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排序方式: 共有249条查询结果,搜索用时 203 毫秒
1.
The collisional shifts and widths of several P-branch spectral lines in the fundamental band of CO-Ar have been measured at temperatures between 214 and 324 K and pressures between 0.025 and 1 atm. The widths have been determined using a line shape model based on the solution of the transport/relaxation equation for the appropriate off-diagonal element of the density matrix. The model uses a realistic molecular potential energy surface to calculate the speed dependence of the collisional broadening, and a rigid sphere potential to calculate the translational motion. It is found that both the shifting and broadening coefficients follow a power law dependence on the temperature. Additionally, it is demonstrated that studies have tended to overestimate the accuracy of collisional widths when the line shape model used to obtain the widths involves multiple fitted line shape parameters or fails to fit the measured spectra within the experimental noise. 相似文献
2.
W.John Albery David Clark Humphrey J.J. Drummond Anthony J.M. Coombs William K. Young Clive E.W. Hahn 《Journal of Electroanalytical Chemistry》1992,340(1-2)
A novel electrochemical sensor for the determination of CO2 in expired breath is described. The sensor works by generating
from the reduction of O2 in dimethyl sulphoxide (DMSO) in a generating pulse. There is a rapid titration reaction between the
and any CO2 present. In the recovery pulse the amount of unreacted
is determined. The larger the concentration of CO2 the less
is found in the recovery pulse. The solubilities and diffusion coefficients of O2 and CO2 in DMSO have been determined using rotating disc voltammetry and rotation speed step experiments. The stoichiometry, the product, and the rate constant of the titration reaction have been determined using ring—disc voltammetry and laser Raman spectroscopy. The operation and the effect of adventitious water on the sensor are described. Results are presented which show that the sensor can indeed measure the breath-by-breath rhythm of expired CO2 from a human subject. 相似文献
3.
Abstract— The absorption spectra of the un-ionized and ionized forms of 4-heptadecyl-7-hydroxycoumarin (HHC) in aqueous self-assembled surfactant solution have been investigated. From a comparison with the absorption spectra of 7-hydroxycoumarin, 7-hydroxy-4-methylcoumarin (MHC) and HHC in neat organic solvents and organic solvent/water mixtures it is shown that the 7-hydroxycoumarin chromophore of HHC in self-assembled surfactant solution resides, on average, in an interfacial microenvironment which has a lower effective dielectric constant than that of the bulk aqueous solution. The absorption spectrum of the ionized form of HHC in aggregates of self-assembled surfactant molecules with cationic quaternary ammonium headgroups is found to be consistent with there being specific molecular interaction between the anionic chromophore and the quaternary ammonium headgroup. pH titrations performed with MHC in pure water and in four molar aqueous solutions of sodium chloride and tetra-methylammonium chloride indicate that the acid-base dissociation of HHC in charged micelles and vesicles should not be substantially influenced by any interfacial salt-effects, and that the acid-base dissociation of HHC in cationic micelles and vesicles with quaternary ammonium headgroups should not be markedly affected by the specific molecular interaction that exists. Estimates of the electrostatic surface potentials of a number of self-assembled surfactant aggregates are made by utilising the acid-base dissociation of HHC and assuming that the nonionic micelles of n -dodecyl octaoxyethylene glycol monoether (C12 E8 ) can serve as a reference state of zero surface potential. The validity of this assumption in relation to both micelles and vesicles is discussed in detail. 相似文献
4.
Naloxone 3-methyl ether was selectively oxidized by treatment with cerium ammonium nitrate in aqueous acetonitrile at ambient temperature to provide the 10-(S)-hydroxy adduct. The stereochemistry of the oxidation product was proven by single crystal X-ray structure determination. The Dess-Martin periodinane further oxidized the 10-hydroxy to the 10-keto analog. Deprotection formed 10-ketonaloxone as an analytical reference standard. 相似文献
5.
Dr. Anna Notaro Marta Jakubaszek Severin Koch Dr. Riccardo Rubbiani Dr. Orsolya Dömötör Dr. Éva A. Enyedy Mazzarine Dotou Dr. Fethi Bedioui Mickaël Tharaud Dr. Bruno Goud PD Dr. Stefano Ferrari Prof. Dr. Enzo Alessio Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4997-5009
Cancer is one of the main causes of death worldwide. Chemotherapy, despite its severe side effects, is to date one of the leading strategies against cancer. Metal-based drugs present several potential advantages when compared to organic compounds and they have gained trust from the scientific community after the approval on the market of the drug cisplatin. Recently, we reported the ruthenium complex ([Ru(DIP)2(sq)](PF6) (where DIP is 4,7-diphenyl-1,10-phenantroline and sq is semiquinonate) with a remarkable potential as chemotherapeutic agent against cancer, both in vitro and in vivo. In this work, we analyse a structurally similar compound, namely [Ru(DIP)2(mal)](PF6), carrying the flavour-enhancing agent approved by the FDA, maltol (mal). To possess an FDA approved ligand is crucial for a complex, whose mechanism of action might include ligand exchange. Herein, we describe the synthesis and characterisation of [Ru(DIP)2(mal)](PF6), its stability in solutions and under conditions that resemble the physiological ones, and its in-depth biological investigation. Cytotoxicity tests on different cell lines in 2D model and on HeLa MultiCellular Tumour Spheroids (MCTS) demonstrated that our compound has higher activity than cisplatin, inspiring further tests. [Ru(DIP)2(mal)](PF6) was efficiently internalised by HeLa cells through a passive transport mechanism and severely affected the mitochondrial metabolism. 相似文献
6.
7.
Non-lamellar lyotropic liquid crystalline (LLC) lipid nanoparticles contain internal multidimensional nanostructures such as the inverse bicontinuous cubic and the inverse hexagonal mesophases, which can respond to external stimuli and have the potential of controlling drug release. To date, the internal LLC mesophase responsiveness of these lipid nanoparticles is largely achieved by adding ionizable small molecules to the parent lipid such as monoolein (MO), the mixture of which is then dispersed into nanoparticle suspensions by commercially available poly(ethylene oxide)–poly(propylene oxide) block copolymers. In this study, the Reversible Addition-Fragmentation chain Transfer (RAFT) technique was used to synthesize a series of novel amphiphilic block copolymers (ABCs) containing a hydrophilic poly(ethylene glycol) (PEG) block, a hydrophobic block and one or two responsive blocks, i.e., poly(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl acrylate) (PTBA) and/or poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA). High throughput small angle X-ray scattering studies demonstrated that the synthesized ABCs could simultaneously stabilize a range of LLC MO nanoparticles (vesicles, cubosomes, hexosomes, inverse micelles) and provide internal particle nanostructure responsiveness to changes of hydrogen peroxide (H2O2) concentrations, pH and temperature. It was found that the novel functional ABCs can substitute for the commercial polymer stabilizer and the ionizable additive in the formation of next generation non-lamellar lipid nanoparticles. These novel formulations have the potential to control drug release in the tumor microenvironment with endogenous H2O2 and acidic pH conditions. 相似文献
8.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
9.
Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays
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Michael Mayer Prof. Dr. Shigehiko Takegami Michael Neumeier Simone Rink Prof. Dr. Axel Jacobi von Wangelin Silja Schulte Moritz Vollmer Prof. Dr. Axel G. Griesbeck PD Dr. Axel Duerkop Prof. Dr. Antje J. Baeumner 《Angewandte Chemie (International ed. in English)》2018,57(2):408-411
The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)3]2+, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches. 相似文献
10.