全文获取类型
收费全文 | 55877篇 |
免费 | 9187篇 |
国内免费 | 5860篇 |
专业分类
化学 | 39442篇 |
晶体学 | 659篇 |
力学 | 3212篇 |
综合类 | 333篇 |
数学 | 6279篇 |
物理学 | 20999篇 |
出版年
2024年 | 187篇 |
2023年 | 1168篇 |
2022年 | 2142篇 |
2021年 | 2234篇 |
2020年 | 2354篇 |
2019年 | 2224篇 |
2018年 | 1902篇 |
2017年 | 1846篇 |
2016年 | 2710篇 |
2015年 | 2734篇 |
2014年 | 3226篇 |
2013年 | 4152篇 |
2012年 | 5082篇 |
2011年 | 5033篇 |
2010年 | 3471篇 |
2009年 | 3288篇 |
2008年 | 3526篇 |
2007年 | 3143篇 |
2006年 | 2827篇 |
2005年 | 2433篇 |
2004年 | 1863篇 |
2003年 | 1487篇 |
2002年 | 1375篇 |
2001年 | 1111篇 |
2000年 | 972篇 |
1999年 | 1116篇 |
1998年 | 898篇 |
1997年 | 856篇 |
1996年 | 847篇 |
1995年 | 767篇 |
1994年 | 636篇 |
1993年 | 553篇 |
1992年 | 465篇 |
1991年 | 417篇 |
1990年 | 356篇 |
1989年 | 253篇 |
1988年 | 190篇 |
1987年 | 174篇 |
1986年 | 169篇 |
1985年 | 152篇 |
1984年 | 96篇 |
1983年 | 100篇 |
1982年 | 65篇 |
1981年 | 44篇 |
1980年 | 35篇 |
1979年 | 25篇 |
1976年 | 25篇 |
1975年 | 24篇 |
1973年 | 21篇 |
1972年 | 21篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
971.
Microdialysis sampling coupled with liquid chromatography-electrochemical detection (LC-ED) was developed and applied to determine the interaction of thiopurine (TP) with bovine serum albumin (BSA). A nickel hexacyanoferrate (NiHCNFe) modified electrode was fabricated and used as the working electrode in LC-ED for the determination of TP. Cyclic voltammetric experiments demonstrate that this chemically modified electrode (CME) can effectively catalyze the electrooxidation of TP. The mechanism of the catalytic oxidation of TP at the CME involves an 'EC' process. In the LC-ED, the CME also shows good stability and reproducibility for the determination of TP. The limit of detection is 5.0 x 10(-7) mol l(-1) for 6-TP with a signal-to-noise ratio of 3. The utility of microdialysis as a quantitative sampling technique for in vitro studies of drug-protein interactions was studied. The microdialysis experiments were performed in phosphate buffer solution (pH 7.4) containing different molar ratios of the drug and protein at 37 degrees C. The collected microdialysis sample with unbound TP was analyzed at the NiHCNFe CME in the LC-ED. The relative recovery of TP determined in vitro is 18.3% at a perfusion rate of 1.0 microl min(-1) and the RSD is about 2.1%. The association constant and the number of binding sites on a BSA molecule calculated with the Scatchard equation are 3.72 x 10(-3) (1 mol(-1)) and 1.51, respectively. This method provides a fast, sensitive and simple technique for the study of drug-protein interactions. 相似文献
972.
混合三烃基锡衍生物的研究:X.甲基二环己基锡二硫代磷酸酯的合成及生… 总被引:4,自引:2,他引:4
合成了10种甲基二环己基锡-O,O-二烃基二硫代磷酸酯,利用IR,NMR,MS及元素分析确证了化合物的结构,生物活性测试结果表明,这类化合物具有较高的杀螨和除草活性。 相似文献
973.
