全文获取类型
收费全文 | 1100篇 |
免费 | 25篇 |
国内免费 | 6篇 |
专业分类
化学 | 830篇 |
晶体学 | 10篇 |
力学 | 13篇 |
数学 | 56篇 |
物理学 | 153篇 |
无线电 | 69篇 |
出版年
2022年 | 13篇 |
2021年 | 7篇 |
2020年 | 13篇 |
2019年 | 8篇 |
2018年 | 18篇 |
2017年 | 8篇 |
2016年 | 14篇 |
2015年 | 12篇 |
2014年 | 23篇 |
2013年 | 56篇 |
2012年 | 54篇 |
2011年 | 57篇 |
2010年 | 26篇 |
2009年 | 30篇 |
2008年 | 59篇 |
2007年 | 59篇 |
2006年 | 58篇 |
2005年 | 72篇 |
2004年 | 51篇 |
2003年 | 47篇 |
2002年 | 51篇 |
2001年 | 19篇 |
2000年 | 16篇 |
1999年 | 12篇 |
1998年 | 16篇 |
1997年 | 9篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 14篇 |
1993年 | 11篇 |
1992年 | 16篇 |
1991年 | 14篇 |
1990年 | 14篇 |
1989年 | 14篇 |
1988年 | 16篇 |
1987年 | 18篇 |
1986年 | 11篇 |
1985年 | 14篇 |
1984年 | 22篇 |
1983年 | 11篇 |
1982年 | 17篇 |
1981年 | 6篇 |
1980年 | 12篇 |
1979年 | 14篇 |
1978年 | 8篇 |
1977年 | 11篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1974年 | 5篇 |
1971年 | 7篇 |
排序方式: 共有1131条查询结果,搜索用时 31 毫秒
1.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
2.
Takayuki Nakai Yoshiko Murakami Yoshiaki Sasaki Isamu Fujiwara Shoji Tagashira 《Analytical sciences》2004,20(1):235-237
The extraction and separation of copper(II), zinc(II), cobalt(II), and cadmium(II) were investigated. Both copper(II) and zinc(II) formed ammine-complexes, while cadmium(II) and cobalt(II) formed hydroxide precipitates in an ammonia medium. By the addition of sodium dodecylsulfate (SDS), a copper(II) complex formed an ion-pair (copper-ammine-DS), which was extracted into the SDS phase. However, a zinc(II) complex did not form an ion-pair, and was soluble in water. Copper(II) ion was recovered by stripping (back-extraction) after the addition of hydrochloric acid. This method was applied to the separation of copper(II) in a brass alloy. 相似文献
3.
A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples. 相似文献
4.
5.
Selective oxidation of an AlInAs layer was investigated for enhancement of magneto-optic effect in an optical isolator. Twelve times nonreciprocal phase shift enhancement was estimated from a measured AlInAs-oxide refractive index. 相似文献
6.
Mat Rasol Awang Hassan Hamdani Mutaat Mohd. Shukri Mahmud Wan Badrin Wan Husain Tajuddin Osman Khomsaton Abu Bakar Asmahwati Kassim Zal U''yun Wan Mahmud Ishak ManafTamikazu Kume Shoji Hashimoto 《Radiation Physics and Chemistry》1993,42(4-6):611-616
In solid state fermentation, Pleurotus sajor-caju has been found to be able to degrade at least 30% oil palm empty Fruit Bunch (EFB) fibre leaving 70 % useful materials. Conditions under which fermentation carried out were investigated. It was found that, in the temperature range between 25– 28 °C, relative ph between 6–8, moisture between 60–70 % and medium composition of CaCO3: rice bran 2 %: 5 % were the optimum conditions. The results showed in fermented products that, there were substantial reduction in cellulosic component such as Crude Fiber (CF, 18 %); Acid Detergent Fibre (ADF, 45 %), Neutral Detergent Fibre (NDF, 61 %) and Acid Detergent Lignin (ADL, 14 %). However, Crude Protein (CP, 10%) increased resulted from single cell protein enrichment of mycelial microbial mass. The mass reductions of substrate in fermentation process corresponds to the CO2 released during fermentation. Hence, attributable to the decreased in content of CF, ADF, NDF, and ADL. The digestibility study has also been carried out to determine the useful level of this product to ruminant. Aflatoxin content was detected low in both the initial substrates and products. Based on nutritional value and low content of aflatoxin, the product is useful as a source of roughage to ruminant. 相似文献
7.
The environmental radioactivity caused by the reactor accident at Chernobyl' was investigated from May 7 to May 31 of 1986 in Toyama. Measurement of radioactivities in airborne particles, rain water, drinking water, milk, and mugwort are carried out by gamma-ray spectrometry (pure Ge detector; ORTEC GMX-23195). Ten different nuclides (103Ru, 106Ru, 131I, 132Te-I, 134Cs, 136Cs, 137Cs, 140Ba-La) are identified from samples of airborne particles. In the air samples, a maximum radioactivity concentration of each nuclide is observed on 13th May 1986. The time of the reactor shut-down and the flux of thermal neutron at the reactor were calculated from 131I/132I and 137Cs/134Cs ratio. The exposure dose in Toyama by this accident is given as follows: internal exposure; [thyroid] adult-59 microSv, child-140 microSv, baby-130 microSv, [total body] adult-0.2 microSv, child, baby-0.4 microSv, external exposure; 7 microSv, effective dose equivalent; adult-9 microSv, child-12 Sv, baby-11 microSv. 相似文献
8.
9.
An automated on-line sample-preparation method using a computer-controlled pretreatment system (Auto-Pret AES system) coupled with ICP-AES was developed. In this work, an iminodiacetate chelating resin, packed in a mini-column and installed in the system was employed for the collection/concentration of 13 trace metals, including such toxic metals as Be, Cd, Cr, Cu and Pb. The limits of detection of the proposed method for trace metals were in the range of 0.001 (Be) -0.18 (Pb) ng mL-1. The enrichment factors for metal ions were about 19 times, when 5 mL of samples were used. The sample throughput was 11 h-1. The accuracy and the precision of the method were evaluated using river-water reference materials, SLRS-4 from NRCC, JSAC 0301-1 and JSAC 0302 from the Japan Society for Analytical Chemistry. The proposed method can be favorably applied to the collection/concentration of trace metals in natural water samples. 相似文献
10.
Copper(II) is determined by non-extractive spectrophotometry as a complex of butylene dithiocarbamate formed in situ by reaction between carbon disulfide and pyrrolidine in aqueous Triton X-100 medium. This method is similar to that with butylene dithiocarbamate as starting material in the sense of simplicity, sensitivity, precision and accuracy. Pyrrolidine is the best of seven secondary amines tested in this way for copper determinations. 相似文献