全文获取类型
收费全文 | 13282篇 |
免费 | 2197篇 |
国内免费 | 1920篇 |
专业分类
化学 | 9889篇 |
晶体学 | 249篇 |
力学 | 744篇 |
综合类 | 148篇 |
数学 | 1219篇 |
物理学 | 5150篇 |
出版年
2024年 | 26篇 |
2023年 | 209篇 |
2022年 | 424篇 |
2021年 | 480篇 |
2020年 | 506篇 |
2019年 | 499篇 |
2018年 | 431篇 |
2017年 | 453篇 |
2016年 | 650篇 |
2015年 | 685篇 |
2014年 | 804篇 |
2013年 | 1036篇 |
2012年 | 1332篇 |
2011年 | 1374篇 |
2010年 | 964篇 |
2009年 | 948篇 |
2008年 | 998篇 |
2007年 | 873篇 |
2006年 | 847篇 |
2005年 | 739篇 |
2004年 | 562篇 |
2003年 | 381篇 |
2002年 | 415篇 |
2001年 | 333篇 |
2000年 | 254篇 |
1999年 | 223篇 |
1998年 | 183篇 |
1997年 | 137篇 |
1996年 | 103篇 |
1995年 | 90篇 |
1994年 | 81篇 |
1993年 | 66篇 |
1992年 | 59篇 |
1991年 | 55篇 |
1990年 | 41篇 |
1989年 | 20篇 |
1988年 | 16篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
42.
43.
在65 ℃、氮气保护下, 往咔唑钠的四氢呋喃溶液中缓慢滴加1,4-二氯-2-丁炔. 反应9 h后, 在苯和石油醚混合溶剂中重结晶, 分离得到反式N-3-炔丁烯基咔唑. 在加热, BPO, BF3, FeCl3, P2O5, 紫外或可见光的引发作用下, 反式N-3-炔丁烯基咔唑发生齐聚反应. 通过元素分析, IR, 1H NMR, MS, UV等方法对反应产物进行分析表征. IR和1H NMR图谱显示单体聚合后炔基及其相连氢原子的特征吸收峰(ν: 3278, 2099 cm-1; : 2.8~3.0)消失, VPO法测得齐聚物分子量在8.3×102至1.9×103之间(聚合度4~9). 相似文献
44.
微乳液介质—1—(2—吡啶偶氮)—2—萘酚光度法测定汽油中环烷酸铁的含量 总被引:8,自引:2,他引:8
本研究了微乳液为介质时,铁与1-(2-吡啶偶氮)-2-萘酚(PAN)的显色反应。选择730nm处为测定波长,ε为1.4×10^4L.mol^-^1.cm^-^1,铁量在0-50μg/25ml范围内符合比耳定律,该法适用于汽油中环烷酸铁的测定。 相似文献
45.
A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%. 相似文献
46.
In order to explore the transfer mechanism of chromium(III) in mammals, a novel complex [Cr(ASA)(en)2]Cl· 2H2O, bis(ethylenediamine‐ κ 2 N,N′)(4‐aminosalicylic acid‐ κ 2 O,O′) chromium(III) monochloride dihydrate was synthesized (4‐aminosalicylic acid=H2ASA, ethylenediamine=en). The crystal structure belongs to orthorhombic system with the space group P212121 by means of X‐ray diffraction. The characteristic for transfer of Cr3+ from the compound to the low‐molecular‐mass chelator EDTA and the iron‐binding protein apoovotransferrin (apoOTf) was followed by UV‐visible (UV‐Vis) and fluorescence spectra in 0.01 mol·L?1 Hepes at pH 7.4. The second order rate constants were calculated. Those spectra in conjunction were used to obtain more accurate information about the interaction of chromium complex with apoOTf. The experimental results indicate that Cr3+ can be transferred from the complex to apoOTf with the retention of the 4‐aminosalicylic acid acting as a synergistic anion. 相似文献
47.
