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41.
Edmund A. DiMarzio 《Foundations of Physics》1977,7(7-8):511-528
The Lorentz transformation is derived without assuming that the velocity of light is a constant. This suggests that the constantc which appears in the transformation has a deeper significance than heretofore commonly assumed. It is hypothesized that there exists, in all of physical reality, velocities of only one magnitude. The magnitude isc, the speed of light in vacuum. This hypothesis forces us to view a fundamental particle as an extended object and matter in general as a field (t, r, ), which we give the generic name stuff. An important feature of the field is that at each spacetime point(t, r) stuff travels in all directions with speedc. In order to elucidate the nature of (t, r, ), the equations determining for a one-dimensional world are derived and solved. Fundamental particles are shown to exist and their structure is obtained.A private communication; not an official publication of the National Bureau of Standards. 相似文献
42.
W.Franklin Smyth Clare Joyce Venkataraman N. Ramachandran Edmund O’Kane Danny Coulter 《Analytica chimica acta》2004,506(2):203-214
The electrospray ionisation-ion trap mass spectrometry (ESI-MSn) of selected hypnotic drugs, i.e. zopiclone, zolpidem, flunitrazepam and their metabolites have been investigated. Sequential product ion fragmentation experiments (MSn) have been performed in order to elucidate the degradation pathways for the [M+H]+ ions and their predominant fragment ions. These MSn experiments show certain characteristic fragmentations in that functional groups are generally cleaved from the ring systems as neutral molecules such as H2O, CO, CO2, NO2, amines and HF. When an aromatic entity is present in a drug molecule together with a nitrogen-containing saturated ring structure as with zopiclone and its N-desmethyl metabolite fragmentation initially occurs at the latter ring with the former being resistant to fragmentation. The structures of fragment ions proposed for ESI-MSn can be supported by electrospray ionisation-quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS).These molecules can be identified and determined in mixtures at low ng/ml concentrations by the application of liquid chromatography (LC)-ESI-MSn which can be used for their analysis in saliva samples.This paper includes a tabulation of mass losses/signals at low m/z values for these hypnotic drugs and many others in recent publications which will be of value in the characterisation of drug metabolites of unknown structure and also natural product pharmaceuticals isolated from plants, etc. 相似文献
43.
Heine DR Grest GS Webb EB 《Langmuir : the ACS journal of surfaces and colloids》2005,21(17):7959-7963
Molecular dynamics simulations are used to study the spreading of binary polymer nanodroplets in a cylindrical geometry. The polymers, described by the bead-spring model, spread on a flat surface with a surface-coupled Langevin thermostat to mimic the effects of a corrugated surface. Each droplet consists of chains of length 10 or 100 monomers with approximately 350,000 monomers total. The qualitative features of the spreading dynamics are presented for differences in chain length, surface interaction strength, and composition. When the components of the droplet differ only in the surface interaction strength, the more strongly wetting component forms a monolayer film on the surface even when both materials are above or below the wetting transition. In the case where the only difference is the polymer chain length, the monolayer film beneath the droplet is composed of an equal amount of short chain and long chain monomers even when one component (the shorter chain length) is above the wetting transition and the other is not. The fraction of short and long chains in the precursor foot depends on whether both the short and the long chains are in the wetting regime. Diluting the concentration of the strongly wetting component in a mixture with a weakly wetting component decreases the rate of diffusion of the wetting material from the bulk to the surface and limits the spreading rate of the precursor foot, but the bulk spreading rate actually increases when both components are present. This may be due to the strongly wetting material pushing out the weakly wetting material as it moves toward the precursor foot. 相似文献
44.
Functionalized o-carboranes are interesting ligands for transition metals. Reaction of LiC2B10H11 with Me2NCH2CH2Cl in toluene afforded 1-Me2NCH2CH2-1,2-C2B10H11 (1). Treatment of 1 with 1 equiv. of n-BuLi gave [(Me2NCH2CH2)C2B10H10]Li ([1]Li), which was a very useful synthon for the production of bisfunctional o-carboranes. Reaction of [1]Li with RCH2CH2Cl afforded 1-Me2NCH2CH2-2-RCH2CH2-1,2-C2B10H10 (R = Me2N (2), MeO (3)). 1 and 2 were also prepared from the reaction of Li2C2B10H10 with excess Me2NCH2CH2Cl. Treatment of [1]Li with excess MeI or allyl bromide gave the ionic salts, [1-Me3NCH2CH2-2-Me-1,2-C2B10H10][I] (4) and [1-Me2N(CH2=CHCH2)CH2CH2-2-(CH2=CHCH2)-1,2-C2B10H10][Br] (6), respectively. Interaction of [1]Li with 1 equiv. of allyl bromide afforded 1-Me2NCH2CH2-2-(CH2=CHCH2)-1,2-C2B10H10 (5). Treatment of [1]Li with excess dimethylfulvene afforded 1-Me2NCH2CH2-2-C5H5CMe2-1,2-C2B10H10 (7). Interaction of [1]Li with excess ethylene oxide afforded an unexpected product 1-HOCH2CH2-2-(CH2=CH)-1,2-C2B10H10 (8). 1 and 3 were conveniently converted into the corresponding deborated compounds, 7-Me2NHCH2CH2-7,8-C2B9H11 (9) and 7-Me2NHCH2CH2-8-MeOCH2CH2-7,8-C2B9H10 (10), respectively, in MeOH-MeOK solution. All of these compounds were characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of 4 and 6-10 were confirmed by single-crystal X-ray analyses. 相似文献
45.
