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121.
Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes
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Konstantin Junold Johannes A. Baus Dr. Christian Burschka Dr. Célia Fonseca Guerra Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Reinhold Tacke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12411-12415
Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt3 and BPh3 leads to the formation of the Lewis acid/base complexes 2 and 3 , respectively, which are the first five‐coordinate silicon compounds with an Si?B bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies. 相似文献
122.
Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base‐Catalyzed Rearrangement of Allylic Carbamates
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Dipl.‐Chem. Johannes Moritz Bauer Dr. Wolfgang Frey Prof. Dr. René Peters 《Angewandte Chemie (International ed. in English)》2014,53(29):7634-7638
A regio‐ and enantioselective tandem reaction is reported capable of directly transforming readily accessible achiral allylic alcohols into chiral sulfonyl‐protected allylic amines. The reaction is catalyzed by the cooperative action of a chiral ferrocene palladacycle and a tertiary amine base and combines high step‐economy with operational simplicity (e.g. no need for inert‐gas atmosphere or catalyst activation). Mechanistic studies support a PdII‐catalyzed [3,3] rearrangement of allylic carbamates—generated in situ from the allylic alcohol and an isocyanate—as the key step, which is followed by a decarboxylation. 相似文献
123.
Unprecedented Strong Lewis Bases—Synthesis and Methyl Cation Affinities of Dimethylamino‐Substituted Terpyridines
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Dr. Paul Hommes Christina Fischer Dr. Christoph Lindner Prof. Dr. Hendrik Zipse Prof. Dr. Hans‐Ulrich Reissig 《Angewandte Chemie (International ed. in English)》2014,53(29):7647-7651
A versatile method for the synthesis of functionalized 2,2′:6′,2′′‐terpyridines by assembly of the terminal pyridine rings is presented. The cyclization precursors—bis‐β‐ketoenamides—are prepared from 4‐substituted 2,6‐pyridinedicarboxylic acids and acetylacetone or its corresponding enamino ketone. Treatment with trimethylsilyl trifluoromethanesulfonate induces a twofold intramolecular condensation providing an efficient access to 4,4′′‐di‐ and 4,4′,4′′‐trifunctionalized 6,6′′‐dimethyl‐2,2′:6′,2′′‐terpyridines. Using this method, hitherto unknown 4,4′′‐bis(dimethylamino)‐ and 4,4′,4′′‐tris(dimethylamino)terpyridines have been prepared that show remarkably high calculated Lewis basicities. 相似文献
124.
YANG Gao-Shan LIU Chong-Bo LI Heng-Nong CHEN Yuan HUANG De-He WEN Hui-Liang 《结构化学》2014,33(4):528-534
Two heterocyclic Schiff bases were synthesized via the condensation reactions of primary amines with carbonyl compounds. 2-[(4-pyridylmethylene)-amino] phenol(compound 1) was synthesized by the interaction of 4-pyridinecarboxaldehyde with o-aminophenol in ethanol solvent; N,N‘-bis(3-(furan-2-yl)allylidene)benzene-1,4-diamin(compound 2) was synthesized by the interaction of 3-(2-furyl)acrolein with p-phenylenediamine in ethanol medium. The compounds were characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction. Compound 1(C12H10N2O) crystallizes in the monoclinic system, space group P21/c with a = 7.0771(7), b = 7.2820(7), c = 19.849(2),β= 96.3390(10)°, V = 1016.66(17) ?3, Z = 4, Mr = 198.22, Dc = 1.295 g/cm3, F(000) = 416, GOOF = 1.060, μ= 0.085 mm-1, the final R = 0.0371 and wR = 0.0929 for 1497 observed reflections with I 2σ(I). Compound 2(C20H16N2O2) crystallizes in the orthorhombic system, space group Fdd2 with a = 26.344(15), b = 48.50(3), c = 5.293(3), V = 6764(7) ?3, Z = 16, Mr = 316.35, Dc = 1.243 g/cm3, F(000) = 2656, GOOF = 1.043, = 0.081 mm-1, the final R = 0.0526 and wR = 0.1267 for 2059 observed reflections with I 2σ(I). 1 and 2 molecules are connected through hydrogen bonds to generate a 2D network and a 1D chain structure, respectively. The preliminary antibacterial activity results showed that the title compounds display excellent antibacterial activities to Escherichia coli, Staphylococcus aureus and Bacillus subtilis. 相似文献
125.
