全文获取类型
收费全文 | 1495篇 |
免费 | 62篇 |
国内免费 | 4篇 |
专业分类
化学 | 1173篇 |
晶体学 | 20篇 |
力学 | 44篇 |
数学 | 75篇 |
物理学 | 249篇 |
出版年
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 15篇 |
2020年 | 24篇 |
2019年 | 22篇 |
2018年 | 13篇 |
2017年 | 8篇 |
2016年 | 38篇 |
2015年 | 34篇 |
2014年 | 44篇 |
2013年 | 82篇 |
2012年 | 75篇 |
2011年 | 93篇 |
2010年 | 63篇 |
2009年 | 41篇 |
2008年 | 95篇 |
2007年 | 107篇 |
2006年 | 89篇 |
2005年 | 110篇 |
2004年 | 81篇 |
2003年 | 75篇 |
2002年 | 67篇 |
2001年 | 23篇 |
2000年 | 39篇 |
1999年 | 23篇 |
1998年 | 9篇 |
1997年 | 17篇 |
1996年 | 8篇 |
1995年 | 10篇 |
1994年 | 22篇 |
1993年 | 14篇 |
1992年 | 17篇 |
1991年 | 13篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 11篇 |
1985年 | 22篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 8篇 |
排序方式: 共有1561条查询结果,搜索用时 343 毫秒
81.
Adachi K Sugiyama Y Yoneda K Yamada K Nozaki K Fuyuhiro A Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6616-6628
Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique. 相似文献
82.
Mitsuru Ueda Yoshikatu Seino Yuko Haneda Masanobu Yoneda Jun-Ichi Sugiyama 《Journal of polymer science. Part A, Polymer chemistry》1994,32(4):675-681
tert-Butyl substituted poly (aryl ether ketone)s with relatively high molecular weights were prepared by the Ni-catalyzed polymerization of tert-butyl substituted aromatic dichlorides containing ether ketone unit. These polymers were amorphous and soluble in common organic solvents, such as THF, dichloromethane, and chloroform. De-tert-butylation of the polymer by the treatment of trifluoromethanesulfonic acid in the presence of toluene proceeded smoothly and produced crystalline poly (aryl ether ketone). © 1994 John Wiley & Sons, Inc. 相似文献
83.
Sugiyama T Schweinberger E Kazimierczuk Z Ramzaeva N Rosemeyer H Seela F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):369-378
2-Aza-2'-deoxyadenosine (2, z2Ad) is synthesized via its 1,N6-etheno derivative 7 and enzymatically deaminated to 2-aza-2'-deoxyinosine (3). Compound 2 is converted into the phosphoramidite building block 10b. This is employed in solid-phase oligonucleotide synthesis. The 2-azapurine base forms a strong base pair with guanine, but a much weaker one with adenine, thymine, and cytosine. Oligonucleotide duplexes with dangling nucleotide residues, such as 2-aza-2'-deoxyadenosine and 7-deaza-2'-deoxyadenosine (4, c7Ad), either on one or both termini, are synthesized, and the thermal stability of the duplexes is correlated with the hydrophobic properties of the dangling nucleotide residues. 相似文献
84.
Ishida Y Madonna AJ Rees JC Meetani MA Voorhees KJ 《Rapid communications in mass spectrometry : RCM》2002,16(19):1877-1882
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS), utilizing an on-probe sample pretreatment, was applied to the rapid and direct detection of intact phospholipids from whole bacterial cells. The sample preparation procedure involved depositing growing bacterial colonies from culture dishes directly onto the MALDI probe followed by treatment of the sample spot with a 3 micro L aliquot of an aqueous 0.05 M solution of sodium iodide prior to the addition of a 2,5-dihydroxybenzoic acid (DHB) matrix solution (ca. 8 mg dissolved in 70% acetonitrile/30% H(2)O containing 0.1% of trifluoroacetic acid). The MALDI spectra obtained from whole bacteria cells showed a series of ions generated from bacterial phospholipids, such as phosphatidylethanol-amines (PEs) and phosphatidylglycerols (PGs), which were clearly observed as well-resolved peaks. The ranges of the observed total carbon numbers in two acyl groups for PEs and PGs (30-36 and 33-36, respectively) were in good agreement with those reported previously. Furthermore, the distinct discrimination of four species of the Enterobacteriaceae family cultured identically was achieved by using principal components analysis (PCA) conducted on the relative peak intensities of phospholipids observed from the MALDI spectra. 相似文献
85.