An efficient and regioselective synthesis of 2-methyl-2H-indazoles and 2-ethyl-2H-indazoles using trimethyloxonium tetrafluoroborate or triethyloxonium hexafluorophosphate is reported. 相似文献
46.
Edmund R. Marinelli 《Tetrahedron letters》1982,23(27):2745-2748
N-methyl and N-tert-butoxycarbonylindole-2,3-quinodimethanes ( and ) have been generated and observed to undergo intermolecular cycloaddition reactions with dienophiles. 相似文献
47.
Summary The method developed based on the determination of TC and TOC in the form of the total amount of CO2 requires application of the proper techniques for the final determination of CO2. The possibility of using a stream of carrier gas at a convenient flow-rate for desorbing quantitatively CO2 concentrated on a molecular sieve permits use of a wide variety of known analytical techniques for the final determination of CO2. Various methods were compared on the basis of both absolute and calibration measurements. The absolute methods chosen were gravimetric (classical or an automated version based on application of a gravimetric automat and automatic recording balance), thermogravimetric analysis and coulometry. The calibration methods included thermal conductivity, the flame-ionization detector (after conversion of CO2 into methane) and infrared absorption. Usefulness of the methods was evaluated on the basis of comparative statistical analysis of experimental data with respect to precision (Snedecor'sF-test and Bartlett'sU
2-test) and accuracy (Student'st-test).
Zusammenfassung Das entwickelte Verfahren zur Bestimmung des TC- und TOC-Gehaltes in Form der gesamten Menge CO2 erfordert die Anwendung geeigneter Analysentechniken zur Endbestimmung dieser Verbindung. Die Möglichkeit einer Desorption des am Molekularsieb angereicherten CO2 in einem Gasstrom mit geeignetem Durchfluß erlaubt zur Endbestimmung von CO2 die Anwendung einer Reihe verschiedener Analysenverfahren. Die Anwendbarkeit verschiedener, auf Absolutverfahren und auch auf relativen Messungen beruhender Methoden wurde vergleichend untersucht. Die folgenden Methoden zur CO2-Bestimmung wurden gewählt: die Gravimetrie (klassische oder automatisierte unter Einsatz eines Wägeautomaten und einer registrierenden Waage), die Thermogravimetrie und die Coulometrie. Von den relativen Methoden wurden die Thermokonduktometrie, der Flammenionisationsdetektor (nach Umsetzung von CO2 zu Methan) und das IR-Absorptionsmeßverfahren geprüft. Die Anwendbarkeit der Methoden wurde mit Hilfe statistischer Prüfverfahren beurteilt, wobei die Präzision (SnedecorsF-Test und BartlettsU 2-Test) und die Genauigkeit (Studentst-Test) der erhaltenen Analysenwerte verglichen wurden.相似文献
48.
It has been found possible to preserve metal—carbon and metalloid—carbon bonds during direct fluorination. The reaction of dimethylmercury with fluorine gives bis(trifluoromethyl)mercury in 6.5% yield. Fluorination of tetramethylsilane has led to the isolation of the new polyfluorotetramethylsilanes of the following type, Si(CH3)x(CH2F)y(CHF2)z, x + y + z = 4. Also characterized were compounds containing SiCF3. It has been possible to synthesize tetrakis(trifluoromethyl)germanium in 63.5% yield from the reaction of fluorine with tetramethylgermanium. Also characterized were many polyfluorotetramethylgermanes of the following type, Ge(CF3)x(CF2H)y(CFH2)z (x + y + z = 4). 相似文献
49.
Ka-Man Cheung 《Journal of organometallic chemistry》2005,690(2):253-260
Treatment of Ni(HP1) (H3P1 = meso-5-[4′-(2″-pyridyl)phenyl]-10,15,20-triphenyporphyrin) with K2[PdCl4] in EtOH afforded [Pd{Ni(P1)}]2(μ-Cl)2 that reacted with NaS2CNEt2 to give Pd(S2CNEt2)[Ni(P1)]. Reaction of Ni(HP1) with [Ir(H)2(PPh3)2(Me2CO)2][BF4] afforded Ir(H)Cl(PPh3)2[Ni(P1)]. The crystal structures of Pd(S2CNEt2)[Ni(P1)] and Ir(H)(Cl)(PPh3)2[Ni(P1)] have been determined. 相似文献
50.
Carina Hey Pui Cheung Jianchao Xu Chi Lung Lee Yanfeng Zhang Ruohan Wei Donald Bierer Xuhui Huang Xuechen Li 《Chemical science》2021,12(20):7091
Herein, we report the development of a facile synthetic strategy for constructing diverse peptide structural architectures via chemoselective peptide ligation. The key advancement involved is to utilize the benzofuran moiety as the peptide salicylaldehyde ester surrogate, and Dap–Ser/Lys–Ser dipeptide as the hydroxyl amino functionality, which could be successfully introduced at the side chain of peptides enabling peptide ligation. With this method, the side chain-to-side chain cyclic peptide, branched/bridged peptides, tailed cyclic peptides and multi-cyclic peptides have been designed and successfully synthesized with native peptidic linkages at the ligation sites. This strategy has provided an alternative strategic opportunity for synthetic peptide development. It also serves as an inspiration for the structural design of PPI inhibitors with new modalities.Methods of introducing peptide salicylaldehyde esters and hydroxyl amine functionality into the peptide side chain have been developed. Diverse peptide structural motifs were constructed via ligation with native amide linkages at the ligation sites. 相似文献