CHIP-mediated hyperubiquitylation of tau promotes its self-assembly into the insoluble tau filaments
Ji Hyeon Kim Jeeyoung Lee Won Hoon Choi Seoyoung Park Seo Hyeong Park Jung Hoon Lee Sang Min Lim Ji Young Mun Hyun-Soo Cho Dohyun Han Young Ho Suh Min Jae Lee 《Chemical science》2021,12(15):5599
The tau protein is a highly soluble and natively unfolded protein. Under pathological conditions, tau undergoes multiple post-translational modifications (PTMs) and conformational changes to form insoluble filaments, which are the proteinaceous signatures of tauopathies. To dissect the crosstalk among tau PTMs during the aggregation process, we phosphorylated and ubiquitylated recombinant tau in vitro using GSK3β and CHIP, respectively. The resulting phospho–ub-tau contained conventional polyubiquitin chains with lysine 48 linkages, sufficient for proteasomal degradation, whereas unphosphorylated ub-tau species retained only one–three ubiquitin moieties. Mass-spectrometric analysis of in vitro reconstituted phospho–ub-tau revealed seven additional ubiquitylation sites, some of which are known to stabilize tau protofilament stacking in the human brain with tauopathy. When the ubiquitylation reaction was prolonged, phospho–ub-tau transformed into insoluble hyperubiquitylated tau species featuring fibrillar morphology and in vitro seeding activity. We developed a small-molecule inhibitor of CHIP through biophysical screening; this effectively suppressed tau ubiquitylation in vitro and delayed its aggregation in cultured cells including primary cultured neurons. Our biochemical findings point to a “multiple-hit model,” where sequential events of tau phosphorylation and hyperubiquitylation function as a key driver of the fibrillization process, thus indicating that targeting tau ubiquitylation may be an effective strategy to alleviate the course of tauopathies.Multiple-hit model for tau aggregation, where sequential events of tau phosphorylation and hyperubiquitylation function as a key driver of the fibrillization process. 相似文献
48.
Yu Liu Bin Li Takehiko Wada Yoshihisa Inoue 《Journal of inclusion phenomena and macrocyclic chemistry》2000,36(3):311-325
The spectrophotometric titrations have beenperformed at 25–40 °C in aqueous solution to give the complexstability constants and the thermodynamic parametersfor the stoichiometric 1 : 1 inclusion complexation ofvarious aliphatic alcohols withmono[6-(phenylseleno)-6-deoxy]--cyclodextrin (2),mono[6-(o-, m-,p-tolylseleno)-6-deoxy]--cyclodextrin (3–5),mono[6-(p-chloro-phenyl-seleno)-6-deoxy]--cyclodextrin(6), mono[6-(benzylseleno)-6-deoxy]--cyclodextrin (7) and mono[6-(naphthaleneseleno)-6-deoxy]--cyclodextrin(8). On thebasis of the present and previous results, themolecular binding abilities and selectivities forguest aliphatic alcohols of the host -cyclodextrinderivatives (2–8) are discussed comparatively and globallyfrom the thermodynamic point of view. Thethermodynamic parameters obtained are criticalfunctions of the size/shape of aliphatic alcohols, andthe position and type of the substituent introduced tothe aromatic ring of -cyclodextrin's sidearm,which are elucidatedin terms of the conformational, electrostatic,hydrogen-bonding, and hydrophobic effects. 相似文献
49.
Dr. Dingfeng Yang Junzhu Yang Xuejun Quan Bin Zhang Guoyu Wang Xu Lu Xiaoyuan Zhou 《Chemphyschem》2021,22(24):2579-2584
Understanding the correlation between crystal structure and thermal conductivity in semiconductors is very important for designing heat-transport-related devices, such as high-performance thermoelectric materials and heat dissipation in micro-nano-scale devices. In this work, the lattice thermal conductivity ( ) of the cage-like compounds Cu3VSe4 and Cu3NbSe4 was investigated by experimental measurements and first-principles calculations. The experimental of Cu3NbSe4 is approximately 25 % lower than that of Cu3VSe4 at 300 K. The relevant important physical parameters, including the sound velocity, heat capacity, weighted phonon phase space (W), and third-order force constants along with atomic mass were theoretically analyzed. It is found that W is the dominant parameter in determining the , and the other factors only play a minor role. The physical origin is the relatively “soft” lattice of Cu3NbSe4 with heavier atomic mass. This research provides deep insight into the correlation between the thermal conductivity and crystal structure and paves the way for discovering high-performance thermal management device and thermoelectric materials with intrinsically low . 相似文献
50.
A direct quantitative method is presented that is based upon the use of multiple headspace solid phase microextraction (HS-SPME) to monitor biogenic volatile organic compounds (BVOCs) released from a living leaf of Pelargonium hortorum in situ. Seventeen BVOCs were detected by GC-MS after a single SPME extraction using a CAR/DVB/PDMS fibre. An internal standard was employed to determine the absolute amounts of seven terpenoid compounds released from a P. hortorum leaf. The quantitative analysis was performed over two days, with extraction preformed for 20 min every 3 h. The amount of volatiles extracted varied with the time of day, with two maxima recorded at 14:00 (day 1) and 17:00 (day 2), corresponding to 236 and 277 ng of the seven terpenoids recorded, respectively. These results indicate that multiple HS-SPME in combination with an internal standard is a simple, quick, and quantitative technique for analysising BVOC emissions from a live plant sample. 相似文献