全文获取类型
收费全文 | 8482篇 |
免费 | 396篇 |
国内免费 | 2篇 |
专业分类
化学 | 5499篇 |
晶体学 | 63篇 |
力学 | 317篇 |
综合类 | 23篇 |
数学 | 1238篇 |
物理学 | 1740篇 |
出版年
2023年 | 51篇 |
2022年 | 57篇 |
2021年 | 89篇 |
2020年 | 139篇 |
2019年 | 125篇 |
2018年 | 185篇 |
2017年 | 152篇 |
2016年 | 314篇 |
2015年 | 244篇 |
2014年 | 238篇 |
2013年 | 553篇 |
2012年 | 515篇 |
2011年 | 574篇 |
2010年 | 291篇 |
2009年 | 261篇 |
2008年 | 514篇 |
2007年 | 533篇 |
2006年 | 475篇 |
2005年 | 449篇 |
2004年 | 330篇 |
2003年 | 333篇 |
2002年 | 343篇 |
2001年 | 176篇 |
2000年 | 206篇 |
1999年 | 191篇 |
1998年 | 135篇 |
1997年 | 87篇 |
1996年 | 121篇 |
1995年 | 104篇 |
1994年 | 72篇 |
1993年 | 64篇 |
1992年 | 80篇 |
1991年 | 58篇 |
1990年 | 51篇 |
1989年 | 63篇 |
1988年 | 39篇 |
1987年 | 24篇 |
1985年 | 52篇 |
1984年 | 39篇 |
1983年 | 20篇 |
1982年 | 51篇 |
1981年 | 40篇 |
1980年 | 47篇 |
1979年 | 41篇 |
1978年 | 39篇 |
1977年 | 31篇 |
1976年 | 47篇 |
1975年 | 37篇 |
1974年 | 32篇 |
1973年 | 27篇 |
排序方式: 共有8880条查询结果,搜索用时 15 毫秒
71.
Pulps obtained from ethanol/water cooking of sugarcane bagasse were treated at different times using xylanase enzyme obtained
from Thermomyces lanuginosus IOC-4145 or commercially (Cartazyme HS, Sandoz Products Ltd.). The enzyme dosage was 18 IU per g of dry pulp and the time
varied from 4 h to 12 h. When xylanase from T. lanuginosus was used, the kappa number and viscosity improved independently of the processing time used (4 h, 8 h, and 12 h). After chemical
evaluation, the obtained pulps were classified using Fourier Transformed Infra-Red Spectroscopy and Principal Component Analysis.
The results showed that the first three principal components explained more than 90 % of the total variance of the pulp spectra. 相似文献
72.
Moraes ML Bonardi C Mendonça CR Campana PT Lottersberger J Tonarelli G Oliveira ON Beltramini LM 《Colloids and surfaces. B, Biointerfaces》2005,41(1):15-20
The study of interactions between biological molecules and model membranes is essential for the understanding of a number of physiological mechanisms involved in viral infections and dissemination. In this paper, the analysis of the interaction between a peptide from the p24 protein of Human Immunodeficiency Virus type 1 (HIV-1) and a phospholipid monolayer has pointed to a cooperative response in which very small amounts of peptide p24-1 (e.g. 0.05 mol%) can lead to measurable effects. Monolayer surface pressure and surface potential isotherms were affected for peptide concentrations as low as 0.05 mol%, with saturation at 0.5 mol%. The expansion effect from p24-1 is confirmed by changes in morphology of the monolayers using Brewster angle microscopy. Even though p24-1 is disordered in aqueous solutions, the interaction with dipalmitoyl phosphatidylcholine (DPPC) causes it to adopt an alpha-helix structure, as shown by circular dichroism (CD) data for multilamellar vesicles (MLV). The expansion of the phospholipid monolayer in a cooperative way may imply that p24-1 has potential antiviral activity, by participating in the cell rupture, with no need of specific receptors in the membrane. 相似文献
73.
Rogalewicz F Bourcier S Hoppilliard Y 《Rapid communications in mass spectrometry : RCM》2005,19(6):743-751
As part of a research program on neurotransmitters in a biological fluid, the fragmentations characterising catecholamines protonated under electrospray ionisation (ESI) conditions, under low collision energy in a triple-quadrupole mass spectrometer, were investigated. The decompositions of protonated noradrenaline (VH) and normetanephrine (VIH) were studied. Both precursor ions eliminate first H2O at very low collision energy, and the fragmentations of [MH-H2O]+ occur at higher collision energy. The breakdown graphs of [MH-H2O]+ ions, with collision energy varying from 0-40 eV in the laboratory frame, are presented. [VIH-H2O]+ ions lose competitively NH3 and CH3OH. For [VH-H2O]+ the loss of NH3 is dominant while H2O is eliminated at very low abundance at all collision energies. All of these secondary fragmentations are followed at higher collision energies by elimination of CO. These fragmentations are interpreted by means of ab initio calculations up to the B3LYP/6-311+G(2d,2p) level of theory. The elimination of H2O requires first the isomerisation of N-protonated forms, chosen as energy references, to O-protonated forms. The isomerisation barriers are calculated to be lower than 81 kJ/mol above the N-protonated forms. The elimination of NH3 from [MH-H2O]+ requires first the migration, via a cyclisation, of the amine function from the linear chain to the aromatic ring in order to prevent the formation of unstable disubstituted carbocations in the ring. The barriers associated with the loss of NH3 are located 220 and 233 kJ/mol above VH and 219 kJ/mol above VIH. The energy barrier for the loss of ROH is located 236 and 228 kJ/mol above VH and VIH, respectively. The absence of ions corresponding to [VH-2H2O]+ is due to a parasitic mechanism with an activation barrier lower than 236 kJ/mol that leads to a stable species unable to fragment, thus preventing the second loss of H2O. Losses of CO following the secondary fragmentations involve activation barriers higher than 330 kJ/mol. 相似文献
74.
