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41.
Calix[4]arene‐based molecules hold great promise as candidate sensors and storage materials for nitric oxide (NO), owing to their unprecedented binding affinity for NO. However, the structure of calix[4]arene is complicated by the availability of four possible conformers: 1,3‐alternate, 1,2‐alternate, cone, and partial cone (paco). Whilst complexes of NO with several of these conformers have previously been established, the 1,2‐alternate conformer complex, that is, [1,2‐alter ? NO]+, has not been previously reported. Herein, we determine the crystal structure of the NO complex with the 1,2‐alternate conformer for the first time. In addition, we have also found that the 1,2‐alternate and 1,3‐alternate conformers can combine with two NO molecules to form stable bis(nitric oxide) complexes. These new complexes, which exhibit remarkable binding capacity for the construction of NO‐storage molecules, were characterized by using X‐ray crystallography and NMR, IR, and UV/Vis spectroscopy. These findings will extend our understanding of the interactions between nitric oxide and cofacially and non‐cofacially arrayed aromatic rings, and we expect them to aid in the design and development of new supramolecular sensors and storage materials for NO with high capacity and efficacy. 相似文献
42.
The compounds Re(CO)3Br[CH2(S-tim)2] (1) and {Re(CO)3(CH3CN)[CH2(S-tim)2]}(PF6) (2), where tim is 1-methylthioimidazolyl, were prepared in high yields and characterized both in the solid state and in solution. The solid-state structures show that the ligand acts in a chelating binding mode where the eight-member chelate ring adopts twist-boat conformations in both compounds. A comparison of both solid-state IR data for CO stretching frequencies and the solution-phase voltammetric measurements for the Re(1+/2+) couples between 1, 2, and related N,N-chelates of the rhenium tricarbonyl moiety indicate that the CH2(S-tim)2 ligand is a stronger donor than even the ubiquitous dipyridyl ligands. A combination of NMR spectroscopic studies and voltammetric studies revealed that compound 1 undergoes spontaneous ionization to form {Re(CO)3(CH3CN)[CH2(S-tim)2]+}(Br-) in acetonitrile. Ionization does not occur in solvents such as CH2Cl2 or acetone that are less polar and Lewis basic (less coordinating). The equilibrium constant at 293 K for the ionization of 1 in CH3CN is 4.3 x 10(-3). The eight-member chelate rings in each 1 and 2 were found to be conformationally flexible in all solvents, and boat-chair conformers could be identified. Variable-temperature NMR spectroscopic studies were used to elucidate the various kinetic and thermodynamic parameters associated with the energetically accessible twist-boat to twist-boat and twist-boat to boat-chair interconversions. 相似文献
43.
Viktor N. Odinokov Olga S. Kukovinets Leonard M. Khalilov Genrikh A. Tolstikov Alexander Yu. Kosnikov Sergei V. Lindeman Yury T. Struchkov 《Tetrahedron letters》1985,26(47):5843-5844
The formation of the product of intramolecular interaction of a zwitterion and a methoxycarbonyl group was observed in the process of ozonating dimethyl ester of endo,cis-bicyclo [2,2,1]hept-5-en-2,3-dicarbonic acid in diethyl ether. The structure of racemic endo,cis-4-methoxy-5-methoxycarbonyl-6-formyl-1,4-epoxy-2,3-dioxacyclopenta[2,3-δ] cyclohexane was established by an X-ray structure analysis. 相似文献
44.
S. M. Adekenov N. M. Gafurov K. M. Turdybekov S. V. Lindeman Yu. T. Struchkov 《Chemistry of Natural Compounds》1992,27(6):690-696
The results of the chemical modification of stizolicin, a sesquiterpene lactone of the trans,trans-germancrane type and, in particular, the epoxidation, saponification, and acetylation of its molecule are discussed. On the basis of the results of an x-ray structural experiment, for 6-acetoxy-13-methoxy-1,10-epoxystizolicin we propose the structure of 6-acetoxy-13-methoxy-1,10: 4,5-diepoxy-1,5,7(H),8,11(H)-E,E-germacr-8,12-olide.Institute of Organic Synthesis and Coal Chemistry, Kazakh Academy of Sciences, Karaganda. A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 782–789, November–December, 1991. 相似文献
45.
Jacob D. Porter Eric Greve Abdulmohsen Alsafran Adam R. Benoit Sergey V. Lindeman Chris Dockendorff 《Tetrahedron》2018,74(37):4823-4836
Bifunctional catalysts containing discrete metal pi-acid and amine sites were designed and investigated for the direct intermolecular addition of aldehydes and ketones to unactivated alkynes. Copper(I)-based catalysts were prioritized based on intramolecular (Conia-ene type) reactions, and complexes were designed with tridentate ligands and potentially hemilabile heterocyclic spacers. The structures of the designed catalysts were computed using density functional theory (DFT), and the relative energies of putative catalytic intermediates were estimated and used to prioritize catalyst designs. Novel bifunctional precatalysts containing a thiazole spacer were synthesized via a 9-step sequence and combined with transition metals before screening for the direct addition of aldehydes and ketones to several internal and terminal alkynes. Despite the lack of desired intermolecular reactions, DFT calculations of putative catalyst intermediates appears to be a promising strategy for the design and prioritization of bifunctional catalysts for CC bond formation. 相似文献
46.
