全文获取类型
收费全文 | 72234篇 |
免费 | 12582篇 |
国内免费 | 7404篇 |
专业分类
化学 | 50490篇 |
晶体学 | 662篇 |
力学 | 4672篇 |
综合类 | 311篇 |
数学 | 8230篇 |
物理学 | 27855篇 |
出版年
2024年 | 175篇 |
2023年 | 1539篇 |
2022年 | 2315篇 |
2021年 | 2649篇 |
2020年 | 3077篇 |
2019年 | 2848篇 |
2018年 | 2478篇 |
2017年 | 2273篇 |
2016年 | 3468篇 |
2015年 | 3322篇 |
2014年 | 3971篇 |
2013年 | 5172篇 |
2012年 | 6610篇 |
2011年 | 6748篇 |
2010年 | 4492篇 |
2009年 | 4282篇 |
2008年 | 4626篇 |
2007年 | 4134篇 |
2006年 | 3785篇 |
2005年 | 3156篇 |
2004年 | 2444篇 |
2003年 | 1932篇 |
2002年 | 1764篇 |
2001年 | 1479篇 |
2000年 | 1362篇 |
1999年 | 1550篇 |
1998年 | 1305篇 |
1997年 | 1291篇 |
1996年 | 1289篇 |
1995年 | 1057篇 |
1994年 | 922篇 |
1993年 | 768篇 |
1992年 | 679篇 |
1991年 | 579篇 |
1990年 | 503篇 |
1989年 | 386篇 |
1988年 | 337篇 |
1987年 | 276篇 |
1986年 | 249篇 |
1985年 | 205篇 |
1984年 | 144篇 |
1983年 | 102篇 |
1982年 | 80篇 |
1981年 | 67篇 |
1980年 | 65篇 |
1979年 | 32篇 |
1978年 | 30篇 |
1977年 | 40篇 |
1976年 | 30篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
921.
镓(Ⅲ)-茜素氨羧络合剂在碳糊电极上的阳极吸附伏安法研究及应用 总被引:1,自引:0,他引:1
研究了镓(Ⅲ)-茜素氨羧络合剂(ALC)在碳糊电极上的阳极吸附伏安行为,并以此建立了一种高灵敏度、高选择性测定镓的吸附伏安法.在0.12 mol/L HAc-NaAc-0.24 mol/L邻苯二甲酸氢钾底液(pH 4.5)中,-0.10 V (vs.SCE) 富集90 s (或180 s),以250 mV/s扫速线性扫描至0.90 V, Ga3+-ALC在碳糊电极上产生灵敏的与ALC的峰电位相差近230 mV的吸附氧化峰,其二次导数峰电流与镓浓度在5.0×10-10~8.0×10-7 mol/L范围内呈线性关系;富集240 s检出限达3.0×10-10 mol/L(S/N=3).探讨了电极反应机理.该法用于粮食样品中镓的测定,结果满意. 相似文献
922.
A method for the analysis of neutral oxosteroids by electrospray mass spectrometry is described. The oxosteroids are converted into their oximes by treatment with hydroxyammonium chloride in aqueous methanol. Intense peaks corresponding to protonated oxime molecules are observed in nano-electrospray mass spectra. The detection limits for the oximes of progesterone, pregnenolone and dehydroepiandrosterone were 2.5, 5 and 25 pg/microL, respectively, approximately 20 times lower than for the underivatised steroids. The signal intensities were proportional to the concentration of the steroids in the range of 500 to 2.5 pg/microL. Fragmentation by collision-induced dissociation (CID) was studied using oximes of 28 model steroids carrying an oxo group at C-3, C-17 or C-20. Some of the steroid oximes were labelled with deuterium or (15)N. Fragment ions were observed which yielded useful structural information. Upon CID, protonated oximes of 3-oxo-Delta(4)-steroids produced abundant ions by cleavage through the B-ring and by loss of the side chain, while protonated oximes of saturated 3-oxosteroids did not give abundant ions by cleavage through the B-ring. Protonated oximes of 20-oxosteroids unsubstituted at C-21, C-17 or C-16 produced a characteristic ion at m/z 86 containing the side chain, C-16 and C-17. Protonated oximes of steroids containing only a 17-oxo group gave fewer ions of diagnostic value. Coupled with the selective isolation of steroid oximes from a biological matrix this method of derivatisation and CID may be used for the analysis of neutral oxosteroids in biological samples. 相似文献
923.
924.