Cui X Delgado R Carapuça HM Drew MG Félix V 《Dalton transactions (Cambridge, England : 2003)》2005,(20):3297-3306
A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl(-), PF(6)(-), HSO(4)(-), H(2)PO(4)(-) and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). (1)H NMR titrations in CD(3)OD indicated that this receptor is not suitable for recognizing HSO(4)(-) and H(2)PO(4)(-), but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3)(CH(3))(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the (1)H NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF(6)(-), ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS(2) stoichiometry are formed with the first three anions, but RS(4) with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H...O=C hydrogen bonds for carboxylate anions and N-H...F hydrogen bonds for the PF(6)(-) anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe...Fe intramolecular distances ranging from 10.125(14) to 12.783(15)A. 相似文献
75.
亚临床肝性脑病患者的血清锌,铜含量的测定及临床意义 总被引:1,自引:0,他引:1
检测了30例慢性活动性肝炎患者、30例肝硬化患者、30例亚临床肝性脑病患者血清中的铜、锌含量,并与正常对照组进行比较分析,探讨了微量元素铜、锌的血清含量改变及其影响因素,分析其临床意义。结果表明体内的铜锌含量与肝脏功能有密切的关系。在慢性活动性肝炎时,虽然肝脏功能有一定的损害,但由于肝脏的代偿能力强,铜,锌含量仍可保持在正常水平,而在肝硬化、亚临床肝性脑病时,铜锌明显降低,而铜锌含量的降低又导致机 相似文献
77.
Ş. Erkoç 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,19(4):423-425
The structural stability and energetics of carbon, silicon, and germanium microclusters containing 3?7 atoms have been investigated by using a recently developed empirical many-body potential energy function (PEF), which comprises two- and three-body atomic interactions. The PEF satisfies both bulk cohesive energy per atom and bulk stability exactly. It has been found that the most stable C3?4 microclusters are linear withD ∞h symmetry but C5?7 microclusters are planar withD nh symmetry. Silicon and germanium microclusters show similar structural stability. TheX n (X=Si, Ge;n=3?7) microclusters are found to be most stable in the following forms:X 3 is triangular withD 3h symmetry,X 4 is tetragonal withT d symmetry,X 5 is square pyramidal withD 4h symmetry,X 6 is bipyramidal square withO h symmetry, and finallyX 7 is square pyramidal having two atoms underneath withD 2h symmetry. 相似文献
78.
Upon hexanal-modification in the presence of NaCNBH(3), the oxidized B chain of insulin becomes mono- and further dialkylated on both the N-terminal and Lys(29) residues. A pseudo-MS(3) study was performed with a triple-quadrupole mass spectrometer on the different modified lysine-containing species to gain further insights into the characteristic fragmentation pattern. These fragmentations, in good agreement with true MS(3) measurements obtained using an ion trap mass spectrometer, highlighted characteristic monoalkylated lysine (immonium-NH(3)) and protonated modified caprolactam ions at m/z 168 and 213, respectively. In contrast, no fragment ion derived from a modified lysine residue (immonium or caprolactam) was observed when dialkylation occurs on Lys(29). However, a fragment ion corresponding to a protonated dihexylamine was observed at m/z 186. This loss, characteristic of dialkylated lysine fragmentation, was also observed upon dialkylation of N(alpha)-acetyllysine with either hexanal or pentanal. On the other hand, acetylation and malondialdehyde-modification of the N(alpha)-acetyllysine side chain led mainly to the corresponding modified (immonium-NH(3)) fragment ions at m/z 126 and 138, respectively. Finally, it was demonstrated that precursor ion scanning for both m/z 168 and 213 ions led to specific and sensitive identification of peptides containing hexanal-modified lysine residues within an unfractionated tryptic digest of hexanal-modified apomyoglobin. Thus, Lys(42), Lys(45), Lys(62), Lys(63), Lys(77), Lys(87), Lys(96), Lys(98), Lys(145) and Lys(147) were found to be modified upon reaction with hexanal. 相似文献
79.
The action of ultra violet rays of 260 nm on aqueous solutions of bases, nucleosides and nucleotides of DNA at 77°K is studied by electron spin resonance. It is shown that the free radicals observed are similar, with a few noteworthy exceptions to those induced by X-rays, under the same conditions of temperature, in the solid state. Contrary to what might be excepted on the basis of the results obtained by X-rays, the variation in the yield in paramagnetic centres in each sequence studied does not seem to be important. 相似文献
80.
测定了75例厌食小儿、101例呼吸道感染小儿和120例健康儿童发锌、铜,结果表明:厌食儿及易感儿平均发锌值分别为80.90×10-6和75.76×10-6,均极显著低于健康儿(P<0.01);发铜则无显著差异。发锌值在70×10-6以下者有60%以上身高、体重低于正常标准。说明微量元素锌与小儿食欲、免疫功能和生长发育有密切关系。 相似文献