全文获取类型
收费全文 | 3572篇 |
免费 | 351篇 |
国内免费 | 343篇 |
专业分类
化学 | 2957篇 |
晶体学 | 41篇 |
力学 | 10篇 |
综合类 | 26篇 |
数学 | 15篇 |
物理学 | 1217篇 |
出版年
2024年 | 6篇 |
2023年 | 25篇 |
2022年 | 74篇 |
2021年 | 85篇 |
2020年 | 73篇 |
2019年 | 84篇 |
2018年 | 88篇 |
2017年 | 118篇 |
2016年 | 129篇 |
2015年 | 129篇 |
2014年 | 168篇 |
2013年 | 332篇 |
2012年 | 210篇 |
2011年 | 227篇 |
2010年 | 180篇 |
2009年 | 227篇 |
2008年 | 203篇 |
2007年 | 269篇 |
2006年 | 228篇 |
2005年 | 211篇 |
2004年 | 156篇 |
2003年 | 156篇 |
2002年 | 134篇 |
2001年 | 102篇 |
2000年 | 104篇 |
1999年 | 87篇 |
1998年 | 73篇 |
1997年 | 59篇 |
1996年 | 40篇 |
1995年 | 41篇 |
1994年 | 37篇 |
1993年 | 33篇 |
1992年 | 34篇 |
1991年 | 20篇 |
1990年 | 14篇 |
1989年 | 15篇 |
1988年 | 22篇 |
1987年 | 10篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 2篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 1篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有4266条查询结果,搜索用时 15 毫秒
61.
The bridged tri-imidazoliums 3.3X^--5.3X^-(X^-=PF6^-,Br^-,I^-)and bis-imidazoliums 6.2PF6^- were synthesized by N-quaternization of imidazole derivative 1 in acetonitrile under reflux.UV spectroscopic titration experiments showed that the halide salts and hexafluorophosphate salts of these imidazoliums exhibited good recognition toward anions in water and in acetonitrile,respectively. 相似文献
62.
超分子结构水杨酸根插层水滑石的组装及结构与性能研究 总被引:26,自引:0,他引:26
以锌铝水滑石ZnAl-CO3 LDHs为前体(主体),以乙二醇为分散介质,用离子 交换法组装了水杨酸根(客体)插层水滑石ZnAl-[o-HO(C6H4)COO]LDHs,并用XRD ,FT-IR,TG-DTA等手段对样品进行了表征。结果表明,能过控制离子交换条件, 水杨酸根阴离子可取代锌铝水滑石前体层间的CO3^2-离子,组装得到晶体结构良好 的水杨酸根插层水滑石。通过研究发现,主体水滑石层板与客体以静电力和氢键相 互作用,得到的超分子结构材料紫外阻隔作用增强并具有较好的稳定性,从而成为 一种集屏蔽和吸收双重功能的新型无机-有机得合紫外阻隔材料。 相似文献
63.
Mariko Kusabe Hiromitsu Kozuka Satoru Abe Hiroshi Suzuki 《Journal of Sol-Gel Science and Technology》2007,44(2):111-118
Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC3H7
i
)4 was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The
viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO2/(HPC + TiO2) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC3H7
i
)4 is converted into TiO2. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical
absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing
titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability
in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania
content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where
cracking did not occur at higher HPC contents even when the substrate was bent. 相似文献
64.
本文采用紫外光谱(UV/VIS)、荧光光谱和圆二色谱等方法,对汞(II)与牛血红蛋白(BHb)的相互作用进行了研究。结果表明:Hg2 处理导致BHb紫外吸收的增加,出现LMCT带,并随Hg2 浓度的增加LMCT带强度显著增强。BHb分子中Soret带的吸收随着Hg2 作用时间的增加而持续降低,表明Hg2 使部分血红素辅基从BHb中脱离出来。蛋白内源荧光光谱显示,Hg2 与BHb的结合会影响蛋白质的三级结构和四级结构。远紫外圆二色谱表明,Hg2 处理会导致BHb蛋白的α-螺旋含量减少。 相似文献
65.
