全文获取类型
收费全文 | 8104篇 |
免费 | 1321篇 |
国内免费 | 959篇 |
专业分类
化学 | 5763篇 |
晶体学 | 120篇 |
力学 | 449篇 |
综合类 | 53篇 |
数学 | 1152篇 |
物理学 | 2847篇 |
出版年
2024年 | 25篇 |
2023年 | 176篇 |
2022年 | 323篇 |
2021年 | 293篇 |
2020年 | 302篇 |
2019年 | 300篇 |
2018年 | 258篇 |
2017年 | 266篇 |
2016年 | 424篇 |
2015年 | 415篇 |
2014年 | 547篇 |
2013年 | 595篇 |
2012年 | 764篇 |
2011年 | 774篇 |
2010年 | 501篇 |
2009年 | 452篇 |
2008年 | 513篇 |
2007年 | 401篇 |
2006年 | 406篇 |
2005年 | 371篇 |
2004年 | 324篇 |
2003年 | 243篇 |
2002年 | 226篇 |
2001年 | 187篇 |
2000年 | 128篇 |
1999年 | 186篇 |
1998年 | 125篇 |
1997年 | 96篇 |
1996年 | 111篇 |
1995年 | 112篇 |
1994年 | 93篇 |
1993年 | 57篇 |
1992年 | 57篇 |
1991年 | 58篇 |
1990年 | 68篇 |
1989年 | 45篇 |
1988年 | 29篇 |
1987年 | 22篇 |
1986年 | 29篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 14篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1979年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1928年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Yajing Yin Ping Wu Yafen Lü Pan Du Yanmao Shi Chenxin Cai 《Journal of Solid State Electrochemistry》2007,11(3):390-397
A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques.
The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and
infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results
demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H2O2. This modified electrode might be used in development of new biosensors and the biofuel cells. 相似文献
92.
93.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
94.
Venkateshrao S Yin J Jarzecki AA Schultz PG Spiro TG 《Journal of the American Chemical Society》2004,126(50):16361-16367
Resonance Raman (RR) spectra are reported for mesoporphyrin IX bound to the Fab fragment of the ferrochelatase antibody 7G12. Binding induces activation of a Raman band at 680 cm(-1), which is assigned to an out-of-plane porphyrin vibration, gamma15. This is exactly the predicted effect of distorting mesoporphyrin to the geometry of N-methylmesoporphyrin IX, the 7G12 hapten, based on DFT/CIS modeling of the RR spectrum. The modeling also shows that the pyrrole ring that is tilted out of the porphyrin plane bears a nitrogen lone pair, which is therefore available for coordination by an incoming metal ion. The 680 cm(-1) band intensity is approximately 3 times higher for the affinity-matured antibody than for the germline precursor antibody, while intermediate values are found for variants in which germline residues are mutated to mature residues or vice versa. Thus, RR spectroscopy reveals an evolution from weak substrate distortion in the germline antibody to strong substrate distortion in the affinity-matured antibody, and supports the view that catalysis involves a substrate strain mechanism. 相似文献
95.
Synthesis of lipid A derivatives and their interactions with polymyxin B and polymyxin B nonapeptide 总被引:5,自引:0,他引:5
Yin N Marshall RL Matheson S Savage PB 《Journal of the American Chemical Society》2003,125(9):2426-2435
Lipid A is the causative agent of Gram-negative sepsis, a leading cause of mortality among hospitalized patients. Compounds that bind lipid A can limit its detrimental effects. Polymyxin B, a cationic peptide antibiotic, is one of the simplest molecules capable of selectively binding lipid A and may serve as a model for further development of lipid A binding agents. However, association of polymyxin B with lipid A is not fully understood, primarily due to the low solubility of lipid A in water and inhomogeneity of lipid A preparations. To better understand lipid A-polymyxin B interaction, pure lipid A derivatives were prepared with incrementally varied lipid chain lengths. These compounds proved to be more soluble in water than lipid A, with higher aggregation concentrations. Isothermal titration calorimetric studies of these lipid A derivatives with polymyxin B and polymyxin B nonapeptide indicate that binding stoichiometries (peptide to lipid A derivative) are less than 1 and that affinities of these binding partners correlate with the aggregation states of the lipid A derivatives. These studies also suggest that cooperative ionic interactions dominate association of polymyxin B and polymyxin B nonapeptide with lipid A. 相似文献
96.
