全文获取类型
收费全文 | 5344篇 |
免费 | 606篇 |
国内免费 | 605篇 |
专业分类
化学 | 3571篇 |
晶体学 | 26篇 |
力学 | 237篇 |
综合类 | 45篇 |
数学 | 69篇 |
物理学 | 2607篇 |
出版年
2024年 | 13篇 |
2023年 | 87篇 |
2022年 | 237篇 |
2021年 | 231篇 |
2020年 | 248篇 |
2019年 | 185篇 |
2018年 | 155篇 |
2017年 | 270篇 |
2016年 | 323篇 |
2015年 | 287篇 |
2014年 | 370篇 |
2013年 | 372篇 |
2012年 | 418篇 |
2011年 | 336篇 |
2010年 | 259篇 |
2009年 | 305篇 |
2008年 | 309篇 |
2007年 | 319篇 |
2006年 | 254篇 |
2005年 | 227篇 |
2004年 | 234篇 |
2003年 | 167篇 |
2002年 | 164篇 |
2001年 | 102篇 |
2000年 | 99篇 |
1999年 | 101篇 |
1998年 | 97篇 |
1997年 | 88篇 |
1996年 | 51篇 |
1995年 | 49篇 |
1994年 | 39篇 |
1993年 | 38篇 |
1992年 | 24篇 |
1991年 | 29篇 |
1990年 | 26篇 |
1989年 | 12篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有6555条查询结果,搜索用时 15 毫秒
51.
Takashi Hayashita Akiyo Yamauchi Ai-Jun Tong Jong Chan Lee Bradley D. Smith Norio Teramae 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(1-2):87-94
The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water. 相似文献
52.
53.
一种新型的表面声波阻抗传感器及其在液相体系中的应用姚守拙,陈康,刘德忠,聂利华(湖南大学化学化工系,长沙,410082)关键词表面声波,阻抗传感器,液相应用表面声波传感器(SAWS)具有较高的灵敏度和检测精度,已广泛应用于气体微量组分分析、色谱检测和... 相似文献
54.
Chouhaid Nasr Prashant V. Kamat Surat Hotchandani 《Journal of Electroanalytical Chemistry》1997,420(1-2)
A photoelectrochemical cell with a coupled SnO2|CdSe nanocrystalline semiconductor electrode has been prepared by sequential deposition of SnO2 and CdSe films onto an optically transparent electrode (OTE), and its photoelectrochemical behavior has been studied. The results show that the coupling of CdSe with SnO2 leads to an improvement in the performance of OTE|SnO2|CdSe over OTE|CdSe cells in terms of increased incident photon-to-current conversion efficiency, increased stability and smaller reversal of current. The favorable positioning of the energy bands of SnO2 and CdSe is responsible for the above observations. Various photoelectrochemical parameters of the OTE|SnO2|CdSe cell obtained for an incident light power of 0.31 mW cm−2 at 470nm, are as follows: Isc ≈ 25–30 μA cm−2, Voc ≈ 0.5–0.6 V, ƒƒ = 0.47 and a power conversion efficiency of about 2.25%. 相似文献
55.
A re-usable and sensitive cryptand-22-coated quartz-crystal membrane piezoelectric sensor with a homemade computer interface for signal acquisition and data processing was prepared and applied as a gas-chromatographic (GC) detector for various organic molecules. The oscillating frequency of the quartz crystal decreased due to the adsorption of organic molecules on cryptand-22. Effects of functional group, molar mass, steric hindrance and polarity of organic molecules on frequency responses of the cryptand-coated piezoelectric crystal detector were investigated. The cryptand-coated piezoelectric crystal GC detector had demonstrated high sensitivity for various polar organic molecules and good reproducibility when re-used. The frequency responses of the cryptand-coated crystal for various molecules were in the following order: carboxylic acids (RCOOH)primary amines (R-NH2)>alcohols (ROH)>secondary amines (R2NH)>tertiary amines (R3N)>ketones. More polar molecules exhibited better frequency responses. The effect of temperature and amount of coating on the frequency responses of cryptand-coated crystal GC detector were also investigated. The cryptand-coated piezoelectric crystal GC detector compared well with the commercial thermal conductivity detector (TCD). 相似文献
56.
The determination of glutamate pyruvate activity (GPT) is of particular clinical importance. A portable GPT sensor for both diagnostic and home-care purpose is highly expected. A highly sensitive and stable l-glutamate sensor was fabricated for the rapid detection of the GPT activity in serum. The sensor is composed of immobilized l-glutamate oxidase in a photo-crosslinkable polymer (PVA-SbQ) membrane on a palladium-deposited screen-printed carbon electrode. The sensor exhibited high sensitivity (detection limit of 50 nM for monosodium glutamate), remarkable long-term stability in storage (5 months in the dry dark state and 1 month in buffer solution) and good reproducibility (R.S.D.=2.6%, n=100). The electrode-to-electrode reproducibility was found to depend on the composition of the polymeric matrix. The optimal substrate composition for the detection of GPT activity was 1 mM α-ketoglutarate and 100 mM l-alanine. The GPT activity in serum can be determined within 3 min. The response of the sensor to GPT activity is linear over the range of 8-250 U/l. Good correlation between the sensor and the Sigma GPT assay kit was achieved (R2=0.9958). The sensor is potentially applicable to a home-care purpose when a portable measuring device is adapted. 相似文献
57.