From Intramolecular (Circular) in an Isolated Molecule to Intermolecular Hole Delocalization in a Two‐Dimensional Solid‐State Assembly: The Case of Pillarene 下载免费PDF全文
Dr. Maxim V. Ivanov Dr. Denan Wang Dr. Tushar S. Navale Dr. Sergey V. Lindeman Prof. Rajendra Rathore 《Angewandte Chemie (International ed. in English)》2018,57(8):2144-2149
To achieve long‐range charge transport/separation and, in turn, bolster the efficiency of modern photovoltaic devices, new molecular scaffolds are needed that can self‐assemble in two‐dimensional (2D) arrays while maintaining both intra‐ and intermolecular electronic coupling. In an isolated molecule of pillarene, a single hole delocalizes intramolecularly via hopping amongst the circularly arrayed hydroquinone ether rings. The crystallization of pillarene cation radical produces a 2D self‐assembly with three intermolecular dimeric (sandwich‐like) contacts. Surprisingly, each pillarene in the crystal lattice bears a fractional formal charge of +1.5. This unusual stoichiometry of oxidized pillarene in crystals arises from effective charge distribution within the 2D array via an interplay of intra‐ and intermolecular electronic couplings. This important finding is expected to help advance the rational design of efficient solid‐state materials for long‐range charge transfer. 相似文献
47.
K. M. Turdybekov S. V. Lindeman T. V. Timofeeva Yu. T. Struchkov 《Chemistry of Natural Compounds》1991,27(2):169-173
A calculation has been made by the method of molecular mechanics, using the MM2 program, of a number of stereomeres of 1,5,6,7(H)- and 1,5,6,7(H)-guai-11(13)-en-6,12-olides. The possibilities of the adoption by the seven-membered ring of particular conformations according to the type of its linkage with the 5-membered carbocycle have been considered. Questions of the influence of the orientation of the Me groups on the degree of distortion of the conformation of the seven-membered ring from the ideal and the relative stabilities of the various conformers are discussed.A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 198–203, March–April, 1991. 相似文献
48.
S. V. Lindeman A. M. Turuta Yu. T. Struchkov A. V. Kamernitskii 《Russian Chemical Bulletin》1993,42(2):365-370
The structure of the title compound (1) has been studied by means of X-ray diffraction. The region of cycleD in epoxide1 was compared with that of the 16,17-epoxy derivatives of progesterone and pregnenolone (studied previously) as well as with that of the respective 16,17- and 16,17-cyclopropano analogs. In contrast to the 16,17-epoxy-20-oxo derivatives, in compound1 the electron conjugation of the epoxide ring with the CH3CO group at C(17) is partly disrupted. Moreover, the steric congestion at C(17) is significantly less pronounced in 16,17-epoxide1 than in its 16,17-counterpart. Both of these factors, especially steric decongestion, are favorable for nucleophilic attack at C(17) in the molecule of1. The X-ray diffraction data do not contradict the previously advanced mechanism of epoxide ring opening in 16,17- and 16,17-epoxy-20-oxo steroids by nucleophilic reagents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 401–405, February, 1993. 相似文献
49.
S. M. Desenko V. D. Orlov V. V. Lipson O. V. Shishkin S. V. Lindeman Yu. T. Struchkov 《Chemistry of Heterocyclic Compounds》1993,29(5):588-592
The oxidation of aromatic derivatives of 1,4- and 3,4-dihydropyrimido[1,2a]benzimidazoles gave the corresponding 3-hydroxy-3,4-dihydro derivatives and the dehydrogenation of these compounds was carried out. An x-ray diffraction structural analysis was carried out on 2-(4-dimethylaminophenyl)-3-hydroxy-4-phenyl-3,4-dihydropyrimido[1,2a]benzimidazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 688–693, May, 1993. 相似文献
50.
A. M. Turuta A. V. Kamernitskii T. M. Fadeeva A. Pabinger V. S. Bogdanov S. V. Lindeman Yu. T. Struchkov 《Russian Chemical Bulletin》1988,37(10):2156-2161
1. | The transformation of 21-0,N-isopropylidene derivatives of 16,17-epiminopregn-5-ene-2,21-diol-20-one into 20-0,N-isopropylidene derivatives of 16,17-epiminopregn-5-ene-3,20-diol-20-one was discovered, and, based on this, a new variant of the synthesis of 16,17-epiminopregn-5-ene-3,21-diol-20-one-3,21-diacetate was proposed. |
2. | A new class of steroids with additional tetrahydrofuran and 1,3 -imidazolidine-2thione rings E and F, respectively, was synthesized. |