全文获取类型
收费全文 | 13213篇 |
免费 | 979篇 |
国内免费 | 8篇 |
出版年
2023年 | 57篇 |
2022年 | 133篇 |
2021年 | 272篇 |
2020年 | 177篇 |
2019年 | 187篇 |
2018年 | 245篇 |
2017年 | 224篇 |
2016年 | 413篇 |
2015年 | 618篇 |
2014年 | 682篇 |
2013年 | 869篇 |
2012年 | 1080篇 |
2011年 | 1092篇 |
2010年 | 698篇 |
2009年 | 607篇 |
2008年 | 794篇 |
2007年 | 839篇 |
2006年 | 806篇 |
2005年 | 669篇 |
2004年 | 663篇 |
2003年 | 548篇 |
2002年 | 553篇 |
2001年 | 133篇 |
2000年 | 94篇 |
1999年 | 119篇 |
1998年 | 162篇 |
1997年 | 82篇 |
1996年 | 91篇 |
1995年 | 101篇 |
1994年 | 90篇 |
1993年 | 87篇 |
1992年 | 71篇 |
1991年 | 69篇 |
1990年 | 62篇 |
1989年 | 57篇 |
1988年 | 46篇 |
1987年 | 59篇 |
1986年 | 43篇 |
1985年 | 60篇 |
1984年 | 47篇 |
1983年 | 51篇 |
1982年 | 43篇 |
1981年 | 46篇 |
1980年 | 30篇 |
1979年 | 29篇 |
1978年 | 24篇 |
1977年 | 36篇 |
1976年 | 21篇 |
1975年 | 18篇 |
1974年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
B. Eva Villaroya Luis A. Oro Fernando J. Lahoz Andrew J. Edwards Miguel A. Ciriano Pablo J. Alonso Antonio Tiripicchio Marisa Titipicchio Camellini 《Inorganica chimica acta》1996,250(1-2):241-264
The multiple coordination possibilities of 1,8-naphthyridine-2-one (HOnapy) and 5,7-dimethyl-1,8-napthyridine-2-one (HOMe2napy) ligands allow the synthesis of a variety of tri- di- and mononuclear complexes, showing fluxional behaviour and frequent exchange of the coordinated ML2 fragments. Thus, reactions of [M2(μ-OMe)2(cod)2] (cod = 1,5-cyclooctadiene) with HOnapy and HOMe2napy yield the compounds of the general formula [M(μ-OR2napy) (cod)]n (M = Ir, R = Me (1a, 1b, H (2); M = Rh, R = Me (3a, 3b). They crystallise as inconvertible yellow (a) and purple/orange (b) forms and also show a puzzling behaviour in solution. X-ray diffraction studies on both forms (3a, 3b) and spectroscopic data reveal that the yellow forms are mononuclear complexes whilst the dark-coloured crystals contain dinuclear complexes. In solution, the nuclearity of the complexes depends on the solvent. In addition both types of complexes are fluxional. The mixed-ligand complexes [M2(μ-OMe2napy)2(CO)2(cod)] M = Ir (5), Rh (6) have been isolated and characterised; they are found to be intermediates in the synthesis of the trinuclear complexes [M3(μ3-OMe2napy)2(CO)2(cod)2]+ M = Rh (8), Ir (9). Reactions of [IrCl(CO)2(NH2-p-tolyl] with the complexes [Rh(μ-OR2napy)(diolefin)]n followed by addition of a poor donor anion is a general one-pot synthesis for the hetertrinuclear complexes [Rh2Ir(μ3-OR2napy)2(CO)2(diolefin)2]+ (R=Me, DIOLEFIN = cod (10), tetrafluorobenzo-barrelene (tfbb) (11), 2,5-norbornadiene (nbd) (12); R=H, DIOLEFIN=cod (13)). This synthesis follows a stepwise mechanism from the mononuclear to the trinuclear complexes in which mixed-ligand heterodinuclear complexes are involved as intermediates of the type [(diolefin)Rh(μ-OMe2napy)2Ir(CO)2]. Heteronuclear complexes which possess the core [RhIr2]3+, such as [RhIr2(μ3-OR2napy)2(CO)2(cod)2]BF4 (R=Me (14), H (15)), result from the reaction of 1 or 2 with [Rh(CO)2Sx]+ (S = solvent). The trinuclear complexes undergo two chemically reversible one-electron oxidation processes. The chemical oxidation of 10, 14 and 9 with silver salts gives the mixed-valence trinuclear radicals [Rh2Ir(μ3-OMe2napy)2(CO)2(cod)2]2+ (16), [RhIr2(μ3-OMe2napy)2(CO)2(cod)2]2+ (17) and [Ir3(μ3-OMe2napy)2(CO)2(cod)2]2+ (18), which have been isolated as the perchlorate and tetrafluoroborate salts. The EPR spectrum of 16 indicates that the unpaired electron is essentially in an orbital delocalised on the metals. The molecular structures of the complexes 3a, 3b, 6, 10b and 16a are described. Crystals of 3a are triclinic, P-1, with a = 9.7393(2), b = 14.0148(4), c = 16.0607(4) Å, α = 88.122(3), β = 83.924(3), γ = 87.038(3)°, Z = 4; 3b crystallises in the Pna2i orthorhhombic space group, with a = 16.7541(3), B = 11.7500(8), c = 17.7508(7) Å, Z = 4; complex 6 is packed in the monoclinic space group P2i/c, a = 9.6371(1), b = 11.8054(4), c = 27.2010(9) Å, β = 90.556(4)°, Z = 4; crystals of 10b are monoclinic, P21/n, with a = 17.546(7), b = 13.232(6), c = 17.437(8) Å, β = 106.18(1)°, Z = 4; crystals of 16a are triclinic, P-1, with a = 10.318(4), b = 12.562(6), C = 19.308(8) Å, α = 92.12(8), β = 97.65(9), γ = 90.68(5)°, Z = 2. The five different structures show the coordination versatility of the OMe2napy molecule as ligand, which behaves as a N,N′-chelating (3a), bidentate N,O-donor (3b, 6), or as a tridentate N,N′,O-donor bridging ligand (10b, 16a). 相似文献
102.
The dynamics of individual endogenous cytokinins within the growth cycle (subculture interval) of an auxin-dependent and cytokinin-independent cell suspension culture ofNicotiana tabacum L. (strain VBI-0) were determined using high performance liquid chromatography and radioimmunoassay. In cells grown at an optimum auxin concentration the transient maxima of N6-(2-isopentenyl)adenine and N6-(2-isopentenyl)-adenosine correlated with the onset of cell division. Cultivation of the cells in a partially auxin-deprived medium resulted in ca. tenfold increase of all endogenous cytokinins. A very distinct maximum of N6-(2-sopentenyl) adenine appeared at the beginning of subculture. This indicates that a lack of auxin induced an accumulation of cytokinins predominantly in the form of the free bases, which are physiologically more active than the corresponding ribosides.Abbreviations iP
N6-(2-isopentenyl)adenine
- [9R]iP
N6-(2-isopentenyl)adenosine
-
t-Z
trans-zeatin
-
t-[9R]Z
trans-zeatin riboside
- IAA
indole-3-acetic acid
- NAA
1-naphthaleneacetic acid
- 2,4-D
2,4-dichlorophenoxyacetic acid
- f.w.
fresh weight
- SBI
subculture interval
- C
complete medium
- PAD
partially auxin-deprived medium
- RP-HPLC
reverse phase high performance liquid chromatography
- RIA
radioimmunoassay
- PAL
L-phenylalanine ammonia lyase 相似文献
103.