Mukai C Inagaki F Yoshida T Yoshitani K Hara Y Kitagaki S 《The Journal of organic chemistry》2005,70(18):7159-7171
[reaction: see text] Rhodium(I)-catalyzed PKR of allenynes was found to be applicable for constructing azabicyclo[5.3.0]decadienone as well as oxabicyclo[5.3.0]decadienone frameworks. In addition, a reliable procedure for constructing a 10-monosubstituted bicyclo[5.3.0]deca-1,7-dien-9-one ring system by the rhodium(I)-catalyzed PKR of allenynes was developed under the condition of 10 atm of CO. Investigation of the rhodium(I)-catalyzed cycloisomerization of 4-phenylsulfonylnona-2,3-dien-8-ynes under nitrogen atmosphere gave the corresponding cyclohexene derivatives, whereas the C1-homologated allenynes produced cycloheptene derivatives and/or bicyclo[5.2.0]nonene skeletons depending on the substitution pattern at the allenic terminus. Thus, proper choice of the starting allenynes and reaction conditions led to the selective formation of 2-phenylsulfonylbicyclo[5.3.0]deca-1,7-dien-9-ones (Pauson-Khand-type product), 3-alkylidene-1-phenylsulfonyl-2-vinylcycloheptene derivatives, and bicyclo[5.2.0]nonene frameworks. 相似文献
86.
Hamamoto H Anilkumar G Tohma H Kita Y 《Chemical communications (Cambridge, England)》2002,(5):450-451
A novel and efficient oxidative biaryl coupling reaction of phenol ether derivatives using a combination of hypervalent iodine(III) reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA), and heteropoly acid has been developed. 相似文献
87.
Tsutomu Shiragami Katsunori Tanaka Yoshito Andou Shin-ichiro Tsunami Jin Matsumoto Hongxia Luo Yasuyuki Araki Osamu Ito Haruo Inoue Masahide Yasuda 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):287-297
Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis{3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N′-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13–0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 108–109 s−1, independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis. 相似文献
88.
Sandanayaka AS Watanabe N Ikeshita K Araki Y Kihara N Furusho Y Ito O Takata T 《The journal of physical chemistry. B》2005,109(7):2516-2525
Three rotaxanes, with axles with two zinc porphyrins (ZnPs) at both ends penetrating into a necklace pending a C60 moiety, were synthesized with varying interlocked structures and axle lengths. The intra-rotaxane photoinduced electron transfer processes between the spatially positioned C60 and ZnP in rotaxanes were investigated. Charge-separated (CS) states (ZnP*+, C60*-)rotaxane are formed via the excited singlet state of ZnP (1ZnP*) to the C60 moiety in solvents such as benzonitrile, THF, and toluene. The rate constants and quantum yields of charge separation via 1ZnP decrease with axle length, but they are insensitive to solvent polarity. When the axle becomes long, charge separation takes place via the excited triplet state of ZnP (3ZnP*). The lifetime of the CS state increases with axle length from 180 to 650 ns at room temperature. The small activation energies of charge recombination were evaluated by temperature dependence of electron-transfer rate constants, probably reflecting through-space electron transfer in the rotaxane structures. 相似文献
89.
Shoichi Katsuta Hirokazu Wakabayashi Mariko Tamaru Yoshihiro Kudo Yasuyuki Takeda 《Journal of solution chemistry》2007,36(4):531-547
Equilibria concerning picrates of tetraalkylammonium ions (Me4N+, Et4N+, Pr4N+, Bu4N+, Bu3MeN+) in a dichloromethane−water system have been investigated at 25 ∘C. The 1:1 ion-pair formation constants (K
IP,o
o) in dichloromethane at infinite dilution were conductometrically determined. The distribution constants (K
D
o) of the ion pairs and the free cations between the solvents were determined by a batch-extraction method. The K
IP,o
o value varies in the cation sequence, Bu4N+ ≈ Pr4N+ ≈ Et4N+ < Bu3MeN+ < < Me4N+; this trend is explained by the electrostatic cation−anion interaction taking into account the structures of the ion pairs
determined by density functional theory calculations. For the ion pairs of the symmetric R4N+ cations, there is a linear positive relationship between log10
K
D
o and the number of methylene groups in the cation (N
CH
2). The ion pair of asymmetric Bu3MeN+ has a higher distribution constant than that expected from the above log10
K
D
o
versus
N
CH
2 relationship. These cation dependencies of log10
K
D
o for the ion pairs are explained theoretically by using the Hildebrand-Scatchard equation. For all the cations, the log10
K
D
o value of the free cation increases linearly with N
CH
2; the variation of log10
K
D
o is discussed by decomposing the distribution constant into the Born-type electrostatic contribution and the non-Born one,
and attributed to the latter that is governed by the differences in the molar volumes of the cations. The cation dependencies
of the ion-pair extractability and ion pairing in water are also discussed.
An erratum to this article can be found at 相似文献
90.