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81.
For the first time, the nuclear magnetic resonance (NMR) spin-spin coupling mechanism is decomposed into one-electron and electron-electron interaction contributions to demonstrate that spin-information transport between different orbitals is not exclusively an electron-exchange phenomenon. This is done using coupled perturbed density-functional theory in conjunction with the recently developed J-OC-PSP [=J-OC-OC-PSP: Decomposition of J into orbital contributions using orbital currents and partial spin polarization)] method. One-orbital contributions comprise Ramsey response and self-exchange effects and the two-orbital contributions describe first-order delocalization and steric exchange. The two-orbital effects can be characterized as external orbital, echo, and spin transport contributions. A relationship of these electronic effects to zeroth-order orbital theory is demonstrated and their sign and magnitude predicted using simple models and graphical representations of first order orbitals. In the case of methane the two NMR spin-spin coupling constants result from totally different Fermi contact coupling mechanisms. (1)J(C,H) is the result of the Ramsey response and the self-exchange of the bond orbital diminished by external first-order delocalization external one-orbital effects whereas (2)J(H,H) spin-spin coupling is almost exclusively mitigated by a two-orbital steric exchange effect. From this analysis, a series of prediction can be made how geometrical deformations, electron lone pairs, and substituent effects lead to a change in the values of (1)J(C,H) and (2)J(H,H), respectively, for hydrocarbons. 相似文献
82.
The macrodiolide antibiotic elaiophylin (1) forms stable, long-lasting cation selective ion channels in planar lipid bilayer membranes prepared from soybean phosphatidylcholine. Current of the single ion channel displayed two sublevels corresponding to the two substates of the channel conductance: a slow substate, with about 5 s of mean dwell time in the open state at 40% level of the total amplitude conductance, and a fast substate of higher conductance with dwell times in the open and closed state of about 0.1 s. Amplitude conductances of the single ion channels in 200 mM of LiCl, NaCl, KCl, RbCl and CsCl were 75, 140, 220, 240 and 226 pS, and the conductance was linear function of the electrolyte concentration. Ratios of cation to anion permeabilities of the channel for NaCl and KCl were 8+/-2 and >24, respectively. A molecular model of the channel structure is suggested. 相似文献
83.
Summary A practicable method was developed for the routine determination of formaldehyde in air. Formaldehyde is sampled in small sampling tubes filled with Chromosorb P, coated with 2,4-dinitrophenylhydrazine (= DNPH). The sorbent is extracted with acetonitrile, and the different DNPhydrazones were separated by reversed-phase HPLC. UV-detection at = 345 nm was compared with electrochemical detection. The detection limit was 100 pg for UV- and 50 pg for electrochemical detection with a linear range of more than 3 decades, respectively. For the determination of formaldehyde in air the detection limit is 10 ppb with an average recovery of 99.3% and an estimated relative standard deviation S of 1.5%. This method was compared with the sampling by impingers using the same separation and detection method.
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
Einige neue Aspekte einer HPLC-Methode zur Spurenbestimmung von Formaldehyd in Luft
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
84.
F. GrØnlund 《Journal of Thermal Analysis and Calorimetry》1992,38(1-2):229-238
The procedure used by many electrochemists in calculating enthalpy in calorimetric measurements of electrolysis reactions is compared to a purely thermodynamic approach, using the data published by Fleischmannet al. [J. Electroanal. Chem., 287 (1990) 293.] as a case study.The set of excess values dH
ex/dt=dH
obs/dt -dHcalo/dt obtained with the former procedure was neither correlated to any of the experimental parameters nor to the set of values found using thermodynamics. The latter, smaller by factors of up to two orders of magnitude, are shown to follow an expression of the form dH
ex/dt=–kI exp (–E
a/RT) with an activation enthalpy of about 85 kJ·mol–1. It is suggested that recombination of electrolysis gases may account for this.
Zusammenfassung Das von vielen Elektrochemikern verwendete Verfahren zur Berechnung der Enthalpie in kalorimetrischen Messungen an Elektrolysereaktionen wurde unter Anwendung der von Fleischmann et.al. in einer Fallstudie [J. Electroanal. Chem., 287 (1990) 293.] veröffentlichten Angaben mit einer rein thermodynamischen Näherung verglichen.Eine Reihe von mit der ersten Methode erhaltenen überschu\werten dH ex/dt=dH obs/dt-dH calc/dt korrelierte weder mit den experimentellen Parametern noch mit den entsprechenden, thermodynamisch gefundenen Werten. Letztere, um etwa zwei Grö\enordnungen kleinere Werte konnten durch die Gleichung dH ex/dt= -kI exp (-E a/RT) mit einer Aktivierungsenthalpie von etwa 85 kJ·mol–1 beschrieben werden. Es wird deshalb nahegelegt, da\ dies einer Rekombinierung der Elektrolysegase zugeschrieben werden kann.相似文献
85.