Lysidine (k2C) is one of the most modified pyrimidine RNA bases. It is a cytidine nucleoside, in which the 2-oxo functionality of the heterocycle is replaced by the ϵ-amino group of the amino acid lysine. As such, lysidine is an amino acid-containing RNA nucleoside that combines directly genotype (C-base) with phenotype (lysine amino acid). This makes the compound particularly important in the context of theories about the origin of life and here especially for theories that target the origin of translation. Here, we report the total synthesis of the U-derivative of lysidine (k2U), which should have the same base pairing characteristics as k2C if it exists in the isoC-like tautomeric form. To investigate this question, we developed a phosphoramidite building block for k2U, which allows its incorporation into RNA strands. Within RNA, k2U can base pair with the counter base U and isoG, confirming that k2U prefers an isoC-like tautomeric structure that is also known to dominate for k2C. The successful synthesis of a k2U phosphoramidite and its use for RNA synthesis now paves the way for the preparation of a k2C phosphoramidite and RNA strands containing k2C. 相似文献
126.
Nur Halilatul Sadiqin O. Ali Nurul Amirah ‘Aqilah Mohamad ‘Asri Putra Hajar Azirah Adol Aminul Huq Mirza 《Green Chemistry Letters and Reviews》2020,13(2):129-140
ABSTRACT Eight Schiff bases have been synthesized by conventional and three different eco-friendly methods, whereby two aromatic carbonyl compounds viz. 2-thiophenecarboxaldehyde and salicylaldehyde were reacted with S-methyl, S-benzyl, and S-n-octyl-dithiocarbazates and thiosemicarbazide. In order to evaluate the efficiency of the synthesis methods, the time to complete the reaction and the yield of the Schiff base synthezised by eco-friendly methods, such as solvent-free grinding, water as a solvent, and lemon juice as catalyst, were compared with those synthesized by the conventional method. The chemical structures of all the synthesized Schiff bases, where two of them are novel and reported for the first time, were fully characterized by a variety of physico-chemical, analytical, and spectroscopic techniques. The molecular and crystal structures of the Schiff bases especially those having 2-thiophene moiety were further elucidated by single crystal X-ray diffraction analyzes. 相似文献
127.
DENG Yi-Fang KUANG Dai-Zhi ZHANG Chun-Hua CHEN Man-Sheng PENG Yun-Lin YANG Ying-Qun LI Wei 《结构化学》2006,25(8)
The title complex [Zn(L)(phen)(CH3OH)] (L= C8H6BrO4NS, aminomethanesulfonic acid 5-bromo-salicylaldelyde schiff base; phen = 1,10-phenanthroline) has been synthesized and characterized by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 1.8712(3), b = 1.38008(19), c = 0.83685(12) nm, β = 97.791 (2)°, Mr = 569.72, V = 2.1411(5)nm3,Z= 4, Dc = 1.767 g/cm3, μ = 3.151 mm-1, F(000) = 1144, the final R = 0.0402 and wR = 0.0885. The central Zn(Ⅱ) is six-coordinated by one nitrogen and two oxygen atoms from the Schiff base, two nitrogen atoms from 1,10-phenanthroline and one oxygen from methanol to form a distorted octahedral coordination geometry. 相似文献
128.
129.
We study the skew information-based coherence of quantum states and derive explicit formulas for Werner states and isotropic states in a set of autotensors of mutually unbiased bases (MUBs). We also give surfaces of skew information-based coherence for Bell-diagonal states and a special class of X states in both computational basis and in MUBs. Moreover, we depict the surfaces of the skew information-based coherence for Bell-diagonal states under various types of local nondissipative quantum channels. The results show similar as well as different features compared with relative entropy of coherence and l1 norm of coherence. 相似文献
130.
CHEN Man-Sheng DENG Yi-Fang ZHANG Chun-Hua KUANG Dai-Zhi② FENG Yong-Lan PENG Yun-Lin 《结构化学》2007,26(2):219-223
A new manganese coordination polymer 1, [Mn(H2O)4(L)]n(ClO4)2n·2nH2O·3nL (L = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176(8), b = 15.4754(9), c = 15.9670(9) , β = 99.5010(10)o, V = 3391.8(3) 3, Z = 2, C56H68Cl2MnN16O14 , Mr = 1315.10, Dc = 1.288 g/cm3, μ = 0.344 mm-1, F(000) = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions. 相似文献