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1.
The d.s.c. curves of commercial samples of methaqualone—Qulude (U.S.A.), Qulude (Mexico), Sopar, Mandrax and Parest — are presented. Similar d.s.c. curves were found for Qulude (U.S.A.), Qulude (Mexico), and Mandrax, while Sopar and Parest exhibited different types of curves. New and old formulations of the Qulude (U.S.A.) brand could be differentiated by differences in the tablet filler and binder. Unfortunately, d.s.c. could not be used to determine the country of origin of the drug, although it was useful to characterize it. The technique can be used to identify samples of 0.15 mg or less. 相似文献
2.
Summary A generalized expression for the negative adsorption of anions by clay suspensions has been derived using an extension of
the procedure developed bySchofield. Negative adsorption of chloride by Na-montmorillonite has been measured in NaCl solutions from 0.1 M to 0.001 M. If the
clay was purified by ultrafiltration, measured negative adsorption nearly equalled that calculated from diffuse double layer
theory over the entire range of concentration. At very low electrolyte concentrations the measured negative adsorption was
less than the calculated amount, probably as a result of the presence of positive charges. Polyanions such as those of metaphosphate
or acrylic acid increased the negative adsorption in this region to the theoretical amount. At NaCl concentration between
0.05 and 0.005 M NaCl measured negative adsorption was a maximum of 20 per cent lower than that calculated. This probably
represented the error of the approximations made in the theoretical calculations by neglecting the effect of activity corrections
in the double layer.
Zusammenfassung Ein verallgemeinerter Ausdruck für die negative Adsorption von Anionen in Tonsuspensionen wird unter Erweiterung des vonSchofield verwendeten Rechnungsverfahrens abgeleitet. Die negative Adsorption von Chlorid durch Natrium-Montmorillonite wird mit NaCl-L?sungen, 0,1 M-0,00 m, gemessen. Wenn der Ton durch Ultrafiltration gereinigt war, kam die gemessene negative Adsorption über den ganzen Konzentrationsbereich nahezu der aus der Theorie der diffusen Doppelschicht berechneten gleich. Bei sehr niedrigen Elektrolytgehalten war die gemessene negative Adsorption geringer als die berechnete, wahrscheinlich als Ergebnis der Anwesenheit von positiven Ladungen. Polyanionen wie Metaphosphat oder Acryls?ure erh?hten die negative Adsorption in diesem Bereich auf den theoretischen Wert. Für NaCl-Konzentrationen zwischen 0,05 und 0,005 m zeigte die gemessene negative Adsorption ein um 20% niedriger liegendes Maximum als das berechnete. Dies repr?sentiert wahrscheinlich den Fehler in den N?herungen, die in den theoretischen Berechnungen durch Vernachl?ssigung der Effekte der Aktivit?tskorrekturen in der Doppelschicht verursacht werden.相似文献
3.
Gd10C4Cl18 and Gd10C4Cl17, Two Lanthanoid Cluster Compounds with Interstitial C2 Units The compounds Gd10C4Cl18 ( I ) and Gd10C4Cl17 ( II ) are prepared by heating stoichiometric amounts of GdCl3, Gd, and graphite in sealed tantalum tubes at 1070 ( I ) and 1 120 K ( II ). Single crystal investigations ( I : P21/c, Z = 2, a = 918.2, b = 1 612.0, c = 1 288.6 pm, β = 119.86°; II : P1 , Z = 1, a = 849.8, b = 917.4, c = 1 146.2 pm, α = 104.56°, β = 95.98°, γ = 111.35°) revealed the occurrence of novel Gd10C4Cl18 clusters. The metal framework is formed by edge-sharing of two Gd6 octahedra. These are centred by C2 units (dC? C = 147 pm) and Cl atoms bridge all available edges of the octahedra. The structure of I corresponds to a packing of such quasi molecular clusters, in II they are linked to chains via common Cl atoms. Both structures are discussed in terms of a model of close packed spheres as well as in the concept of condensed clusters. 相似文献
4.
Saalfrank RW Reimann U Göritz M Hampel F Scheurer A Heinemann FW Büschel M Daub J Schünemann V Trautwein AX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3614-3619
Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The M?ssbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses. 相似文献
5.
Tamm M Bannenberg T Fröhlich R Grimme S Gerenkamp M 《Dalton transactions (Cambridge, England : 2003)》2004,(3):482-491
Sterically demanding cycloheptatrienylium (tropylium) salts of the type (1,3,5-C7H4R3)BF4 [R = t-Bu, (3a)BF4; R = SiMe3, (3b)BF4] have been prepared from the corresponding 1,3,5-trisubstituted benzene derivatives 1 by ring expansion with diazomethane followed by hydride abstraction with triphenylcarbenium tetrafluoroborate, (Ph3C)BF4. Complexation can be achieved by arene exchange and Mo(CO)3 group transfer employing [(eta6-p-xylene)Mo(CO)3] (4) to yield the cationic complexes (5)BF4. In refluxing mesitylene, [(eta7-C7H4t-Bu3)Mo(CO)3]BF4, (5a)BF4, undergoes CO substitution to furnish the mesitylene sandwich complex (6a)BF4. A cyclic voltammetric study reveals that this complex exhibits a reversible one-electron oxidation to the dicationic 17e complex 6a2+, which can also be accessed by chemical oxidation with AgBF4. On the contrary, the reduction of 6a+ is irreversible and does not yield a stable 19e complex 6a. To study the fate of the reduced 19e form, (5a)BF4 was treated with Na2Hg to diastereoselectively afford the C-C coupled bicycloheptatriene complex 7a. Paramagnetic, dinuclear complexes of the type [(eta7-C7H4R3)Mo(mu-Cl)3Mo(eta7-C7H4R3)] (8) have been obtained from the reaction of (5)BF4 with Me3SiCl. These can be regarded as mixed-valence Mo(0)/Mo(+I) compounds with a metal-metal bond order of 0.5. Cyclic voltammetric studies reveal that both complexes 8a and 8b undergo reversible one-electron oxidation as well as reduction. Treatment with one equivalent of ferrocenium hexafluorophosphate leads to removal of the unpaired electron and formation of the diamagnetic complexes (8)PF6. Theoretical DFT calculations have been carried out to further elucidate the bonding in these systems. In addition, the X-ray crystal structures of (5b)BF4, (6a)BF4 x CH2Cl2, (6a)(BF4)2 x (acetone)2, 7a x CH2Cl2, 8a x 0.5C6H14, and (8a)PF6 x Et2O are reported. 相似文献
6.