Dichloro Acetylene as Complex Ligand. Crystal Structure of PPh4[WCl5(C2Cl2)] · 0.5 CCl4 Tungsten hexachloride and dichloro acetylenediethyletherate react in boiling CCl4 in presence of C2Cl4 as reducing agent forming [Et2O · WCl4(C2Cl2)]. In vacuo the complex looses ether giving the dichloro acetylene complex [WCl4(C2Cl2)]2 which is dimeric with chloro bridges. Both complexes react with tetraphenylphosphonium chloride to form PPh4[WCl5(C2Cl2)] which is equally prepared by ligand exchange of PPh4[WCl5(C2I2)] with silver chloride. All dichloro acetylene complexes are red to brown crystalline solids sensitive to moisture, and are thermally and mechanically very stable compared with the highly explosive dichloro acetylene. The compounds are characterized by their i.r. spectra; [Et2O · WCl4(C2Cl2)] was additionally investigated by 13C-nmr spectroscopy. PPh4[WCl5(C2Cl2)] · 0.5 CCl4 formes dark brown crystals; according to the structural investigation by X-ray diffraction methods the compound crystallizes orthorhombic in the space group Pbca with 8 formula units per unit cell (1317 observed, independent reflexions, R = 0.049). The cell dimensions are a = 1702 pm, b = 1675 pm and c = 2228 pm. The compound consists of [WCl5(C2Cl2)]? anions and PPh4⊕ cations including CCl4 molecules without bonding interactions. The tungsten atoms are seven-coordinated by five chlorine atoms and two carbon atoms. The dichloro acetylene ligand is bonded symmetrically side-on and has a C? C bond length of 128 pm. The W? C distances are 201 pm, the four equatorial Cl atoms have W? Cl bond lengths of 234 pm whereas the chlorine atom in trans-position to the W? C2 group is situated in a distance of 244 pm. 相似文献
86.
Branchadell V Crévisy C Grée R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5795-5803
The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde. 相似文献
87.
Kerékgyártó T Gróf P Rontó G 《Journal of photochemistry and photobiology. B, Biology》1999,53(1-3):27-35
Biological systems used as biological dosimeters can possess different angular sensitivities from the detectors usually used in physical devices. A simple experimental setup has been developed and used to measure the angular sensitivity of uracil thin-layer biological dosimeters. Results of angular sensitivity measurements for uracil thin-layer dosimeters are presented using a Xe arc lamp as the UV source. According to the experiments described here, uracil thin-layer dosimeters show a cosine-type angular dependence. In several indoor experiments broadband UV meters are used to control the applied dose rate from a given artificial UV source. The experimental setup has been designed and used to verify experimentally the importance of spectral and angular sensitivity differences of biological and physical UV meters applied in biological experiments. Model calculations for two different irradiation systems, using different geometrical arrangements of artificial UV sources, are also presented. For these arrangements relative dose rates that could be measured with dosimeters of arbitrary spectral, but different angular sensitivity have been calculated. 相似文献
88.
Summary A method is described for the determination of shortchain aliphatic amines in ambient air based on impinger sampling in dilute H2SO4, selective enrichment across a PTFE gas membrane and quantification by gas chromatography. The enrichment step is carried out in a flow system directly connected to the chromatograph. The separation is performed on a packed column with nitrogen selective detection. The enrichment per sample volume was in the range 7.3 to 8.2 mL–1 for C1–C6 amines. Detection limits were ca 3–10 nM with enrichment of a 2.9 mL liquid sample. After impinger sampling of 5 m3 air in 10 mL absorption solution, this corresponds, to 0.4–0.8 ng/m3 (ca 0.2–0.5 ppt by volume) in air. 相似文献
89.
90.
Karlheinz Ballschmiter 《Angewandte Chemie (International ed. in English)》1992,31(5):487-515
The role of chemistry in our soon-to-be global industrial society requires a global perspective for the discussion of the uptake, transport, and conversion of chemical compounds in the environment. The fate of organic compounds in the volume flow of the atmosphere and hydrosphere can be categorized into transport pathways and adjustments of equilibria in the multiphase system atmosphere-oceans-land surface. The global volume flow in the atmosphere (wind, areas of high and low pressure) and in the hydrosphere (rivers, circulation of water in lakes, ocean currents) alone would account for the transport of organic compounds if they were stable and if all these compounds were molecularly distributed in these phases. However, this particular case is observed only for volatile chlorofluorocarbons and tetrachloromethane. For most organic compounds, complex adsorption/desorption processes on finely dispersed particle phases in the air and water as well as abiotic and biotic transformations determine the transport behavior. The global fate of a compound includes its accumulation as well as its decomposition in defined environmental compartments. Both phenomenon may have long-term consequences in the af-fected areas; this is indicated by the accumulation of polychlorobiphenyls and analogous compounds in marine mammals and deep-sea fauna, and is evident in the decomposition of chlorofluorocarbons in the stratosphere. The accepted definition of the level of a risk, the product of the probability of an event and the potential amount of damage, takes on a new dimension when viewed from a global perspective-especially when one further connects the extent of the damage to the possible means of correction. It is the responsibility of scientists to point out the irreparable regional to global consequences directly and indirectly connected to the production of chemicals and to provide suggestions for prevention. Politicians can only react by applying their methods to limit the damage; however, they cannot generate any solutions based on science. 相似文献