyrase and topoisomerase IV. Kibdelomycin is thus the first truly novel bacterial type II topoisomerase inhibitor with potent antibacterial activity discovered from natural product sources in more than six decades.     

Dilute Solution Properties of Styrene-N-Butyl Methacrylate (65:35) Copolymer: Short- and Long-Range Interaction of the Polymer Chain

Abstract

Viscosity and light-scattering data on styrene-n-butyl methacrylate (65:35) in chloroform are presented and tested by the two-parameter theoretical relations. The short-range interactions K and A and the long-range interaction parameter B have been calculated by different equations, using intrinsic viscosity and second virial coefficient data. These are then compared to the values of the homopolymer polystyrene. The conformation or the steric factor for the polymer chain has also been calculated. The excluded volume parameter Z, which is related to both the short- and long-range parameters, has been evaluated along with the expansion factor α _n . The higher value of the short-range parameters and the conformation factor compared to the parent styrene homopolymer is attributed to the effect of unlike monomer interactions causing extension of the polymer chain. An increase in the restriction of the internal rotation of side chains about the C-C bonds is also suggested. The excess interaction parameter has a negative value. The expansion factor α _n has been related to the excluded volume factor Z and the coefficient C is in close agreement with the theoretically calculated value of Yamakawa and Tanaka.     

Simultaneous separation and determination of 16 testosterone and nandrolone esters in equine plasma using ultra high performance liquid chromatography-tandem mass spectrometry for doping control

The potential for using testosterone and nandrolone esters in racehorses to boost the biological concentrations of these steroids and enhance athletic performance is very compelling and should be seriously considered in formulating regulatory policies for doping control. In order to regulate the use of these esters in racehorses, a sensitive and validated method is needed. In this paper, we report such a method for simultaneous separation, screening, quantification and confirmation of 16 testosterone and nandrolone esters in equine plasma by ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Analytes were extracted from equine plasma by liquid-liquid extraction using a mixture of methyl tert-butyl ether and ethyl acetate (50:50, v/v) and separated on a sub-2 micron C(18) column. Detection of analytes was achieved on a triple-quadrupole mass spectrometer by positive electrospray ionization mode with selected reaction monitoring (SRM). Mobile phase comprised 2 mM ammonium formate and methanol. Deuterium-labeled testosterone enanthate and testosterone undecanoate were used as dual-internal standards for quantification. Limits of detection (LOD) and quantification (LOQ) were 25-100 pg/mL and 100-200 pg/mL, respectively. The linear dynamic range of quantification was 100-10,000 pg/mL. For confirmation of the presence of these analytes in equine plasma, matching of the retention time with mass spectrometric ion ratios from MS/MS product ions was used. The limit of confirmation (LOC) was 100-500 pg/mL. The method is sensitive, robust, selective and reliably reproducible.     

Selectivity in the photo‐Fenton and photocatalytic hydroxylation of biphenyl‐4‐carboxylic acid and derivatives (viz. 4‐phenylsalicylic acid and 5‐phenylsalicylic acid)

The selectivity of hydroxylation of the distal rings of 4‐phenylbenzoic acid, 4‐phenylsalicylic acid, and 5‐phenylsalicylic acid were determined using partial TiO₂‐mediated photocatalytic degradation and photo‐Fenton conditions. This separation of the binding site from the phenyl group being hydroxylated allows a less‐biased evaluation. The hydroxylation regiochemistry behaves as qualitatively expected for an electrophilic reaction, given the assumption that 4‐carboxyphenyl is a slightly electron‐withdrawing substituent. Selectivity for hydroxylation of the distal phenyl in 4‐ and 5‐phenylsalicylic acid is reversed, due to the reversal of the electronic demand, while adsorption to the TiO₂ surface is assumed to be analogous for the two structures. Copyright © 2011 John Wiley & Sons, Ltd.     

A Novel Application of Indocyanine Green Immunofluorescence in Emergent Colorectal Surgery

Here, we report on the feasibility of ICG fluorescence imaging to localize lesions in emergent minimally invasive surgery. A 49-year old female presented to the emergency department with a previously unknown malignant bowel obstruction. She was taken emergently to the operating room for a laparoscopic extended right hemicolectomy, based on tumor location from imaging. With intraoperative difficulty localizing the lesion, an on-table colonoscopy was performed. When the tumor was encountered, peritumoral ICG injections were performed, and the fluorescence lymphoscintigraphy was performed intraoperatively in an attempt to visualize the primary tumor laparoscopically. Intraoperative ICG Immunofluorescence allowed precise, real-time localization of the mass in the descending colon. This information changed the course of the operation, as a laparoscopic left hemicolectomy was then performed instead of the planned extended right hemicolectomy. The patient underwent an end-to-end anastomosis without the need for a defunctioning ileostomy. From this case, we demonstrate the use of ICG fluorescence imaging for tumor localization in the emergent setting is safe, feasible, and effective. This information gained from this technology enables real-time decision making, and can even change the operative plan in the emergent setting for the best patient outcomes. What does this paper add to the existing literature? This paper offers a novel application of an emerging technology- ICG fluorescence- that in this capacity allowed precise, real-time localization of a previously unknown mass in the emergent setting, and changed the course of the operation.     

Analysis of DNA methylation markers for tissue identification in individuals with different clinical phenotypes

Deoxyribonucleic acid (DNA) methylation patterns can be used to identify the type of tissue or body fluid found at a crime scene. However, tissue-related methylation levels have not been analyzed in individuals with different illnesses and medical conditions in forensic-specific studies. The primary goal of this study was to investigate if certain clinical phenotypes can alter the methylation levels of CpG sites in genes involved in tissue typing. Four studies with focus on DNA methylation analysis on individuals with different clinical conditions were selected from the Gene Expression Omnibus database. Then, a list of 137 CpG sites was compiled for further investigation. Statistical tests were performed to compare the beta-values results obtained for the control groups and the individuals affected by medical conditions. For each study, CpG sites that presented significant statistical differences between patients and control group were identified and it was possible to notice that DNA methylation levels can be affected in sites with potential forensic use. Although the observed DNA methylation variation (less than 10% difference) in this study would likely not cause any issues in body fluid identification, the results are important to show that this type of analysis should be taken into consideration when investigating and further validating body fluid markers. The CpG sites identified in this study should be further investigated by future studies on body fluids identification, and due to the significant difference in methylation levels in samples from affected individuals, caution must be taken before including these sites in tissue identification investigations.     

A model for the drying process during film formation in waterborne acrylic coatings

Establishing drying mechanisms during film formation in waterborne acrylic coatings is a technologically important problem, however complex, and still poorly understood. A model for the prediction of evaporation kinetics is proposed in this paper, where films are supposed to dry normally with respect to the film surface, and a drying front separates a top dry region from a bottom wet region. The model accounts for the competition between water evaporation and particle diffusion that determines the degree of vertical homogeneity, but also for the competition between water evaporation and particle deformation that ultimately establishes the rate-determining step in film formation processes. The model was validated by performing gravimetric water-loss experiments on latexes of acrylic polymers of various composition, various particle size and stabilizing systems, under different environmental temperatures and humidity, and various initial film thicknesses in order to evaluate the effect of the different factors that can in principle influence the film formation process.