全文获取类型
收费全文 | 14071篇 |
免费 | 1888篇 |
国内免费 | 1536篇 |
专业分类
化学 | 7583篇 |
晶体学 | 119篇 |
力学 | 683篇 |
综合类 | 67篇 |
数学 | 1290篇 |
物理学 | 3753篇 |
无线电 | 4000篇 |
出版年
2024年 | 87篇 |
2023年 | 394篇 |
2022年 | 494篇 |
2021年 | 573篇 |
2020年 | 544篇 |
2019年 | 546篇 |
2018年 | 469篇 |
2017年 | 479篇 |
2016年 | 596篇 |
2015年 | 654篇 |
2014年 | 770篇 |
2013年 | 1010篇 |
2012年 | 1098篇 |
2011年 | 1160篇 |
2010年 | 862篇 |
2009年 | 833篇 |
2008年 | 944篇 |
2007年 | 776篇 |
2006年 | 721篇 |
2005年 | 547篇 |
2004年 | 454篇 |
2003年 | 379篇 |
2002年 | 393篇 |
2001年 | 282篇 |
2000年 | 296篇 |
1999年 | 344篇 |
1998年 | 271篇 |
1997年 | 205篇 |
1996年 | 219篇 |
1995年 | 190篇 |
1994年 | 139篇 |
1993年 | 142篇 |
1992年 | 125篇 |
1991年 | 102篇 |
1990年 | 87篇 |
1989年 | 67篇 |
1988年 | 48篇 |
1987年 | 37篇 |
1986年 | 26篇 |
1985年 | 39篇 |
1984年 | 25篇 |
1983年 | 17篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1978年 | 5篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1973年 | 3篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
181.
[reaction: see text] The reactions of aryl aldehydes with styrene derivatives, mediated by various boron Lewis acids, were investigated. 1,3-Dihalo-1,3-diarylpropanes were obtained in high yields with boron trihalides, while 3-chloro-1,3-diarylpropanols were obtained in good to excellent yields with phenylboron dichloride. Reactions involving nonenolizable aliphatic aldehydes, trans-cinnamaldehyde, and beta-substituted styrenes were also investigated for the first time. 相似文献
182.
[reaction: see text] 2,3-Disubstituted benzo[b]furans are readily prepared under very mild reaction conditions by the palladium/copper-catalyzed cross-coupling of various o-iodoanisoles and terminal alkynes, followed by electrophilic cyclization with I2, PhSeCl, or p-O2NC6H4SCl. Aryl- and vinylic-substituted alkynes undergo electrophilic cyclization in excellent yields. Biologically important furopyridines can be prepared by this approach in high yields. 相似文献
183.
水解胶原蛋白热氧化及CaSO4形成机理探讨;水解胶原蛋白; L-抗坏血酸; H2O2; 热氧化; CaSO4 相似文献
184.
High-throughput proteomics aims to investigate dynamically changing proteins expressed by a full organism, specific tissue or cellular compartment under certain conditions. High-sensitivity mass spectrometry has gradually become a significant tool for characterizing peptides. Here, we analyzed angiotensin II using ultra-fast liquid chromatography (UFLC) coupled with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF MS). First, we applied UFLC in isolating and collecting the angiotensin II, and then Axima-Resonance (MALDI-QIT-ToF MS(5)) was adopted, which enables collision-induced dissociation-MS(5) analysis for fine structural characterization of angiotensin II. Resultant MS, MS(2), MS(3) and MS(4) spectra of interested [M+H](+) ions selected as precursor ions yielded detailed information about the sites of fragmentation as well as the amino acid sequence for angiotensin II; meanwhile, the average deviation between theoretical mass and actually measured mass from MS to MS(5) spectra was only 0.32 Da. It indicated that Axima-Resonance was capable of analyzing the peptide sequence accurately and provide the corresponding fragmentation information thoroughly, thus suggesting a potential strategy involving UFLC assay coupled with MALDI-QIT-ToF MS(5) analysis on high-throughput proteomics study in future. 相似文献
185.
Metabolite distribution imaging via imaging mass spectrometry (IMS) is an increasingly utilized tool in the field of neurochemistry. As most previous IMS studies analyzed the relative abundances of larger metabolite species, it is important to expand its application to smaller molecules, such as neurotransmitters. This study aimed to develop an IMS application to visualize neurotransmitter distribution in central nervous system tissue sections. Here, we raise two technical problems that must be resolved to achieve neurotransmitter imaging: (1) the lower concentrations of bioactive molecules, compared with those of membrane lipids, require higher sensitivity and/or signal-to-noise (S/N) ratios in signal detection, and (2) the molecular turnover of the neurotransmitters is rapid; thus, tissue preparation procedures should be performed carefully to minimize postmortem changes. We first evaluated intrinsic sensitivity and matrix interference using Matrix Assisted Laser Desorption/Ionization (MALDI) mass spectrometry (MS) to detect six neurotransmitters and chose acetylcholine (ACh) as a model for study. Next, we examined both single MS imaging and MS/MS imaging for ACh and found that via an ion transition from m/z 146 to m/z 87 in MS/MS imaging, ACh could be visualized with a high S/N ratio. Furthermore, we found that in situ freezing method of brain samples improved IMS data quality in terms of the number of effective pixels and the image contrast (i.e., the sensitivity and dynamic range). Therefore, by addressing the aforementioned problems, we demonstrated the tissue distribution of ACh, the most suitable molecular specimen for positive ion detection by IMS, to reveal its localization in central nervous system tissues. 相似文献
186.