Hoch Brigitte Lutsch Gudrun Schlegel Wolfgang-Peter Stahl Joachim Wallukat Gerd Bartel Sabine Krause Ernst-Georg Benndorf Rainer Karczewski Peter 《Molecular and cellular biochemistry》1996,160(1):231-239
Recent investigations concentrate on the correlation between the myocardial expression of the inducible 70-kDa heat shock protein (HSP70i) by different stress conditions and its possible protective effects. Only few studies have focused on the involvement of small heat shock proteins in this process. We analyzed the location of the small heat shock protein HSP25 in isolated cardiomyocytes as well as its location and induction in isolated perfused hearts of rats. By immunofluorescence microscopy HSP25 was found to colocalize with actin in the I-band of myofibrils in cardiomyocytes of isolated perfused hearts as well as in isolated neonatal and adult cardiomyocytes. Hyperthermic perfusion of isolated hearts for 45 min resulted in modulation of different parameters of heart function and in induction of HSP25 and HSP70i. Temperatures higher than 43°C (44–46°C) were lethal with respect to the contractile function of the hearts. Compared to control hearts perfused at 37°C, significant increases during hyperthermic perfusion at 42°C and 43°C were obtained for heart rate, contraction velocity and relaxation velocity. In response to hyperthermia at 43°C and after subsequent normothermic perfusion for 135 min at 37°C, left ventricular pressure, contraction velocity and relaxation velocity remained significantly elevated. However, heart rate returned to control values immediately after the period of heat treatment. HSP25 is constitutively expressed even in normothermic perfused hearts as shown by Western blotting. Hyperthermia increased the content of HSP25 only in the left ventricular tissue. In contrast, HSP70i was strongly induced in all analyzed parts of the myocardium (left ventricle, right ventricle, septum). Our findings suggest a differential regulation of HSP25 and HSP70i expression in response to hyperthermia in isolated perfused hearts. The constitutively expressed HSP25 seems to be located adjacent to the myofibrils which implies a specific role of this protein even under unstressed conditions for the contractile function of the myocardium. 相似文献
104.
Kaumann Alberto J. Sanders Louise Lynham James A. Bartel Sabine Kuschel Meike Karczewski Peter Krause Ernst-Georg 《Molecular and cellular biochemistry》1996,163(1):113-123
Evidence from ventricular preparations of cat, sheep, rat and dog suggests that both 1-adrenoceptors (1AR) and 2-adrenoceptors (2AR) mediate positive inotropic effects but that only 1AR do it through activation of a cAMP pathway. On the other hand, our evidence has shown that both 1 AR and 2 AR hasten relaxation of isolated human myocardium consistent with a common cAMP pathway. We have now investigated in the isolated human right atrial appendage, a tissue whose -AR comprise around 2/3 of 1AR and 1/3 of 2AR, whether or not 2AR-mediated effects occur via activation of a cAMP pathway. We carried out experiments on atria obtained from patients without advanced heart failure undergoing open heart surgery. To activate 2AR, we used the 2AR-selective ligand zinterol. Experiments were carried out on paced atrial strips (1 Hz) and tissue homogenates and membrane particles. Zinterol caused positive inotropic and lusitropic (i.e. reduction of t1:2 of relaxation) effects with EC50 values of 3 and 2 nM, respectively. The zinterol-evoked effects were unaffected by the AR-selective antagonist CGP 20712A (300 nM) but blocked surmountably by the 2AR-selective antagonist ICI 118551 (50 nM) which reduced both EC50 values to 1 M. Zinterol stimulated adenylyl cyclase activity with an EC50 of 30 nM and intrinsic activity of 0.75 with respect to (–)-isoprenaline (600 M); the effects were resistant to blockade by CGP 20712A (300 nM) but antagonised surmountably by ICI 118551 (50 nM). Zinterol bound to membrane PAR labelled with (–)-[125I] cyanopindolol with higher affinity for 2AR than for - 1 AR; the binding to 2AR but not to - BAR was reduced by GTPyS (10 M). In the presence of CGP 20712A (300 nM) (–)-isoprenaline (400 M); (to activate both 1AR and 2AR maximally) and zinterol (10 M); increased contractile force 3.4-fold and 2.5-fold respectively and reduced relaxation tut by 32% and 18% respectively. These effects of (–)-isoprenaline and zinterol were associated (5 min incubation) with phosphorylation (pmol P/mg supernatant protein) of troponin I and C-protein to values of 8.4 ± 2.0 vs 12.4 ± 2.3 and 10.1 ± 2.5 vs 8.6 ± 1.6 respectively. (–)-Isoprenaline and zinterol also caused phosphorylation of phospholamban (1.8 ± 0.3 vs 0.4 ± 0.1 pmol P/mg respectively) specifically at serine residues. We conclude that in human atrial myocardium activation of both 1AR and 2AR leads to cAMP-dependent phosphorylation of proteins involved in augmenting both contractility and relaxation. 相似文献
105.
106.