Mareike Prüfer Christian Wenger Frank F. Bier Eva-Maria Laux Ralph Hölzel 《Electrophoresis》2022,43(18-19):1920-1933
Dielectrophoresis (DEP) is an AC electrokinetic effect mainly used to manipulate cells. Smaller particles, like virions, antibodies, enzymes, and even dye molecules can be immobilized by DEP as well. In principle, it was shown that enzymes are active after immobilization by DEP, but no quantification of the retained activity was reported so far. In this study, the activity of the enzyme horseradish peroxidase (HRP) is quantified after immobilization by DEP. For this, HRP is immobilized on regular arrays of titanium nitride ring electrodes of 500 nm diameter and 20 nm widths. The activity of HRP on the electrode chip is measured with a limit of detection of 60 fg HRP by observing the enzymatic turnover of Amplex Red and H2O2 to fluorescent resorufin by fluorescence microscopy. The initial activity of the permanently immobilized HRP equals up to 45% of the activity that can be expected for an ideal monolayer of HRP molecules on all electrodes of the array. Localization of the immobilizate on the electrodes is accomplished by staining with the fluorescent product of the enzyme reaction. The high residual activity of enzymes after AC field induced immobilization shows the method's suitability for biosensing and research applications. 相似文献
7.
Stephan Ludwig Dr. Kai Helmdach Mareike Hüttenschmidt Elisabeth Oberem Dr. Jabor Rabeah Dr. Alexander Villinger Prof. Dr. Ralf Ludwig Prof. Dr. Wolfram W. Seidel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16811-16817
A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)(PPh3)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)-(PPh3)], in which valence trapped WIII/RuII and WII/RuIII cationic species are at equilibrium. 相似文献
8.
Wojciech Czardybon Wojciech Sokol John Warkentin Nick Henry Werstiuk 《Journal of Physical Organic Chemistry》2008,21(1):41-46
Synthesis of a bicyclic 2,2‐dioxa oxadiazoline (6,7‐diaza‐1‐methoxy‐5‐methyl‐2,8‐dioxabicyclo[3.2.1]oct‐6‐ene) is reported. Its thermolysis at 27°C is about 200 times as fast as the thermolysis of a monocyclic oxadiazoline model system. Presumably, a cyclic dioxa carbonyl ylide is formed initially and the ylide then undergoes a bond scission to afford either a dioxacarbene or a dialkylcarbene or it cyclizes to an oxirane. A small fraction of a dialkylcarbene was trapped as the product of addition to dimethyl acetylenedicarboxylate (DMAD). Computations of the barriers to the loss of N2 from the oxadiazolines and to the formation of the carbenes from the carbonyl ylide resulting from thermolysis of the bicyclic oxadiazoline are compared to corresponding barriers for a similar monocyclic oxadiazoline. The rate acceleration is accounted for in terms of geometric factors. The complex products from the decomposition of the bicyclic oxadiazoline were not studied. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
9.
Kolb NR Rauf AW Igarashi R Hornidge DL Pywell RE Warkentin BJ Korkmaz E Feldman G O'Rielly GV 《Physical review letters》2000,85(7):1388-1391
Cross sections for quasifree Compton scattering from the deuteron were measured for incident energies of E(gamma) = 236-260 MeV at the laboratory angle straight theta(gamma(')) = -135 degrees. The recoil nucleons were detected in a liquid-scintillator array situated at straight theta(N) = 20 degrees. The measured differential cross sections were used, with the calculations of Levchuk et al., to determine the polarizabilities of the bound nucleons. For the bound proton, the extracted values were consistent with the accepted value for the free proton. Combining our results for the bound neutron with those from Rose et al., we obtain 1-sigma constraints of alpha;(n) = 7.6-14.0 and beta;(n) = 1.2-7.6. 相似文献
10.
N. Warkentin M. Diehl D. Yu. Ivanov A. Schäfer 《The European Physical Journal A - Hadrons and Nuclei》2007,32(3):273-291
We investigate electroproduction of pion pairs on the nucleon in the framework of QCD factorization for hard exclusive processes.
We extend previous analyses by taking the hard-scattering coefficients at next-to-leading order in αs . The dynamics of the produced pion pair is described by two-pion distribution amplitudes, for which we perform a detailed
theoretical and phenomenological analysis. In particular, we obtain constraints on these quantities by comparing our results
with measurements of angular observables that are sensitive to the interference between two-pion production in the isoscalar
and isovector channels. 相似文献