Yangke Wanyan Xixi Xu Kehang Liu Huidan Zhang Junai Zhen Rong Zhang Jumei Wen Ping Liu Yuqing Chen 《Molecules (Basel, Switzerland)》2020,25(23)
Inhibition of the glycolytic pathway is a critical strategy in anticancer therapy because of the role of aerobic glycolysis in cancer cells. The glycolytic inhibitor 2-Deoxy-d-glucose (2-DG) has shown potential in combination with other anticancer agents. Buforin IIb is an effective antimicrobial peptide (AMP) with broad-spectrum anticancer activity and selectivity. The efficacy of combination treatment with 2-DG and buforin IIb in prostate cancer remains unknown. Here, we tested the efficacy of buforin IIb as a mitochondria-targeting AMP in the androgen-independent human prostate cancer cell line DU145. Combining 2-DG with buforin IIb had a synergistic toxic effect on DU145 cells and mouse xenograft tumors. Combination treatment with 2-DG and buforin IIb caused stronger proliferation inhibition, greater G1 cell cycle arrest, and higher apoptosis than either treatment alone. Combination treatment dramatically decreased L-lactate production and intracellular ATP levels, indicating severe inhibition of glycolysis and ATP production. Flow cytometry and confocal laser scanning microscopy results indicate that 2-DG may increase buforin IIb uptake by DU145 cells, thereby increasing the mitochondria-targeting capacity of buforin IIb. This may partly explain the effect of combination treatment on enhancing buforin IIb-induced apoptosis. Consistently, 2-DG increased mitochondrial dysfunction and upregulated Bax/Bcl-2, promoting cytochrome c release to initiate procaspase 3 cleavage induced by buforin IIb. These results suggest that 2-DG sensitizes prostate cancer DU145 cells to buforin IIb. Moreover, combination treatment caused minimal hemolysis and cytotoxicity to normal WPMY-1 cells. Collectively, the current study demonstrates that dual targeting of glycolysis and mitochondria by 2-DG and buforin IIb may be an effective anticancer strategy for the treatment of some advanced prostate cancer. 相似文献
925.
The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure. 相似文献
926.
Liu SG Liu H Bandyopadhyay K Gao Z Echegoyen L 《The Journal of organic chemistry》2000,65(11):3292-3298
The synthesis and electrochemistry of a series of tetrathiafulvalene (TTF) and dithia-crown-TTF derivatives attached with one or two disulfide group(s) 7a-f are reported. The self-assembled monolayers (SAMs) of these TTF disulfides on gold were prepared and characterized by reflection-absorption infrared spectroscopy. The SAMs are extremely stable under a wide variety of conditions and over extended periods of time and show remarkable electrochemical stability upon repeated potential scans. SAMs of the crown-TTF disulfides 7c,d,f can recognize alkali metal ions, and the process can be monitored following the electrochemical potential shift of the surface-confined TTF group. 相似文献
927.
高效石墨浮选剂的合成金婵,薛玉,汪进,刘欣荣,秦英海(哈尔滨工业大学应用化学系哈尔滨150001)(大庆石化总公司大庆)关键词石墨,浮选剂,合成,混合烃由于石墨具有良好的力学性能、导电、高熔点等性质,广泛用于原子能、宇航和民用工业。隐晶质石墨属于微晶... 相似文献
928.
Solid state synthesis and structure of two novel polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4](M?Mo,W)†
Hou Hong-Wei Xin Xin-Quan Yu Kai-Bei Wang Zhe-Min Liu Shi-Xiong Huang Jin-Ling 《中国化学》1996,14(2):123-130
The reaction of [NH4]2[MO2S2], AgI and (n-Bu)4NBr in solid state produced the polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4] (1, M? Mo; 2, M? W) which were structurally determined. The crystals of 1 and 2 are isomorphous, monoclinic, space group P21/c. 1, a = l.6624(2), b=1.6699(3), c=l.7217(2) nm, β=98.29(1)°, V=4.729(1) nm3, Z=2, R=0.040, Rw“0.037; 2, a = 1.6636(3), b = 1.6733(3), c = 1.7190(3) nm, β=98.25(1)°, V=4.736(l) nm3, Z = 2, R = 0.038, Rw = 0.047. The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag2I4]2. and [M6O19]2-. The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster. ion, heteropolymetalate and organic cations, while the latter is only composed of heteropolymetalate and organic cations. 相似文献
929.
The reactions of tris(acetonitrile)tricarbonylchromium 1 with trimethylsilyl derivatives 2–5 of phenalene, indene, 1,2-dihydronaphthalene and trans-β-methylstyrene gave products 10-13, respectively, containing no trimethylsilyl groups. The reactions of 1 with trimethylsilyl derivatives 6–8 of benzene, toluene and cycloheptatriene gave products 14–16, respectively, containing trimethylsilyl groups. The reaction of 1 with 1,2-bis(trimethylsily-1,2-dihydro)naphthalene 9 gave product 17 in which only trimethylsilyl at the allylic position was cleaved. Compound 10 crystallizes in the orthorhombic system, space group Pbca, with a = 12.228(4), b = 14.288(1), c = 15.128(3) Å, Z = 8, RF= 0.046, and Rw = 0.047. X-ray crystallographic data confirm that the Cr(CO)3 moiety is bonded to phenalene in a η6-mold. 相似文献
930.
氧化共沉淀法制备纳米级掺锑α—Fe2O3气敏陶瓷粉料 总被引:1,自引:0,他引:1
氧化共沉淀法制备纳米级掺锑α┐Fe2O3气敏陶瓷粉料王忠春**刘尔生陈耐生*黄金陵(福州大学化学系福州350002)关键词α-Fe2O3陶瓷,锑掺杂气敏材料,纳米材料1996-10-05收稿,1997-04-22修回福建省科委资助项目**现在上海硅酸... 相似文献