Sabine Kölle Fred Sinowatz Gudrun Boie Ines Totzauer Werner Amselgruber Johnna Plendl 《The Histochemical journal》1996,28(6):441-447
Summary The mRNA of the zona pellucida glycoprotein ZP3 was localized in frozen sections of pig ovaries, isolated oocytes and early embryos byin situ hybridization using biotinylated oligonucleotide probes. In follicles, the distribution of mRNA for ZP3 was correlated with the developmental stage: in primordial and primary follicles, the mRNA was shown to be predominantly localized in the oocyte. In secondary follicles, mRNA was found in both the oocyte and follicle cells. In tertiary and preovulatory follicles, the follicle cells showed distinct staining, whereas the oocyte was labelled weakly. In the early embryo, i.e. 2 days after fertilization, mRNA for ZP3 could not be demonstrated. Our results suggest that, in the pig, the zona pellucida protein ZP3 is synthesized by the oocyte and the follicle cells in sequence. After fertilization, synthesis of ZP3 is terminated. 相似文献
107.
108.
109.
The Lys residues in the 75-residue Ca2+-binding protein calbindin D9k were reductively methylated with13C-enriched formaldehyde. The possible structural effects resulting from the chemical modification were critically investigated by comparing two-dimensional NMR spectra and the exchange rates of some of the amide protons of the native and the modified protein. Our results show that the protein retains its structure even though 10 Lys out of a total of 75 amino acid residues were modified. In the Ca2+- and apo-forms of the protein, the13C-methylated Lys residues can be detected with high sensitivity and resolution using two-dimensional (1H,13C)-heteronuclear multiple quantum coherence (HMQC) NMR spectroscopy. ThepKa values of the individual Lys residues in Ca2+-calbindin D9k and apo-calbindin D9k were obtained by combiningpH titration experiments and (1H,13C)-HMQC NMR spectroscopy. Each Lys residue in the Ca2+- and apo-forms of calbindin D9k has a uniquepKa value. The LyspKa values in the calcium protein range from 9.3 to 10.9, while those in the apo-protein vary between 9.7 and 10.7. Although apo-calbindin D9k has a very similar structure compared to Ca2+-calbindin D9k, the removal of two Ca2+ ions from the protein leads to an increase of thepKa values of the Lys residues. 相似文献
110.
Gudrun Borchert Sabine Bartel Inge Beyerdörfer Irmgard Küttner Laszlo Szekeres Ernst-Georg Krause 《Molecular and cellular biochemistry》1994,132(1):57-67
Evidence is accumulating that 7-oxo-prostacyclin (7-oxo-PGI2) induces a delayed indirect anti-adrenergic and cytoprotective effect on the myocardium, the mechanism of which is still unclear. To demonstrate that a single application of 7-oxo-PGI2 (50 g/kg i.m.) 48 h prior to starting experiments attenuates the isoprenaline inducible inotropic response and accumulation of cAMP, isolated hearts of pretreated animals were perfused in the Langendorff mode with and without isoprenaline (1 to 100 nM). The late anti-adrenergic effect of the drug was manifested by a significant attenuation in the elevation of cAMP levels as well as in contractile force development. This effect was not due to changes in cAMP generation as there were identical 1-adrenoceptor densities and affinities (as calculated from [3H]-CGP binding studies), Gi and Gs protein patterns (as taken from Western blots) as well as adenylyl cyclase activity measurements in the hearts studied. The anti-adrenergic potency of 7-oxo-PGI2, however, was found to be related to a significant rise in cyclic nucleotide hydrolysis by phosphodiesterase (PDE). Using the fast-performance liquid chromatographic separation for PDE isoforms, a significant increase in the activity of PDE isoforms I and IV (260±28 vs 110±12 pmol cGMP/min x enzyme fraction and 77±11 vs 34±3 pmol cAMP/min x enzyme fraction, respectively) was found in the solubilized fraction of cardiac membranes in comparison to untreated controls; PDE IV activity was also increased in the cytosolic fraction (106±14 vs 65±6 pmol cAMP/min x enzyme fraction). The hypothesis that the delayed anti-adrenergic effect of 7-oxo-PGI2 is initiated by an induction and accelerated synthesis of PDE I and IV in the heart is underlined by the fact that cycloheximide suppresses completely both the rise in PDE activities and the anti-adrenergic effects studied. It is suggested that an inducible predominance of cAMP degradation over its generation may be of relevance in processes related to heart protection. 相似文献