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121.
Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P3N3F6 and P3N3Cl6 The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X ? F ( 1 a ), Cl ( 1 b )), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P3N3X5] (X ? F ( 3 a ), Cl ( 3 b )); in an analogous manner the tetrameric ring P4N4Cl8 ( 2 b ) is converted to FcO[P4N4Cl7] ( 4 b ). 1 Abkürzungen: Fc = Ferrocenyl, (C5H5)Fe(C5H4?); fc = 1,1′-ferrocendiyl, Fe(C5H4?)2; rc = 1,1′-ruthenocendiyl, Ru(C5H4?)2. Fluorphosphazene werden mit a , Chlorphosphazene mit b gekennzeichnet. With 1,1′-ferrocenediol, (fc(OH) 2 ), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO 2 [P 3 N 3 X 4 ] (X ? F ( 5 a ), Cl ( 5 b )). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS 2 [P 3 N 3 X 5 ] (X ? F ( 6 a ), Cl ( 6 b )) and fcSe 2 [P 3 N 3 X 5 ] (X ? F ( 7 a ), Cl ( 7 b )) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their 1 H, 13 C and 31 P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses. 相似文献
122.
Paramasivan Halasyamani Kevin R. Heier Michael J. Willis Charlotte L. Stern Kenneth R. Poeppelmeier 《无机化学与普通化学杂志》1996,622(3):479-485
Crystals of CuNb(pyz)2OF5 · (pyz)(H2O) ( 1 ) and [Cu(pyz)2.5]+ [NbF6]? · (pyz) ( 2 ) were grown (150°C and autogeneous pressures) from CuO, 1/2(Nb2O5), (HF)x · pyridine, and H2O in excess pyrazine. Light blue single crystals of ( 1 ) are orthorhombic, crystallizing in space group Cccm (No. 66), with a = 14.547(1) Å, b = 16.135(2) Å, c = 13.803(2) Å, and Z = 8. The structure of ( 1 ) contains corner shared [Cu(pyz)4/2F2/2]+, [Cu(pyz)4/2O2/2], and [NbF4O1/2F1/2]?0.5 octahedra. Orange crystals of ( 2 ) are monoclinic, crystallizing in space group C2/c (No. 15), with a = 11.792(8) Å, b = 17.123(3) Å, c = 17.051(5) Å, β = 90.04(4)°, and Z = 8. The structure of ( 2 ) contains puckered rings of corner shared [Cu(pyz)(pyz)3/2]+ tetrahedra and isolated [NbF6]? anions within the rings. 相似文献
123.
Sakamoto S Ito A Kudo K Yoshikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3717-3726
The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide. 相似文献
124.
CAI Shu-Hui LI Jun LIU Chun-WanFujian Institute of Research on the Structure of Matter Chinese Academy of Sciences State Key Laboratory of Structural Chemistry Fuzhou Fujian China 《中国化学》1994,12(5):385-391
The band structures of several analogous superconducting A-15 type solid compounds, Nb3X (X=Si, Ge, Sn, Pb), have been calculated by use of the tight-binding method within the Extended Huckel approximation (EHT). By analysis of their energy bands, densities of states and crystal orbital overlap populations, the dependence of the superconducting transition temperatures (Tc) on the electronic structures and bondings is qualitatively elucidated. 相似文献
125.
Ivan Gutman 《Monatshefte für Chemie / Chemical Monthly》1989,120(12):1043-1047
Summary The recently proposed statistical method for the calculation of resonance energies in the conjugated circuit theory is tested on the example of polyacenes. It is found that for the estimation of the resonance energy with a 10% average error, the method requires a sample consisting of about 20 (randomly chosen) Kekulé structures. Further increase of the sample size gives no significant gain in the accuracy of the method.
Überprüfung der statistischen Methode in der Konjugierten-Ring-Theorie
Zusammenfassung Die unlängst vorgeschlagene statistische Methode in der Konjugierten-Ring-Theorie (conjugated circuit theory) wird am Beispiel der Polyacene getestet. Es wurde festgestellt, daß für die Abschätzung der Resonanzenergien bei einem mittleren Fehler von 10% für diese Methode ungefähr 20 (willkürlich gewählte) Kekulé-Strukturen nötig sind. Weitere Erhöhung dieser Anzahl bringt keine signifikante Verbesserung der Genauigkeit der Methode.相似文献
126.
