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181.
S. Aime Mauro Botta S. Geninatti Crich Giovanni B. Giovenzana Roberto Pagliarin Maurizio Piccinini Massimo Sisti Enzo Terreno 《Journal of biological inorganic chemistry》1997,2(4):470-479
A novel heptacoordinating ligand consisting of a thirteen-membered tetraazamacrocycle containing the pyridine ring and bearing
three methylenephosphonate groups (PCTP-[13]) has been synthesized. Its Gd(III) complex displays a remarkably high longitudinal
water proton relaxivity (7.7 mM–1 s–1 at 25 °C, 20 MHz and pH 7.5) which has been accounted for in terms of contributions arising from (1) one water molecule
bound to the metal ion, (2) hydrogen-bonded water molecules in the second coordination sphere, or (3) water molecules diffusing
near the paramagnetic chelate. Variable-temperature 17O-NMR transverse relaxation data indicate that the residence lifetime of the metal-bound water molecule is very short (8.0 ns
at 25 °C) with respect to the Gd(III) complexes currently considered as contrast agents for magnetic resonance imaging. Furthermore,
GdPCTP-[13] interacts with human serum albumin (HSA), likely through electrostatic forces. By comparing water proton relaxivity
data for the GdPCTP-[13]-HSA adduct, measured as a function of temperature and magnetic field strength, with those for the
analogous adduct with GdDOTP (a twelve-membered tetraaza macrocyclic tetramethylenephosphonate complex lacking a metal-bound
water molecule), it has been possible to propose a general picture accounting for the main determinants of the relaxation
enhancement observed when a paramagnetic Gd(III) complex is bound to HSA. Basically, the relaxation enhancement in these systems
arises from (1) water molecules in the hydration shell of the macromolecule and protein exchangeable protons which lie close
to the interaction site of the paramagnetic complex and (2) the metal bound water molecule(s). As far as the latter contribution
is concerned, the interaction with the protein causes an elongation of the residence lifetime of the metal-bound water molecule,
which limits, to some extent, the potential relaxivity enhancement expected upon the binding of the paramagnetic complex to
HSA.
Received: 27 January 1997 / Accepted: 12 May 1997 相似文献
182.
Susanne Metzger Andrea Erxleben B. Lippert 《Journal of biological inorganic chemistry》1997,2(2):256-264
The analogy between H-bonded nucleobase pairs and their metalated analogues is extended to the hemiprotonated pair of 7,9-dimethylguanine
(7,9-DimeG) and the Watson-Crick and reversed Watson-Crick pair between 7,9-dimethylguaninium (7,9-DimeGH+) and 1-methylcytosine (1-MeC). The crystal structure analyses of two model compounds, trans–[Pt(CH3NH2)2(7,9-DimeG-N1)2](NO3)2 (1) and trans–[Pt(NH3)2(1-MeC-N3)(7, 9-DimeG-N1)](PF6)2· 2.5 H2O (3a) are reported. Pt binding is through N1 of 7,9-DimeG and N3 of 1-MeC. In solution, 3a exists in a mixture with Watson-Crick and reversed Watson-Crick arrangements of the two bases, depending on solvent, concentration
and anions.
Received: 16 October 1996 / Accepted: 27 January 1997 相似文献
183.
Summary The oxidation of cysteine (RSH) has been studied by using O2, ferricytochrome c (Cyt c) and nitro blue tetrazolium (NBT) as electron acceptors. The addition of 200M CuII to a solution of 2mM cysteine, pH 7.4, produces an absorbance with a peak at 260 nm and a shoulder at 300 nm. Generation of a cuprous bis-cysteine complex (RS-CuI-SR) is responsible for this absorbance. In the absence of O2 the absorbance is stable for long time while in the presence of air it vanishes slowly only when the cysteine excess is consumed. The neocuproine assay and the EPR analysis show that the metal remains reduced in the course of the oxidation of cysteine returning to the oxidised form at the end of reaction when all RSH has been oxidised to RSSR. Addition of CuII enhances the reduction rate of Cyt c and of NBT by cysteine also under anaerobiosis indicating the occurrence of a direct reduction of the acceptor by the complex. It is concluded that the cuprous bis-cysteine complex (RS-CuI-SR) is the catalytic species involved in the oxidation of cysteine. The novel finding of the stability of the complex together with the metal remaining in the reduced form during the oxidation suggest sulfur as the electron donor in the place of the metal ion.Abbreviations RSH
cysteine
- RS–
cysteine in the thiolate form
- RS·
thiyl radical of cysteine
- RSSR
cystine
- Cyt c
cytochrome c
- SOD
superoxide dismutase
- NBT
nitro blue tetrazolium
- NBF
nitro blue formazan
- DTNB
5,5-dithiobis-2-nitrobenzoic acid
- DTPA
diethylenetriaminepentaacetic acid
Dedicated to prof. A. Ballio ob the occasion of his 75th birthday. 相似文献
184.
Avram Hershko 《Current opinion in cell biology》1997,9(6):788-799
Selective degradation of cyclins, inhibitors of cyclin-dependent kinases and anaphase inhibitors is responsible for several major cell cycle transitions. The degradation of these cell cycle regulators is controlled by the action of ubiquitin—protein-ligase complexes, which target the regulators for degradation by the 26S proteasome. Recent results indicate that two types of multisubunit ubiquitin ligase complexes, which are connected to the protein kinase regulatory network of the cell cycle in different ways, are responsible for the specific and programmed degradation of many cell cycle regulators. 相似文献
185.
