全文获取类型
收费全文 | 15469篇 |
免费 | 2577篇 |
国内免费 | 1919篇 |
专业分类
化学 | 11338篇 |
晶体学 | 232篇 |
力学 | 861篇 |
综合类 | 131篇 |
数学 | 1613篇 |
物理学 | 5790篇 |
出版年
2024年 | 62篇 |
2023年 | 317篇 |
2022年 | 562篇 |
2021年 | 569篇 |
2020年 | 587篇 |
2019年 | 650篇 |
2018年 | 526篇 |
2017年 | 511篇 |
2016年 | 721篇 |
2015年 | 734篇 |
2014年 | 934篇 |
2013年 | 1230篇 |
2012年 | 1432篇 |
2011年 | 1553篇 |
2010年 | 1039篇 |
2009年 | 1013篇 |
2008年 | 1016篇 |
2007年 | 993篇 |
2006年 | 801篇 |
2005年 | 684篇 |
2004年 | 583篇 |
2003年 | 443篇 |
2002年 | 416篇 |
2001年 | 354篇 |
2000年 | 329篇 |
1999年 | 251篇 |
1998年 | 212篇 |
1997年 | 168篇 |
1996年 | 185篇 |
1995年 | 148篇 |
1994年 | 154篇 |
1993年 | 119篇 |
1992年 | 115篇 |
1991年 | 94篇 |
1990年 | 87篇 |
1989年 | 78篇 |
1988年 | 44篇 |
1987年 | 41篇 |
1986年 | 42篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 16篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Hua-Hong Zou Shu-Hua Zhang Ming-Hua Zeng Yan-Ling Zhou Hong Liang 《Journal of Molecular Structure》2008,885(1-3):50-55
A novel linear trimeric-based, Mn(II)–carboxylate chain well separated by long-linking flexible aliphatic tricarballylic acid ligands in a 3D coordination polymer [Mn3(C6H5O6)2(H2O)4]n (1, C6H5O6CH (COO−)(CH2COO−)2, TCA) exhibits low-dimensional antiferromagnetic order at 3.0 K. Such magnetic behavior is arises from the alternate Antiferro–Antiferro–Antiferro′ (J1 J1 J2) repeating interactions sequence, based on the nature of the binding modes of Mn(II)-carboxylate chain and the effect of interchains arrangement of 1. The reported carboxylate-bridged metal chain systems display a new structurally authenticated example of linear homometallic spin arranged antiferromagnet among metal carboxylates. 相似文献
942.
Xiaoxin Cao Xia Huang Nico Boon Peng Liang Mingzhi Fan 《Electrochemistry communications》2008,10(9):1392-1395
Microbial fuel cell (MFC) technology is a novel electricity generation process catalyzed by microorganisms. Much progress is made in the design and construction of MFCs, however the diversity of the electrochemically active microorganisms and the electricity generation mechanisms remain a black box. As sun is a predominantly unused energy resource, here we present a highly enriched phototrophic consortium that can produce electricity in an “H” typed MFC at a high power density (2650 mW m−2, normalized to membrane area) in light, which was eightfold of that produced by non-enriched consortium in the same reactor. Light–dark shift experiments showed that light contributed to the electricity generation. A microbial excreted mediator assisted the electron transfer to the electrode. During the experiment, the accumulation of the mediator over time enhanced the electron transfer rate. The excitation–emission matrix fluorescence spectroscopy results indicated indole group containing compound representing the dominant mediator component. 相似文献
943.