The synthesis, dual fluorescence, and fluoroionophoric behavior of two donor-sigma spacer-acceptor (D-s-A) compounds, trans-4-(N,N-bis(2-pyridyl)amino)methylstilbene (1H) and trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-cyanostilbene (1CN), are reported and compared to that of trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-(N,N-dimethylamino)stilbene (1DPA). To gain insights into the dual fluorescence properties for 1H and 1CN in polar but not in nonpolar solvents, model compounds resulting from a replacement of the stilbene group by alkyl (2R) or xylyl (2X) groups or from a replacement of the dipyridylamino (dpa) group by dianisoleamino (3AA), diethylamino (3EE), methylanilino (3MP), or diphenylamino (3PP) groups also have been investigated. In addition to 1H and 1CN, all four compounds of 3 display dual fluorescence. The locally excited (LE) fluorescence mainly results from the stilbene group and the ICT fluorescence from the through-bond interactions between the amino donor and the stilbene acceptors. In the presence of transition metal ions such as Zn(II), Ni(II), Cu(II), and Cd(II), the ICT processes are switched from dpa (D) --> stilbene (A) in 1H and 1CN to stilbene (D) --> dpa/metal ion (A) in their complexes. Whereas the ICT states for the complexes are generally nonfluorescent, an exception was found for the case of 1H/Zn(II). As a result, substituent-dependent fluoroionophoric behavior has been demonstrated by 1H, 1CN, and 1DPA in response to Zn(II). 相似文献
974.
An intumescent flame retardant coating was prepared with resin, solvent and flame retardant system composed of ammonium polyphosphate-APP, pentaerythritol-PER and melamine-MEL. The modifiers such as molybdenum disilicide (MoSi2) and expandable graphite (EG) were used to improve the performances of the APP-PER-MEL coating. The effects of EG, MoSi2 and MoSi2/EG on the fireproofing time and char formation of the coating were investigated by using heat insulation test, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electric microscope (SEM). The results showed that by adding modifiers, the fireproofing time was prolonged and char formation rate was evidently enhanced. The largest improvement was achieved with 9 wt.% MoSi2/5 wt.% EG, XPS analysis indicated that the performance of anti-oxidation of the coating was improved by adding EG and MoSi2, and SEM images showed that a good synergistic effect was obtained through a ceramic-like layer produced by MoSi2 covered on the surface of “open-cellular” structural char. 相似文献
975.
Stable C60-fused tetrahydropyridazine derivatives were synthesized through the hetero-Diels-Alder cycloaddition of C60 with 1,2-diaza-1,3-butadienes, which were generated in situ by the thermal extrusion of sulfur dioxide from 2,5-dihydro-1,2,3-thiadiazole-1,1-dioxides. 相似文献
976.
Yu-min?SongEmail author Xiao-lin?Lu Mei-ling?Yang Xiu-rong?Zheng 《Transition Metal Chemistry》2005,30(4):499-502
Fluorescence, absorption spectra have been produced by the interaction of platinum(IV), silver(I) and gold(III) ions with the berberine–DNA system (berberine, Scheme 1). Platinum(IV) and gold(III) ions show different effects from that of silver(I) ion on the spectral characteristics of the berberine–DNA system. Quenching fluorescence is seen with platinum(IV) and gold(III) ions addition, whereas increasing fluorescence is observed for silver(I) ions. The addition of gold(III) and silver(I) ions cause an increase in absorption of the berberine–DNA system. The above results suggest that different metal ions exhibit different affinities when binding to DNA correlates well with the ions’ charge, structure and the coordination ability. 相似文献
977.
Jiang‐Tao Chen Hai‐Zhou Li Dong Wang Ying‐Jun Zhang Chong‐Ren Yang 《Helvetica chimica acta》2006,89(7):1442-1448
Three new dammarane monodesmosides, named notoginsenosides Ft1 ( 1 ), Ft2 ( 2 ), and Ft3 ( 3 ), together with three known ginsenosides, were obtained from a mild acidic hydrolysis of the saponins from notoginseng (Panax notoginseng (Burk .) F. H. Chen ) leaves. Their structures were elucidated to be (3β,12β,20R)‐12,20‐dihydroxydammar‐24‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 1 ), (3β,12β)‐12,20,25‐trihydroxydammaran‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 2 ), and (3β,12β,24ξ)‐12,20,24‐trihydroxydammar‐25‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 3 ), by means of spectroscopic evidences. The known ginsenosides Rh2 and Rg3 4 – 6 were obtained as the major products from this acidic deglycosylation. 相似文献
978.