Qiong Liu Peilong Yang Huiying Luo Pengjun Shi Huoqing Huang Kun Meng Bin Yao 《Applied biochemistry and biotechnology》2012,166(6):1442-1453
An endo-β-1,4-mannanase encoding gene, man5, was cloned from Bispora antennata CBS 126.38, which was isolated from a beech stump. The cDNA of man5 consists of 1,299 base pairs and encodes a 432-amino-acid protein with a theoretical molecular mass of 46.6 kDa. Deduced
MAN5 exhibited the highest amino acid sequence identity of 58% to a β-mannanase of glycoside hydrolase family 5 from Aspergillus aculeatus. Recombinant MAN5 was expressed in Pichia pastoris and purified to electrophoretic homogeneity. The specific activity of the final preparation towards locust bean gum was 289
U mg−1. MAN5 showed optimal activity at pH 6.0 and 70 °C and had good adaptation and stability over a broad range of pH values.
The enzyme showed more than 60% of peak activity at pH 3.0–8.0 and retained more than 80% of activity after incubation at
37 °C for 1 h in both acid and alkaline conditions (pH 4.0–11.0). The K
m and V
max values were 1.33 mg ml−1 and 444 μmol min−1 mg−1 and 1.17 mg ml−1 and 196 μmol min−1 mg−1 for locust bean gum and konjac flour, respectively. Of all tested metal ions and chemical reagents, Co2+, Ni2+, and β-mercaptoethanol enhanced the enzyme activity at 1 mM, whereas other chemicals had no effect on or partially inhibited
the enzyme activity. MAN5 was highly resistant to acidic and neutral proteases (trypsin, α-chymotrypsin, collagenase, subtilisin
A, and proteinase K). By virtue of the favorable properties of MAN5, it is possible to apply this enzyme in the paper and
food industries. 相似文献
187.
188.
Whitehurst CE Yao Z Murphy D Zhang M Taremi S Wojcik L Strizki JM Bracken JD Cheng CC Yang X Shipps GW Ziebell M Nickbarg E 《Combinatorial chemistry & high throughput screening》2012,15(6):473-485
Affinity selection-mass spectrometry (AS-MS) is a sensitive technology for identifying small molecules that bind to target proteins, and assays enabled by AS-MS can be used to delineate relative binding affinities of ligands for proteins. 'Indirect' AS-MS assays employ size-exclusion techniques to separate target-ligand complexes from unbound ligands, and target-associated ligands are then specifically detected by liquid chromatography mass spectrometry. We report how indirect AS-MS binding assays with known reference control compounds were used as guideposts for development of an optimized purification method for CXCR4, a G-protein coupled chemokine receptor, for which we sought novel antagonists. The CXCR4 purification method that was developed was amenable to scale-up and enabled the screening of purified recombinant human CXCR4 against a large combinatorial library of small molecules by high throughput indirect AS-MS. The screen resulted in the discovery of new ligands that competed off binding of reference compounds to CXCR4 in AS-MS binding assays and that antagonized SDF1α-triggered responses and CXCR4-mediated HIV1 viral uptake in cell-based assays. This report provides a methodological paradigm whereby indirect AS-MS-based ligand binding assays may be used to guide optimal integral membrane protein purification methods that enable downstream affinity selection-based applications such as high throughput AS-MS screens. 相似文献
189.
The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals have been calculated. It was found that the formation enthalpy of oxygen vacancies can be decreased evidently by doping valence-changeable ions. The experimental results were discussed and a new reduction process of the photorefractive LN crystal at a relatively low temperature was proposed, and the reduced crystals showed a good effect in practical use. 相似文献
190.
The cyclization reactions of arylamines with 2-deoxy-D-ribose or glycals were reinvestigated in the current report. In the montmorillonite KSF- or InCl(3)-initiated reactions of 2-deoxy-D-ribose with arylamines, a pair of diastereomeric tetrahydro-2H-pyran-fused tetrahydroquinolines was obtained in a nearly 1:1 ratio where the structure of one diastereomer was incorrectly assigned in the literature. Meanwhile, the diastereoselectivity in InBr(3)-catalyzed cyclization of glycals with arylamines was also incorrectly reported previously. It was found that high diastereomeric selectivity was achieved only when a C5-substituted glycal was used; otherwise, a pair of diastereomers was obtained in moderate yield with 1:1 diastereomeric ratio. Furthermore, tetrahydrofuran-fused tetrahydroquinolines 5b and 5b' were also prepared successfully by using TBDPS-protected ribose as the glycal precursor and montmorillonite KSF as the activator. 相似文献