Massimo Di Giulio 《Journal of molecular evolution》1997,45(6):571-578
A highly complex RNA world, as is sometimes presented in view of the widespread and diversified use of RNA enzymes, would
have encountered many difficulties in passing to a world with catalysis mediated by proteins. These difficulties can be overcome
by postulating a very early relationship between the nucleotide and the amino acid components. In particular, after asserting
that some characteristics expressed by (nucleotide) coenzymes in catalysis are easier to understand if a close and early relationship
between these coenzymes and amino acids is hypothesized, a model is presented for the origin of the enzyme–coenzyme complex.
This model is essentially based on an intermediate formed by a tRNA-like molecule covalently linked to a polypeptide. The
model attributes the majority of the catalytic role in the ribonucleoprotein world to the latter complex and thus it takes
into account the birth of the key intermediate in the origin of protein synthesis—namely, peptidyl-tRNA, which would have
otherwise been extremely difficult to select. The predictions of the model are discussed along with its robustness, using
the data derived from the study of intermediary metabolism and those from molecular biology. Finally, the appearance of the
genetic code in the late phase of the ribonucleopeptide world is discussed.
Received: 13 January 1997 / Accepted: 25 July 1997 相似文献
186.
Synaptic Vesicle Recycling in Cultured Cerebellar Granule Cells: Role of Vesicular Acidification and Refilling 总被引:5,自引:2,他引:3
Abstract: The role of the transvesicular protonmotive force in synaptic vesicle recycling was investigated in cultured cerebellar granule cells. The vesicular V-ATPase was inhibited by 1 µ M bafilomycin A1; as an alternative, the pH component of the gradient was selectively collapsed by equilibration of the cells with 10 m M methylamine and monitored with the fluorescent probe Lysosensor Green. Electrical field-evoked exocytosis of d -[3 H]aspartate was inhibited by bafilomycin A1 but not by methylamine, indicating that a transvesicular membrane potential rather than pH gradient is required for transmitter retention within vesicles. In contrast, neither compound affected the field-evoked uptake, recycling, or destaining of the vesicle-specific dye FM2-10; thus, vesicles whose lumens were neutral and/or depleted of transmitter could still recycle in the nerve terminal. No exhaustion of d -[3 H]aspartate exocytosis was observed when cells were subjected to six consecutive trains of field stimuli (40 Hz/10 s separated by 10 s). In contrast, the release of preloaded FM2-10 was reduced by ∼50%, with each stimulus indicating that unlabeled vesicles with accumulated d -[3 H]aspartate were competing with labeled vesicles for exocytosis. As d -[3 H]aspartate was accumulated rapidly across the vesicle membrane from the large cytoplasmic pool, the transmitter-loaded but unlabelled vesicles may represent refilled recycling vesicles. FM2-10 destaining and d -[3 H]aspartate exocytosis were reduced in parallel at low frequencies, challenging a role for transient vesicle fusion. 相似文献
187.
188.
189.
The organization of the mucomicrovillar complex of the vomeronasal sensory epithelium of adult rats was examined using confocal laser scanning microscopy. In specimens labeled with the FITC-conjugated isolectin B4 of Bandeiraea simplicifolia, which recognizes terminal -galactose sugar residues of glycoconjugates, we demonstrated that the mucomicrovillar complex was composed of islet-like structures with a high-density -galactose core. The mucomicrovillar complex was further resolved into sensory and mucoid components in double-labeling and dual scanning experiments. The sensory component, which consists of the dendritic terminals of olfactory marker protein-immunoreactive vomeronasal receptor neurons, contained cytosolic glycoconjugates with terminal -galactose sugar residues. The extracellular mucoid component consisted of glycoconjugates containing terminal -galactose derived from the glands associated with the vomeronasal organ. These results demonstrated the complex microchemical organization of the sensory and mucoid components of the mucomicrovillar complex. 相似文献
190.
Functional organization of the macroglomerular complex related to behaviourally expressed olfactory redundancy in male cabbage looper moths 总被引:2,自引:0,他引:2
Abstract. The neurophysiological bases for behaviourally expressed olfactory redundancy in the sex pheromone communication system of the cabbage looper moth, Trichoplusia ni (Hübner) (Lepidoptera: Noctuidae), were examined by coupling the cut-sensillum extracellular recording technique with a highly specific neuronal marking method for moth peripheral receptors. In seventy-two antennal sensilla, axonal pathways of cobalt-stained neurones could be traced into the male-specific macroglomerular complex in the antennal lobe. In T. ni males this comprises five glomeruli, two of which are subdivided into morphologically, and in some instances functionally identifiable, regions. Axonal arborizations of forty-eight neurones (single stainings) showed high fidelity (98%) for containment within a specific glomerulus or glomerular subdivision, and the neuropil targeted seemed to be related to the specificity of a neurone to a particular female-emitted sex pheromone component (27-12:Ac, Z7-14:Ac, Z9-14:Ac, 12:Ac, 11–12:Ac, Z5-12:Ac), or to a behavioural antagonist (Z7-12:OH). Double (twenty-one) and multiple stainings (three) showed axons projecting into two or more glomeruli, respectively, with 100% fidelity for the component-specific glomerulus or glomerular subdivision to be targeted. We suggest that the potential for a single minor component to cross-stimulate two or more neurones within a sensillum may enable partial blends to continue to provide sensory input into all of the pheromone-processing glomeruli of the complex. Our interpretation is that redundancy occurs at the receptor level on neighbouring dendrites, and thus allows various four-component partial blends to evoke full pheromone-mediated behaviour. 相似文献