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21.
The effect of propranolol (PPL), phenoxybenzamine (PBZ) or bicuculline (BCL) on the diazepam (DZP)-induced changes of pineal melatonin synthesis in male rats was examined in vivo and in vitro. Administration of PBZ did not affect the inhibitory action of DZP on pineal melatonin synthesis in vivo. A single injection of PPL inhibited the pineal melatonin synthesis similarly to the administration of DZP alone, but the two drugs together did not exhibit additive or synergistic effects on the melatonin synthesis. Significant decreases in the N-acetyltransferase (NAT) activity and the N-acetylserotonin (NAS) and melatonin contents were observed in the BCL-injected group, being greater than those in the DZP-treated group. Unexpectedly, however, the combination treatment of DZP and BCL causes an increase in the NAT activity and melatonin content compared with the BCL-alone group. Incubation with DZP at higher concentrations resulted in an increase of pineal NAT activity in vitro, but this increase was inhibited by preincubation with PPL, PBZ or BCL. DZP treatment thus appeared to have different effects on pineal NAT activity in vivo and in vitro. These results suggest that both a GABAergic mechanism and peripheral benzodiazepine (BZP) receptors in rat pineal gland may be involved in the modulation of melatonin synthesis by DZP. 相似文献
22.
Murakami M Usui I Hasegawa M Matsuda T 《Journal of the American Chemical Society》2005,127(5):1366-1367
Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state. 相似文献
23.
Enantio-uracil dinucleotide 5, which consists of two l-uridylic acids and one pyrophosphate, was synthesized for the first time in our laboratory. Benzolyated l-uridine was prepared by a stereoselective glycosylation of silylated uracil with l-1-O-acetyl-2,3,5-tri-O-benzoylribose (l-ABR 7). After deprotection, l-uridine 9 was converted to P1,P4-di(l-uridine 5′-) tetraphosphate tetrasodium salt (l-UP4U 5) by treatment of l-UMP morpholidate 10c with triethylammonium pyrophosphate (TEA-PPi 11b). Spectral data of synthesized l-UP4U 5 are given in the references. All spectral data were identical with those of UP4U 3 except the specific rotation, which showed a positive value compared to UP4U 3 having a negative value. Furthermore, the separation by chiral column chromatography was investigated. 相似文献
24.
25.
The reaction of C6Cl5Ni(PPhMe2)2Cl with CHRCR′CH2MgX (X = Br or Cl) yields π-allylnickel compounds, (π-CHRCR′CH2)Ni(PPhMe2)C6Cl5 (Ia, R = R′ = H; Ib, R = H, R′ = CH3; Ic, R = CH3, R′ = H), which are stable in the solid state below ca. 150°C and are fairly stable in solution in the absence of oxygen. The π-allyl group was found by PMR spectroscopy to be rigid even in the presence of an excess of PPhMe2, P(OEt)3 or P(OMe)3. 相似文献
26.
27.
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
28.
Oxime-based salen-type tetradentate ligands with high stability against imine metathesis reaction 总被引:2,自引:0,他引:2
Akine S Taniguchi T Dong W Masubuchi S Nabeshima T 《The Journal of organic chemistry》2005,70(5):1704-1711
Although salen and its analogues are versatile chelate ligands in inorganic and organometallic chemistry, synthesis of unsymmetrical salen derivatives consisting of two different salicylideneimine moieties is difficult because of the C=N bond recombination. To develop stable analogues of salen-type ligands, we synthesized a series of new ligands salamo (=1,2-bis(salicylideneaminooxy)ethane) on the basis of O-alkyl oxime instead of the imine moiety. Eight salamo ligands 1a-h were prepared in 64-88% yields as colorless crystals from the corresponding salicylaldehydes 2a-h. The crystal structure of 1a-c suggests that the oxime-OH form is more predominant than the keto-NH form. The reaction of 2a-e with excess 1,2-bis(aminooxy)ethane gave monooximes 3a-e in 59-86%, which further reacted with a different salicylaldehyde to afford unsymmetrical salamo ligands 4-8 as stable crystals in 51-70%. No reaction took place when a mixture of salamo derivatives 1a and 1b was treated at 40 degrees C in H2O/MeCN (5:95). However, the metathesis reaction of salen derivatives 9a and 9b completed in 2 h to give a statistical mixture. Monooxime 3b was much more stable than monoimine 11 which is difficult to be isolated. These results indicate the extremely high stability of the salamo derivatives 1 and precursors 3. 相似文献
29.
Prof. Dr. Takanori Matsuda Kotaro Kato Tsuyoshi Goya Shingo Shimada Prof. Dr. Masahiro Murakami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1941-1943
A ruthenium complex catalyzes a new cycloisomerization reaction of 2,2′‐diethynylbiphenyls to form 9‐ethynylphenanthrenes, thereby cleaving the carbon–carbon triple bond of the original ethynyl group. A metal–vinylidene complex is generated from one of the two ethynyl groups, and its carbon–carbon double bond undergoes a [2+2] cycloaddition with the other ethynyl group to form a cyclobutene. The phenanthrene skeleton is constructed by the subsequent electrocyclic ring opening of the cyclobutene moiety. 相似文献
30.
Hiroto Noda Dr. Ken Motokura Prof. Dr. Yusuke Wakabayashi Kaori Sasaki Dr. Hiroo Tajiri Dr. Akimitsu Miyaji Dr. Sho Yamaguchi Prof. Dr. Toshihide Baba 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(15):5113-5117
The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO2 surface is discussed based on the interaction between the functionalized SiO2 surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state 13C and 11B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity. 相似文献