Hai Bing LI Yuan Yin CHEN* Shu Ling GONG Department of Chemistry Wuhan University Wuhan 《中国化学快报》2002,13(3)
Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a… 相似文献
97.
98.
Wei QH Zhang LY Yin GQ Shi LX Chen ZN 《Journal of the American Chemical Society》2004,126(32):9940-9941
Unusual AuI-AgI heterometallic complexes [Au5Ag8(mu-dppm)4{1,2,3-C6(C6H4R-4)3}(CCC6H4R-4)7]3+ (R = H 1, CH3 2, But 3) were isolated by reactions of polymeric silver arylacetylides (AgCCC6H4R-4)n with binuclear gold component [Au2(mu-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane), in which cyclotrimerization of arylacetylide -CCC6H4R-4 affords trianion {1,2,3-C6(C6H4R-4)3}3- with an unprecedented mu5-bonding mode. Compounds 1(SbF6)3-3(SbF6)3 exhibit intense photoluminescence derived from an MLCT (Au5Ag8 --> CCC6H4R-4) transition, mixed with a metal cluster-centered excited states. 相似文献
99.
Xue-qiang Yin 《Tetrahedron》2004,60(15):3451-3455
Prior to this work only two examples of carbanucleosides possessing a C-1′/C-6′ double bond had been reported and they were minor derivatized side products arising during other targeted syntheses. To develop this structural feature into a new class of potential antiviral agents, the 5′-nor derivative of aristeromycin with such an olefinic structure (6) represents the first example. In this regard, treatment of (1′S,2′S,3′S,4′R,5′S)-6-chloro-9-(2′,3′-isopropylidenedioxy-6′-oxabicyclo[3.1.0]hex-4′-yl)purine (7) with sodium methoxide yielded 6 via an E′2-like elimination pathway. A convenient way to the C-4′ epimer of 6 (that is, 17) also arose during these studies and is described. Antiviral analysis of 6 and 17 failed to produce any significant activity. 相似文献
100.
Yin J Aviles P Lee W Ly C Guillen MJ Munt S Cuevas C Faircloth G 《Rapid communications in mass spectrometry : RCM》2005,19(5):689-695
A rapid and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay was developed and validated to quantify a novel antineoplastic agent, PM00104, in mouse, rat, dog, and human plasma. The method was validated to demonstrate the specificity, limit of quantification (LOQ), accuracy, and precision of measurements. The calibration range for PM00104 was established using PM00104 standards from 0.01-5.0 ng/mL in blank plasma. The selected reaction monitoring (SRM), based on the m/z 692.2 --> 218.2 transition, was specific for PM00104, and that based on the m/z 697.2 --> 218.2 transition was specific for PM00104 ((13)C(2),(2)H(3)) (the internal standard, IS); no endogenous materials interfered with the analysis of PM00104 and IS from blank plasma. The assay was linear over the concentration range 0.01-5.0 ng/mL. The correlation coefficients for the calibration curves ranged from 0.9981-0.9999. The mean intra-day and inter-day accuracies for all calibration standards (n = 8) ranged from 97-105% (< or =5% bias) in human plasma, and the mean inter-day precision for all calibration standards was less than 8.5%. The mean intra- and inter-day assay accuracy for all quality control (QC) replicates in human plasma (n = 9), determined at each QC level throughout the validated runs, ranged from 96-112% (< or =12% bias) and from 102-105% (< or =5% bias), respectively. The mean intra- and inter-day assay precision was less than 15.0 and 11.8% for all QC levels, respectively. For the QC samples prepared in animal species plasma, the %CV values of the assays ranged from 1.8-8.8% in mouse plasma, from 3.7-13.8% in rat plasma, and from 3.0-7.2% in dog plasma. The assay accuracies ranged from 92-102% (< or =8% bias) for all QC levels prepared in mouse plasma; ranged from 93-106% (< or =7% bias) in rat plasma; and ranged from 95-114% (< or =14% bias) in dog plasma. The assay has been used to support preclinical pharmacokinetic and toxicokinetic studies and is currently used to measure PM00104 plasma concentrations to support clinical trials. 相似文献