Qunying Jiang Min Pan Jialing Hu Junlin Sun Lei Fan Zhiqiao Zou Jianshuang Wei Xiaoquan Yang Xiaoqing Liu 《Chemical science》2021,12(1):148
Many cancer treatments including photodynamic therapy (PDT) utilize reactive oxygen species (ROS) to kill tumor cells. However, elevated antioxidant defense systems in cancer cells result in resistance to the therapy involving ROS. Here we describe a highly effective phototherapy through regulation of redox homeostasis with a biocompatible and versatile nanotherapeutic to inhibit tumor growth and metastasis. We systematically explore and exploit methylene blue adsorbed polydopamine nanoparticles as a targeted and precise nanocarrier, oxidative stress amplifier, photodynamic/photothermal agent, and multimodal probe for fluorescence, photothermal and photoacoustic imaging to enhance anti-tumor efficacy. Remarkably, following the glutathione-stimulated photosensitizer release to generate exogenous ROS, polydopamine eliminates the endogenous ROS scavenging system through depleting the primary antioxidant, thus amplifying the phototherapy and effectively suppressing tumor growth in vitro and in vivo. Furthermore, this approach enables a robust inhibition against breast cancer metastasis, as oxidative stress is a vital impediment to distant metastasis in tumor cells. Innovative, safe and effective nanotherapeutics via regulation of redox balance may provide a clinically relevant approach for cancer treatment.Amplified oxidative stress achieved by modulating redox homeostasis with PDA–MB for highly effective synergistic phototherapy to inhibit primary tumors and metastases. 相似文献
979.
Multiple time step (MTS) algorithms present an effective integration approach to reduce the computational cost of dynamics simulations. By using force splitting to allow larger time steps for the more slowly varying force components, computational savings can be realized. The Particle-Mesh-Ewald (PME) method has been independently devised to provide an effective and efficient treatment of the long-range electrostatics interactions. Here we examine the performance of a combined MTS/PME algorithm previously developed for AMBER on a large polymerase beta/DNA complex containing 40,673 atoms. Our goal is to carefully combine the robust features of the Langevin/MTS (LN) methodology implemented in CHARMM-which uses position rather than velocity Verlet with stochasticity to make possible outer time steps of 150 fs-with the PME formulation. The developed MTS/PME integrator removes fast terms from the reciprocal-space Ewald component by using switch functions. We analyze the advantages and limitations of the resulting scheme by comparing performance to the single time step leapfrog Verlet integrator currently used in AMBER by evaluating different time-step protocols using three assessors for accuracy, speedup, and stability, all applied to long (i.e., nanosecond) simulations to ensure proper energy conservation. We also examine the performance of the algorithm on a parallel, distributed shared-memory computer (SGI Origin 2000 with 8 300-MHz R12000 processors). Good energy conservation and stability behavior can be demonstrated, for Newtonian protocols with outer time steps of up to 8 fs and Langevin protocols with outer time steps of up to 16 fs. Still, we emphasize the inherent limitations imposed by the incorporation of MTS methods into the PME formulation that may not be widely appreciated. Namely, the limiting factor on the largest outer time-step size, and hence speedup, is an intramolecular cancellation error inherent to PME. This error stems from the excluded-nonbonded correction term contained in the reciprocal-space component. This cancellation error varies in time and introduces artificial frequencies to the governing dynamics motion. Unfortunately, we find that this numerical PME error cannot be easily eliminated by refining the PME parameters (grid resolution and/or order of interpolating polynomial). We suggest that methods other than PME for fast electrostatics may allow users to reap the full advantages from MTS algorithms. 相似文献
980.
AbstractAn investigation on seeds of Brucea javanica led to the acquisition of a new quassinoid, 20-hydroxyyadanzigan (1), along with five known quassinoids (2–6). The structure of the new compound was elucidated on the basis of extensive spectral analysis. All of the compounds were assayed for their anticomplement activities through classical and alternative pathways. Compounds 1–6 exhibited potent anticomplement activity with CH50 and AP50 values of 0.032–0.075?mg/mL and 0.061–0.118?mg/mL, respectively. Moreover, the structure-activity relationships of these compounds are discussed. 相似文献