用10 nm的金纳米粒子标记单克隆癌胚抗原抗体制备了检测癌胚抗原(CEA)的共振散射光谱探针(Au-CEAAb)。在pH 6.8 的Na2HPO4- NaH2PO4缓冲溶液中及聚乙二醇-6000存在下, CEA与Au-CEAAb发生免疫反应聚集形成疏水性的、平均粒径为227.0 nm的免疫复合物微粒,并在321 nm、581 nm产生2个共振散射峰。随着癌胚抗原(CEA)浓度的增大,581 nm处的共振散射强度I581nm线性增加,其增加值△I581nm与CEA浓度在1.0~50.0 ng·mL-1范围内呈良好的线性关系,相应的回归方程、相关系数、检出限(3σ)分别为ΔI581nm=1.63 C +5.6、0.9940、0.52 ng·mL-1。该法简便、快速、灵敏且选择性好,用于检测人血清中癌胚抗原(CEA),结果满意。 相似文献
944.
Hydrophilic interaction chromatography (HILIC) was employed to separate the co-eluted flavonoids from licorice extract under RP-HPLC mode. HILIC separations were carried out with the Atalantis HILIC Silica column and the CD-based column. The co-eluted flavonoids were well retained and separated on the two HILIC columns under HILIC mode. Similar results were obtained in the separation of another isoflavones sample, from kudzu extract under HILIC mode. 相似文献
945.
A tungsten coil electrothermal vaporizer (W-coil ETV) was coupled to an Ar/H(2) flame atomic fluorescence spectrometer for the determination of eight traditional hydride-forming elements (i.e., As, Bi, Ge, Pb, Sb, Se, Sn, and Te) as well as cadmium without chemical vapor generation. A small sample volume, typically 20muL, was manually pipetted onto the W-coil and followed by a fixed electric heating program. During the vaporization step, analyte was vaporized off the coil surface and swept into the quartz tube atomizer of AFS for further atomization and excitation of atomic fluorescence by a flow of Ar/H(2) gas, which was ignited to produce the Ar/H(2) flame. The tungsten coil electrothermal vaporizer and Ar/H(2) flame formed a tandem atomizer to produce reliable atomic fluorescence signals. Under the optimal instrumental conditions, limits of detection (LODs) were found to be better than those by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma optical emission spectrometry (ICP-OES) for all the nine elements investigated. The absolute LODs are better or equivalent to those by hydride generation atomic fluorescence spectrometry (HG-AFS). Possible scattering interferences were studied and preliminary application of the proposed method was also reported. 相似文献
946.
Jun Yue Bai Liang Wang Hong Jing Wang Peng Fei Huang Yu Qing Zhao Sheng Di Fan 《Mikrochimica acta》2006,156(3-4):321-326
The electrochemical behavior of epinephrine (EP) at a mercaptoacetic acid (MAA) self-assembled monolayer modified gold electrode
was studied. The MAA/Au electrode is demonstrated to promote the electrochemical response of epinephrine by cyclic voltammetry.
The possible reaction mechanism is also discussed. The diffusion coefficient D of EP is 6.85 × 10−6 cm2 s−1. In 0.1 mol L−1 phosphate buffer (pH 7.20), a sensitive oxidation peak was observed at 0.177 V, and the peak current is proportional to the
concentration of EP in the range of 1.0 × 10−5–2.0 × 10−4 mol L−1 and 1.0 × 10−7–1.0 × 10−6 mol L−1. The detection limit is 5 × 10−8 mol L−1. The modified electrode is highly stable and can be applied to the determination of EP in practical injection samples. The
method is simple, quick, sensitive and accurate. 相似文献
947.
