全文获取类型
收费全文 | 2459篇 |
免费 | 316篇 |
国内免费 | 575篇 |
专业分类
化学 | 2333篇 |
晶体学 | 93篇 |
力学 | 52篇 |
综合类 | 21篇 |
数学 | 11篇 |
物理学 | 840篇 |
出版年
2024年 | 5篇 |
2023年 | 52篇 |
2022年 | 46篇 |
2021年 | 65篇 |
2020年 | 99篇 |
2019年 | 80篇 |
2018年 | 106篇 |
2017年 | 123篇 |
2016年 | 116篇 |
2015年 | 110篇 |
2014年 | 118篇 |
2013年 | 219篇 |
2012年 | 283篇 |
2011年 | 163篇 |
2010年 | 117篇 |
2009年 | 157篇 |
2008年 | 136篇 |
2007年 | 166篇 |
2006年 | 154篇 |
2005年 | 114篇 |
2004年 | 121篇 |
2003年 | 77篇 |
2002年 | 101篇 |
2001年 | 83篇 |
2000年 | 80篇 |
1999年 | 71篇 |
1998年 | 58篇 |
1997年 | 53篇 |
1996年 | 59篇 |
1995年 | 52篇 |
1994年 | 33篇 |
1993年 | 26篇 |
1992年 | 26篇 |
1991年 | 13篇 |
1990年 | 12篇 |
1989年 | 8篇 |
1988年 | 11篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 6篇 |
1972年 | 1篇 |
排序方式: 共有3350条查询结果,搜索用时 15 毫秒
151.
Harshanie Abeywardena Aaron R. Jex Simon M. Firestone Sandra McPhee Nicole Driessen Anson V. Koehler Shane R. Haydon Georg von Samson‐Himmelstjerna Melita A. Stevens Robin B. Gasser 《Electrophoresis》2013,34(15):2259-2267
In the present study, we undertook a molecular epidemiological survey of Cryptosporidium and Giardia in calves on three dairy and two beef farms within an open drinking water catchment area (Melbourne, Australia). Faecal samples (n = 474) were collected from calves at two time points (5 months apart) and tested using a PCR‐based mutation scanning‐targeted sequencing phylogenetic approach, employing regions within the genes of small subunit (SSU) of ribosomal RNA (designated partial SSU), 60 kDa glycoprotein (pgp60) and triose phosphate isomerase (ptpi) as genetic markers. Using partial SSU, the C. bovis, C. parvum, C. ryanae and a new genotype of Cryptosporidium were characterised from totals of 74 (15.6%), 35 (7.3%), 37 (7.8%) and 9 (1.9%) samples, respectively. Using pgp60, C. parvum genotype IIa subgenotype A18G3R1 was detected in 29 samples. Using ptpi, G. duodenalis assemblages A and E were detected in totals of 10 (2.1%) and 130 (27.4%) samples, respectively. The present study showed that a considerable proportion of dairy and beef calves in this open water catchment region excreted Cryptosporidium (i.e. subgenotype IIaA18G3R1) and Giardia (e.g. assemblage A) that are consistent with those infecting humans, inferring that they are of zoonotic importance. Future work should focus on exploring, in a temporal and spatial way, whether these parasites occur in the environment and water of the catchment reservoir. 相似文献
152.
《Journal of Dispersion Science and Technology》2013,34(2-3):197-202
Cu(II)-salicylate was synthesized and characterized by X-ray diffraction. The reaction mechanism of the Cu(II) complex with superoxide anion was studied by ESR spectroscopy, and its (superoxide dismutase) SOD-like activity was determined by a modified illumination method in phosphate buffer (pH = 7.8), micelle solutions and lamellar liquid crystals formed from surfactants CTAB and TX-100. X-ray diffraction indicated that the Cu(II) complex had a formula Cu2(Hsal)4EtOHH2O and a similar structure to the SOD active site. EPR spectra proved that the reaction mechanism of the Cu(II) complex catalyzing O 2 .- dismutation was the same as that of the proposed dismutation reaction catalyzed by SOD. Results obtained by the NBT method indicated that the Cu(II)-complex showed SOD-like activity, and the effect of microenvironment created by surfactants on its activity was same as on SOD activity. The order of the inhibition of NBT reduction by the Cu(II)-complex in different microenvironments was: in phosphate buffer (pH = 7.8) > in TX-100 micelle > in TX-100 liquid crystal, and in nonionic TX-100 organized assemblies > in cationic CTAB organized assemblies. These results were explained by the catalytic effect of micelles, and by the space restriction and high viscosity of organized assemblies of surfactants. 相似文献
153.
