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991.
Cloudpoint data for polystyrene/methylcyclohexane solutions extending over moderate ranges of pressure and molecular weight are available in the literature. Those data are supplemented with new results from this laboratory to fill in gaps and extend the MW range (to 761 ≤ MW/amu ≤ 2 × 107). The resulting data net is discussed and reasons to extend studies to higher pressure are presented. © 1996 John Wiley & Sons, Inc.  相似文献   
992.
Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the ex situ generation of trifluoromethanesulfonyl fluoride (CF3SO2F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the SVI–F connector with a S Created by potrace 1.16, written by Peter Selinger 2001-2019 O → S Created by potrace 1.16, written by Peter Selinger 2001-2019 NR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H2O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols vs. amine groups, a phenomenon best explained—using ab initio metadynamics simulations—by a hydrogen bonded termolecular transition state for the CF3SO2F triflylation of amines.

Triflyl fluoride gas (CF3SO2F) and its aza analogues are reported as new SuFEx activators. These SVI–F reagents react efficiently with a variety of nucleophiles, yet the presence of water grants complete chemoselectivity to phenols.  相似文献   
993.
994.
In plasma edge transport codes for nuclear fusion devices, fluid-neutral models offer an interesting alternative to the currently used kinetic Monte Carlo simulations, especially for cases of high ion-neutral collisionality. In this paper, we elaborate a separate neutral energy equation in the state-of-the-art SOLPS-ITER code suite, which previously assumed perfect ion-neutral temperature equilibration. Furthermore, we study the coupled plasma-neutral solutions for a range of divertor operating regimes, proving the validity of these fluid-neutral models for high-recycling and detached regimes.  相似文献   
995.
Spectrometric and theoretical tools have been employed in this study in order to elucidate the structures of DTPA (diethylenetriaminepentaacetic acid) complexed to copper and lead. Mass spectrometry allowed determining the 1:1 stoichiometry of metal:ligand, while infrared spectroscopy demonstrated that both N and O are sites for complexation. 13C NMR analysis showed the existence of free and complexed carboxyl groups, due to a straight singlet at 180.7 ppm (free carboxylic 13C) and to a broad signal at 179.3 ppm (complexed carboxylic 13C, 2 J Pb…O=C). A distorted NMR signal were observed for the Cu–DTPA carboxyl group, due to the Cu2+ paramagnetism. Based on the spectrometric evidences for the metal–DTPA structures, DFT optimizations were carried out and an octahedral-like arrangement for the Cu complex and a “shell-like” arrangement for the Pb complex, both hexa-coordinated, were then proposed for the structures of the titled compounds.
Ruy CarvalhoEmail:
  相似文献   
996.
Focusing on CO2 fixation, photoautotrophic cultivation of the red algaPorphyridium cruentum was investigated by means of a batch culture under a 5% CO2-enriched atmosphere. The algal growth kinetics was successfully described with a logistic model, and simulation of a continuous culture under the optimum growth conditions (30°C, 12 klux and 1.18 g-cells/L) showed that the algal CO2-fixation activity could reach 0.66 g-CO2/(L X d). Under the same growth conditions, eicosapentaenoic acid (20:5 n-3, EPA) and arachidonic acid (20:4 n-6, ARA) yields were similarly calculated to be 3.6 mg-EPA/(L X d) and 6.5 mg-ARA/(L X d), respectively.  相似文献   
997.
The 124 superconductor YBa2Cu4O8 was prepared from the oxalate precursor Y2(C2O4)3. ·4BaC2O4·8CuC2O4·xH2O at one atmosphere oxygen pressure. In O2 the precursor decomposes in one step at 300°C and more gradually (300°–600°C) in Ar. The stability of the superconductor is strongly dependent on the gas atmosphere: in O2 and in air there is no significant weight change as long as the temperature does not exceed 800°C, whereas in a 1% O2-99%N2 mixture decomposition starts at about 670°C with the formation of CuO and YBa2Cu3Ox withx<7. The reduction of YBa2Cu4O8 in a 5% H2-95% Ar mixture takes place in at least four major steps with formation of products such as Y2O3, BaO, Cu2O, Cu, BaY2O4 and Ba4Y2O7.  相似文献   
998.
These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes.  相似文献   
999.
The potential of first-void (FV) urine as a non-invasive liquid biopsy for detection of human papillomavirus (HPV) DNA and other biomarkers has been increasingly recognized over the past decade. In this study, we investigated whether the volume of this initial urine stream has an impact on the analytical performance of biomarkers. In parallel, we evaluated different DNA extraction protocols and introduced an internal control in the urine preservative. Twenty-five women, diagnosed with high-risk HPV, provided three home-collected FV urine samples using three FV urine collection devices (Colli-Pee) with collector tubes that differ in volume (4, 10, 20 mL). Each collector tube was prefilled with Urine Conservation Medium spiked with phocine herpesvirus 1 (PhHV-1) DNA as internal control. Five different DNA extraction protocols were compared, followed by PCR for GAPDH and PhHV-1 (qPCR), HPV DNA, and HBB (HPV-Risk Assay), and ACTB (methylation-specific qPCR). Results showed limited effects of collection volume on human and HPV DNA endpoints. In contrast, significant variations in yield for human endpoints were observed for different DNA extraction methods (p < 0.05). Additionally, the potential of PhHV-1 as internal control to monitor FV urine collection, storage, and processing was demonstrated.  相似文献   
1000.
The ubiquitously expressed mannose‐6‐phosphate receptors (MPRs) are a promising class of receptors for targeted compound delivery into the endolysosomal compartments of a variety of cell types. The development of a synthetic, multivalent, mannose‐6‐phosphate (M6P) glycopeptide‐based MPR ligand is described. The conjugation of this ligand to fluorescent DCG‐04, an activity‐based probe for cysteine cathepsins, enabled fluorescent readout of its receptor‐targeting properties. The resulting M6P‐cluster–BODIPY–DCG‐04 probe was shown to efficiently label cathepsins in cell lysates as well as in live cells. Furthermore, the introduction of the 6‐O‐phosphates leads to a completely altered uptake profile in COS and dendritic cells compared to a mannose‐containing ligand. Competition with mannose‐6‐phosphate abolished all uptake of the probe in COS cells, and we conclude that the mannose‐6‐phosphate cluster targets the MPR and ensures the targeted delivery of cargo bound to the cluster into the endolysosomal pathway.  相似文献   
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