Shabbir Muhammad Chunguang Liu Liang Zhao Shuixing Wu Zhongmin Su 《Theoretical chemistry accounts》2009,122(1-2):77-86
The interaction between chemosensor, N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (1) and different halide ions (F ? , Cl? and Br?) has been investigated using density functional theory (DFT). A clear insight of the sensor anion binding process has been presented. Our calculations revealed that the observed colorimetric and fluorescent signals are induced due to the ground state deprotonation of the sensor molecule caused by F? which has two times higher binding affinity than other halide ions (Cl? and Br?). Derivatives of system 1 have been made to find a better sensor with higher binding affinity and longer wavelength of absorption. All the derivatives are better sensors than the parent 1 except 4-methyl-N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (2). Among these derivatives, trimethyl-[4-(2-methyl-1,3-dioxo-indan-5-ylcarbamoyl)-phenyl]-ammonium (8) and (5-benzoylamino-1,3-dioxo-indan-2-yl)-trimethyl-ammonium (9) showed a change to higher binding energies of about 58 Kcal/mol and longer absorption wavelengths of 53 nm after deprotonation process than the parent system 1 which is highly demanded in selective chemical sensing. Systems 8, 9 and their deprotonated zwitterionic forms (8z and 9z) have also been studied for their nonlinear optical responses. Systems 8, 9 showed significantly good first hyperpolarizability (β) of 84 × 10?30 and 40 × 10?30 esu, respectively. These β values increase in zwitterionic states up to 216 × 10?30 and 109 × 10?30 esu, respectively after deprotonation with F?, representing a new signal of deprotonation. 相似文献
948.
基于金纳米微粒的化学发光金属免疫分析 总被引:2,自引:0,他引:2
建立了基于金纳米微粒溶解的化学发光反应体系,并探讨了金纳米微粒溶解及化学发光测定的最佳条件。首次将金纳米微粒引入生物素和IgG的化学发光金属免疫分析,比较了不同粒径金纳米微粒、不同检测系统对IgG测定的影响。在(一抗-IgG-二抗修饰金纳米微粒)检测系统中,基于10 nm和30 nm金纳米微粒测定IgG的线性范围分别为1~75 ng和0.5~25 ng,检出限分别为0.5 ng和0.1 ng。在(一抗-IgG-生物素化抗体-链霉亲和素修饰金纳米微粒)检测系统中,5 nm和10 nm金纳米微粒测定IgG的线性范围分别为10~250 ng和1~250 ng;检出限分别为5 ng和1 ng。 相似文献
949.
Xiao‐Xu Li Ning Wang Shan‐Tang Yue Prof. Dr. Zhao‐Yang Li Hong‐Yan Wu Ying‐Liang Liu 《无机化学与普通化学杂志》2009,635(15):2648-2652
Self‐assembly of the rigid organic ligand 2‐propyl‐4,5‐dicarboxy‐1H‐imidazole ( L ) with different metal ions (Zn2+, Ni2+, Cu2+, Cd2+) led to four new complexes, namely, [M( L )(phen)] [M = Zn ( 1 ); Ni ( 2 ); Cd ( 3 )] and [Cu( L )( 4 )] (phen = 1,10‐phenanthroline). Their structures were determined by single‐crystal X‐ray diffraction analyses, and they were further characterized by elemental analysis, IR spectroscopy, and thermogravimetric analysis. Whereas compounds 1 , 2 , and 3 are discrete units, hydrogen‐bonding interactions play a vital role in these complexes. Compounds 1 and 2 form one‐dimensional (1D) and two‐dimensional (2D) structures through hydrogen‐bondinginteractions with helical character. In 1 , the hydrogen bonds (O–H ··· O) alternately bridge the MII cations of the discrete units to form a one‐dimensional (1D) infinite helical chain. Complex 2 forms a 2D helical layer through parallel hydrogen bonds (N/O–H ··· O/N) between two adjacent helical chains. In 3 , the hydrogen bonds (N–H ··· O) connect adjacent discrete units into a ten‐membered ring with extension into a one‐dimensional double‐chain supramolecular structure. Complex 4 is a two‐dimensional gridlike (4,4) topological layer which is extended to a 3D network by hydrogen bonding. The solid‐state fluorescence spectrum of complex 3 was determined. 相似文献
950.
海洋环境中的重金属及其对海洋生物的影响 总被引:8,自引:0,他引:8
综述了在海洋环境中重金属输入的各种途径及其重金属对海洋生物的影响,重点介绍了重金属在几种海洋生物体内的富集效应及其吸附机理,讨论了海洋重金属污染的现况,并展望了海洋重金属污染研究的前景。 相似文献