通过热分解法制备Cu模型催化剂,然后经浸渍制备ZrO2/Cu催化剂,采用SEM、XPS考察了催化剂表面形态和组成,并采用in-situ Raman考察了催化剂在还原和吸附CO和水的过程中随时间的变化。结果表明,还原前Cu催化剂表面主要存在CuO物种,而在ZrO2/Cu表面,除了CuO物种,还存在着大量的表面羟基物种。ZrO2/Cu相对Cu更加容易还原为Cu0,同时,ZrO2在催化剂表面聚集形成絮状态,而Cu催化剂还原后主要形成Cu2O物种。Cu催化剂表面吸附CO后,除了形成Cu-CO外,Cu2O物种均会迅速消失形成CO2。Cu催化剂对水的作用比较弱,但是ZrO2/Cu催化剂和水作用较强,并且通过Cu-OH中间物形成Cu2O物种。 相似文献
154.
155.
Janaína Versiani dos Anjos Rajendra M. Srivastava Silene Carneiro do Nascimento Sebastião J. de Melo 《Journal of carbohydrate chemistry》2013,32(4):258-277
A copper‐catalyzed reaction of propargyl 4,6‐di‐O‐acetyl‐2,3‐dideoxy‐α‐D‐erythro‐hex‐2‐enopyranoside with 3‐(4‐azidophenyl)‐1,2,4‐oxadiazoles gave the corresponding hexenopyranosides bearing an 1,2,4‐oxadiazole subunit in the aglyconic part of the molecule. The same reaction between ethyl 4‐azido‐2,3,4‐trideoxy‐α‐D‐erythro‐hex‐2‐enopyranoside and acetylenic 1,2,4‐oxadiazoles afforded the corresponding hexenopyranosides carrying a triazole and a 1,2,4‐oxadiazole ring at C‐4 of the carbohydrate. Combination of the two sequences gave hexenopyranosides displaying two 1,2,4‐oxadiazole subunits, each one being embedded in the C‐1 and C‐4 frameworks, of the carbohydrate moiety. A simple dihydroxylation reaction of these unsaturated carbohydrates yielded a series of mannopyranosides bearing one or two 1,2,4‐oxadiazole subunits at C‐1 or C‐4. These new compounds were evaluated for their cytotoxic activities against two cell strains: NCI‐H292 (lung carcinoma) and Hep‐2 (larynx carcinoma), some of them presenting impressive cell growth inhibitions. 相似文献
156.
合成了邻菲罗啉衍生物联吡啶[3,2-a:2',3'-c]-7-氮杂-吩嗪(dpapz)及其铜(I)配合物[Cu(dpapz)2]PF6, 利用核磁共振氢谱(1H NMR), 傅里叶变换红外(FTIR)光谱, 高分辨质谱(HR ESI-MS)等对合成的化合物进行了表征.采用紫外-可见吸收光谱,荧光光谱, DNA熔解温度实验和循环伏安方法研究了dpapz和[Cu(dpapz)2]PF6与小牛胸腺DNA(CT DNA)的相互作用. 配体dpapz与小牛胸腺DNA(CT DNA)作用时未观察到吸收峰红移并且减色效应较小(<30%), 且DNA熔解温度也上升较小(ΔTm=7.8 ℃), 说明dpapz以沟槽结合的方式与CT DNA相互作用. 而[Cu(dpapz)2]PF6与CT DNA作用时, 可观测到较小的吸收峰红移(2-3 nm)和较大的减色效应(>50%), 同时DNA熔解温度上升较大(ΔTm=11.1 ℃), 表明[Cu(dpapz)2]PF6以静电相互作用和部分扦插的方式与DNA结合. 溴乙锭(EB)荧光竞争实验和循环伏安实验进一步证实了这一结论. 配体dpapz和[Cu(dpapz)2]PF6与DNA的结合常数分别为2.88×105和5.32×105 mol·L-1. 光照条件下, [Cu(dpapz)2]PF6产生单重态氧的能力与dpapz相当, 但产生超氧负离子自由基的能力要弱于dpapz. 活性氧猝灭实验表明, 超氧负离子自由基、单重态氧和羟基自由基均参与了dpapz和[Cu(dpapz)2]PF6对DNA的光损伤作用. [Cu(dpapz)2]PF6对DNA的亲和性要高于对dpapz的, 使得[Cu(dpapz)2]PF6对质粒DNA的光损伤效率明显强于dpapz. 相似文献
157.