《Journal of separation science》2003,26(14):1259-1262
Microemulsion electrokinetic chromatography (MEEKC) has been applied to the separation of some UV filters (Eusolex 4360, Eusolex 6300, Eusolex OCR, Eusolex 2292, Eusolex 6007, Eusolex 9020, Eusolex HMS, Eusolex OS, and Eusolex 232) commonly used in sunscreen lotions. Use of a MEEKC buffer with a mixed surfactant system to stabilize the oil droplets and an organic modifier in the aqueous phase allowed separation of most of the selected analytes in a single run in a system fitted with a diode array detector recording three wavelengths (240 nm, 300 nm, and 380 nm) simultaneously. The microemulsion employed consisted of 2.25 g of SDS, 0.75 g of Brij 35, 6.6 g 1‐butanol, 0.8 g n‐octane, 17.5 g 2‐propanol, and 72.1 g of 10 mM borate buffer (pH 9.2). Detection limits from 0.65 to 6.0 μg/mL were obtained and the calibration plots were linear over at least one order of magnitude for all analytes. The developed method could be applied to the determination of UV filters in several sun protection products including lotions, milks, and oils. Comparison of the obtained data with those from an HPLC method described in the literature showed acceptable agreement. 相似文献
66.
Summary A new system for the rapid and sensitive analysis of underivatized carbohydrates has been established using capillary zone electrophoresis with indirect UV detection. At an applied potential of 28 kV, sugars and sugar acids could be separated by the combined effects of electroendosmosis and electrophoresis within 20 minutes in a fused silica capillary of 50 m internal diameter and an effective length of 100 cm using 6mM sorbic acid, pH 12.1, as both carrier electrolytie and chromophore. The alkaline pH ensured ionization of the sugars and, hence, their detection by means of charge displacement. Furthermore, the chosen concentration of sorbic acid allowed the smallest fractional change in the background signal to be measured. While the electrophoretic mobilities of the sugars were found to increase within a pH range of 11.9 to 12.3, those of the sugar acids were not affected. Due to the increasing competition of hydroxide ions in the displacement of the chromophore with rising pH, a significant loss of sensitivity is observed at pH values higher than 12.1 and this pH was found to provide sufficient resolution, optimum sensitivity, and a acceptably short analysis time. Under these conditions, a lower detection limit of 2 pmol was obtained for glucose. 相似文献
67.
UV/Vis-spectra of Cyclosilanes (SiX
2)
n
withX=Cl, Br, I, OMe andn=4, 5, 6 are recorded and interpreted qualitatively. The spectra exhibit increasing influence of the substituents on the Si-Si-bond system within the rings in the order Cl OMe Br I. At the low energy side of the spectra weak absorption bands, possibly due to intramolecular charge transfer transitions, appear. The strong inductive effect of the electronegative substituents is documented by a marked increase of the first IP's compared to permethylcyclosilanes. 相似文献
68.
69.
Vladislav?Tomi?i?Email author Vjekoslav?Butorac Jadranka?Viher Vladimir?Simeon 《Journal of solution chemistry》2005,34(6):613-616
The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO3−(aq) centered at ≈200 nm was studied in the temperature range 10–70 ∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion. 相似文献
70.
A continuous-wave 280 nm light-emitting diode (LED) was used as the excitation source for native fluorescence detection of proteins in CE. The operating current and temperature of the LED were optimized in order to achieve high luminescence power. It was found that a forward current of 30 mA and a temperature of approximately 5 degrees C gave the best S/N. By using a set of two ball lenses to focus light from the LED, we achieved a spot of approximately 200 mum with a power of 0.1-0.2 mW on the detection window. Fluorescence was collected with a ball lens at 90 degrees angle through a bandpass filter onto a photomultiplier tube. In CZE an LOD of 20 nM for conalbumin was reached. In capillary gel electrophoresis all eight proteins from a commercial standard kit were detected with high S/N. For a 10 microg/mL total protein mixture, S/N was better than 3 for all proteins in solution. Further improvement in LOD should be possible on utilization of an LED with higher luminescence power. 相似文献