We report a nanoscale lipid membrane-based sensor of conjugated polydiacetylene (PDA) vesicles for fluorescence detection of organic amines. The vesicle sensor was constructed by incorporation of a BODIPY fluorescent dye into the PDA vesicles. The fluorescent properties of the resulting vesicles can be manipulated by adjusting lipid components, and are controlled by environmental and solution conditions. The fluorescence of the BODIPY dye was significantly quenched in the polymerization of diacetylene lipid vesicles by a UV irradiation process. However, it was sufficiently recovered by external stimuli such as a hike of solution pH. The fluorescence recovery process was reversible, and a decrease in solution pH resulted in repeated quenching. The reported system transforms an external stimulus into a large fluorescence intensity change, demonstrating great potential in developing new signal reporting method for biosensor design. The quench-recovery phenomenon of the BODIPY-PDA is believed to be related to the energy transfer between the dye and the PDA conjugate backbone. The vesicle sensor was applied for detecting an organic amine, triethylamine (TEA) and a large linear relationship was obtained between the increase in fluorescence intensity and the concentrations of TEA. The detection limit of TEA by vesicle sensors using fluorescence recovery was found to be 10 μM. 相似文献
58.
Martin Püntener 《Analytica chimica acta》2004,503(2):187-194
The lower detection limit of polymeric membrane ion-selective electrodes (ISEs) is impaired by zero-current ion fluxes through the organic phase. This adverse effect is largely eliminated by covalently attaching the ionophore to a polymer backbone. To this purpose, the Pb2+-selective ligand, 4-tert-butylcalix[4] arene-tetrakis(N,N′-dimethylthioacetamide) is substituted on its upper rim by a diol derivative which is subsequently copolymerized with poly(tetrahydrofuran)diol and 2,2,4-trimethylhexamethylene diisocyanate to the corresponding polyurethane. By measurements on sandwich membranes, it is shown that through binding the ionophore to the polymer, the mobility of Pb2+ in the ISE membrane is strongly reduced. As a consequence, the response range of such an ISE is extended by several orders of magnitude. This is the case even when using an internal electrolyte that with an ISE based on a mobile ionophore leads to strong deviations from the linear response because of ion uptake from the sample into the membrane or ion release from the membrane into the sample. With a conventional inner filling solution of 10−1 M Pb(NO3)2, a lower detection limit of 1.7×10−9 M Pb2+ has been achieved in the presence of 10−4 M Na+. 相似文献
59.
Many studies have focused on effective ways to exploit enzyme immobilization on an electrode surface to help improve the performance of enzymatic electrochemical biosensors. Herein, a novel glucose sensor was fabricated by immobilizing glucose oxidase (GOx) onruthenium-based conjugated polymer (CP) and metal-organic framework (MOF) nanocomposites. This has not only reduced the applied potential to 0.2 V (vs. Ag/AgCl), but also improved the effective surface area for enzyme immobilization.PPG@Ru@UiO-66-NH2 was tailored by controlled chemical synthesis from a pre-synthesized water-soluble conjugated polymer (poly(N-phenylglycine)) and metal-organic framework (UiO-66-NH2). The resulting nanocomposites were characterized using Fourier transform infrared spectroscopy, X-ray fluorescence, scanning electron microscopy, and cyclic voltammetry. The PPG@Ru@UiO-66-NH2/GOx coated electrodedisplayed a linear measurementrange for glucose from 1 mM to 10 mM, with a sensitivity of 45.92 μA ⋅ mM−1cm−1 and limit of detection of5 μM( ). Furthermore, the practical application of the fabricatedglucosesensor was tested in simulative blood samples with satisfactoryaccuracy. This approach alsoopens a new door for applications regarding both enzymatic electrochemical biosensors and enzymatic biofuel cells (EBFCs). 相似文献
60.
《Electroanalysis》2004,16(10):827-831
An amperometric detector for hydrophobic ions based on a plasticized poly(vinyl) chloride (PVC) membrane incorporated in a flow‐injection system was developed. A four‐electrode potentiostat with ohmic drop compensation was used, while a flow‐through cell incorporated the four electrodes and the membrane, which contained tetrabutylammonium tetraphenylborate. When the influence of the applied potential and of the flow‐injection variables on the determination of tetrabutylammonium was studied, a linear relationship was observed between current peak height and ion concentration over a range of 5×10?6–6×10?5 M tetrabutylammonium. Good repeatability and between‐day reproducibility and high sample frequency were obtained. The effect of other ions was studied. Two different amperometric methods, indirect and direct, were also developed for the determination of dodecylsulfate in the concentration range 3×10?5–9×10?4 M. 相似文献