采用基于密度泛函理论的第一性原理方法和平板模型研究了CH3SH分子在Cu(111)表面的吸附反应.系统地计算了S原子在不同位置以不同方式吸附的一系列构型, 第一次得到未解离的CH3SH分子在Cu(111)表面顶位上的稳定吸附构型,该构型吸附属于弱的化学吸附, 吸附能为0.39 eV. 计算同时发现在热力学上解离结构比未解离结构更加稳定. 解离的CH3S吸附在桥位和中空位之间, 吸附能为0.75-0.77 eV. 计算分析了未解离吸附到解离吸附的两条反应路径, 最小能量路径的能垒为0.57 eV. 计算结果还表明S―H键断裂后的H原子并不是以H2分子的形式从表面解吸附而是以与表面成键的形式存在. 通过比较S原子在独立的CH3SH分子和吸附状态下的局域态密度, 发现S―H键断裂后S原子和表面的键合强于未断裂时S原子和表面的键合. 相似文献
158.
研究了1-4丁炔二醇和乙二胺作为添加剂对在离子液体1-甲基-3-甲基咪唑三氟甲磺酸盐中电沉积Cu的影响。紫外可见光吸收光谱结果表明,当采用1-4丁炔二醇作为添加剂时,1-4丁炔二醇吸附在工作电极表面且未与溶液中的Cu2+形成配合物。扫描电镜测试结果表明由于1-4丁炔二醇与离子液体的正离子的竞争吸附使得Cu的沉积电势发生正移并使镀层表面更加均匀平整。当采用乙二胺作为添加剂时,紫外可见光吸收光谱和循环伏安测试结果表明乙二胺与溶液中的Cu2+离子形成带有正电荷的络合离子使得Cu的沉积电势发生正移,扫描电镜和原子力显微镜测试结果表明得到了更加均匀的镀层。当同时加入1-4丁炔二醇和乙二胺时,Cu的沉积电势仍然发生正移并得到具有纳米粒径的镀层。 相似文献
159.
Precise characterization method of antibody‐conjugated magnetic nanoparticles for pathogen detection using stuffer‐free multiplex ligation‐dependent probe amplification
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Boram Chung Gi Won Shin Woong Choi Jinmyoung Joo Sangmin Jeon Gyoo Yeol Jung 《Electrophoresis》2014,35(23):3283-3289
Antibody‐conjugated magnetic nanoparticles (Ab‐MNPs) have potential in pathogen detection because they allow target cells to be easily separated from complex sample matrices. However, the sensitivity and specificity of pathogen capture by Ab‐MNPs generally vary according to the types of MNPs, antibodies, and sample matrices, as well as preparation methods, including immobilization. Therefore, achieving a reproducible analysis utilizing Ab‐MNPs as a pathogen detection method requires accurate characterization of Ab‐MNP capture ability and standardization of all handling processes. In this study, we used high‐resolution CE‐single strand conformational polymorphism coupled with a stuffer‐free multiplex ligation‐dependent probe amplification system to characterize Ab‐MNPs. The capture ability of Ab‐MNPs targeting Salmonella enteritidis and nine pathogens, including S. enteritidis, was analyzed in phosphate buffer and milk. The effect of storage conditions on the stability of Ab‐MNPs was also assessed. The results showed that the stuffer‐free multiplex ligation‐dependent probe amplification system has the potential to serve as a standard characterization method for Ab‐MNPs. Moreover, the precise characterization of Ab‐MNPs facilitated robust pathogen detection in various applications. 相似文献
160.
An environmentally benign [Cu(I)]-catalyzed oxidation of activated (benzylic/allylic) alcohols to the corresponding carbonyl compounds is presented. Interestingly, the reaction was also compatible with benzylic alcohols containing ortho-bromo substituents on the aromatic ring without competing with the expected intermolecular Buchwald coupling. Significantly, the catalytic system enables the synthesis of cinnamate-esters in a sequential domino one-pot fashion via oxidation followed by Wittig–Horner protocol. 相似文献