Cyanide Bridged Coordination Polymers from cis‐ or trans‐[Ru(tBuNC)4(CN)2] and MnCl2: About the Influence of Different Topologies on the Magnetic Properties of Materials The reaction of cis‐ or trans‐[Ru(tBuNC)4(CN)2] with MnCl2 as an additional transition metal fragment yields the one dimensional coordination polymers {cis‐[Ru(CN)2(tBuNC)4] MnCl2}n, ( 1 ), and {trans‐[Ru(CN)2(tBuNC)4]MnCl2}n, ( 2 ), with a different arrangement of the metal centers caused by the different stereochemistry of the starting compounds. The variation of the Ru‐C‐N‐Mn geometry nevertheless leads to significant differences in the magnetic properties of 1 and 2 . The coordination polymer derived from trans‐[Ru(tBuNC)4(CN)2] shows a more efficient antiferromagnetic intrachain interaction between the manganese centers compared to the cis‐derivative. 相似文献
127.
Alan H. Cowley Andreas Decken Claudia A. Olazbal Nicholas C. Norman 《无机化学与普通化学杂志》1995,621(11):1844-1848
Further investigation of the reaction of Ar*GaCl2 (Ar* = 2,4,6-t-Bu3C6H2) with Na[Mn(CO)5] resulted in the new compound, [Ga(Ar*){Mn(CO)5}2] 2 . The new indium compounds, [In(Ar*){Co(CO)4}2] 3 and [In(Ar*){Mn(CO)5}2] 4 , have been prepared by the treatment of Ar*InBr2 with Na[Co(CO)4] and Na[Mn(CO)5], respectively. The structure of 3 was established by single-crystal X-ray diffraction: space group P1 (No. 2), Z = 2, a = 8.625(1) Å, b = 10.557(2) Å, c = 17.55(2) Å, α = 88.43(1)°, β = 83.45(1)°, γ = 71.14(1)°. The X-ray crystal structure of [Ga{Mn(CO)5}3] is also reported: space group Pbca (No. 61), Z = 8, a = 12.83(3) Å, b = 11.753(2) Å, c = 29.662(6) Å, α = β = γ = 90°. 相似文献
128.
运用三足四齿配体三(2-甲基吡啶)胺(TPA)或三(2-甲基苯丙咪唑)胺(TBA),得到两个双核铁(III)配合物,[Fe2L2(μ2-O)(μ2-p-NH2-C6H4COO)]3+
(L = TPA, 1 和 L = TBA,
2)。两个配合物均为单斜晶系,空间群为P2(1)/c.晶胞参数 1: a =
1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º,
V = 4.900(3) nm3, z = 4, F(000) = 2344, 分子量Mr = 1142.91, Dc
= 1.549 g/cm3, R1 = 0.0544,
R2 = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c =
2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm3,
z = 4, F (000) = 3116, 分子量Mr = 1505.08, Dc
= 1.444 g/cm3, R1 = 0.0793, R2 = 0.1623. 在两个双核铁(III)配合物中,中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。 相似文献
129.
Abdelkrim El‐Ghayoury Albertus P. H. J. Schenning E. W. Meijer 《Journal of polymer science. Part A, Polymer chemistry》2002,40(22):4020-4023
An oligo(p‐phenylene vinylene) that contains terpyridine ligands has been synthesized. Upon addition of metal ions, a π‐conjugated metallo polymer is formed in which the well‐defined character of oligomers and the material properties of polymers are combined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4020–4023, 2002 相似文献
130.
Acrylamide complexes of metal nitrates: [M(O‐OC(NH2)CHCH2)n(H2O)m][NO3]2 (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)6]2+ (AAm = O‐OC(NH2)CHCH2 and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)4(H2O)2]2+ in which the Zn2+ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures. 相似文献