全文获取类型
收费全文 | 894篇 |
免费 | 37篇 |
国内免费 | 3篇 |
专业分类
化学 | 590篇 |
晶体学 | 6篇 |
力学 | 20篇 |
数学 | 81篇 |
物理学 | 237篇 |
出版年
2023年 | 2篇 |
2022年 | 24篇 |
2021年 | 31篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 21篇 |
2017年 | 15篇 |
2016年 | 32篇 |
2015年 | 32篇 |
2014年 | 35篇 |
2013年 | 56篇 |
2012年 | 53篇 |
2011年 | 70篇 |
2010年 | 56篇 |
2009年 | 49篇 |
2008年 | 43篇 |
2007年 | 46篇 |
2006年 | 33篇 |
2005年 | 31篇 |
2004年 | 27篇 |
2003年 | 11篇 |
2002年 | 24篇 |
2001年 | 20篇 |
2000年 | 20篇 |
1999年 | 15篇 |
1998年 | 15篇 |
1997年 | 9篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 14篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1924年 | 2篇 |
排序方式: 共有934条查询结果,搜索用时 203 毫秒
31.
The reaction of aluminium(III) with Hydroxynaphtol Blue (HNB) in aqueous media at apparent pH 5.5 results in a red complex that is stable for at least 4 hr. Beer's Law is obeyed up to 1.6 microg/ml of aluminium(III) with an apparent molar absorptivity of 1.66 x 10(4) l.mol(-1). cm(-1) at 569 nm. This paper proposes procedures for aluminium(III) determination by ordinary and first-derivative spectrophotometry. The results demonstrated that the linear dynamic range is 0.03-1.60 microg/ml for ordinary spectrophotometry and 11.8-320.0 ng/ml for first derivative spectrophotometry. The HNB is not selectivity for aluminium, but the addition of EDTA allows the aluminium determination in the presence of accepted amounts of Ca(II), Mg(II), Mn(II), Ba(II), Sr(II), Cd(II), Pb(II), La(III), In(III), Bi(III) and Zn(II). The interference of Cu(II) and Hg(II) can be masked by thiosulphate. Ions such as UO(2)(II), Mo(VI), Co(II), Ti(IV) and PO(4)(III) do interfere seriously. This method was applied for aluminium determination in copper-base alloy, zinc-base alloy, magnesium-base alloy, iron ore, manganese ore, cement, dolomite, feldspar and limestone. The results indicated high accuracy and precision. 相似文献
32.
We develop nonorthogonal projectors, called L?wdin projectors, to construct an effective donor-acceptor system composed of localized donor (D) and acceptor (A) states of a long-distance electron transfer problem. When these states have a nonvanishing overlap with the bridge states these projectors are non-Hermitian and there are various possible effective two-level systems that can be built. We show how these can be constructed directly from the Schr?dinger or Dyson equation projected onto the D-A subspace of the Hilbert space and explore these equations to determine the connection between Hamiltonian and Green function partitioning. We illustrate the use of these effective two-level systems in estimating the electron transfer rate in the context of a simple electron transfer model. 相似文献
33.
34.
35.
The combination of Fourier transform (FT)-Raman spectroscopy and partial least squares (PLS) regression is proposed to be used in off-line kerosene quality control. Here, six important physico-chemical properties have been studied: Abel flash point, initial boiling point (IBP), 10% of distilled sample, final boiling point (FBP), total percentage of aromatic compounds (% aromatics) and viscosity. The Raman spectra were obtained directly from standard 2 ml glass vials ( mm), using a Bruker RFS 100 FT-Raman spectrometer, equipped with a 1064 nm Nd:YAG laser and a Ge detector, in back-scattering mode and accumulating 25 scans (150 s acquisition time) with a laser power of 300 mW. All Raman spectra were unit normalized in order to avoid the influence of the laser power into the regression models. Different Raman shift spectral ranges have been evaluated, the 193.5-1688.1 cm−1 region being the most satisfactory one. Corrected standard errors of prediction of 1.9, 2.3, 2.8 °C, 0.19 cSt and 0.7% were obtained for flash point, IBP, FBP, viscosity and % aromatics, respectively. The influences of the glass vials, sample positioning and laser power have been studied, as well. 相似文献
36.
Jorddy Neves Cruz Mozaniel Santana de Oliveira Eloisa Helena de Aguiar Andrade Rafael Rodrigues Lima 《Molecules (Basel, Switzerland)》2022,27(13)
Molecular modeling approaches are used in a versatile way to investigate the properties of diverse organic and inorganic structures such as proteins, biomolecules, nanomaterials, functionalized nanoparticles, and membranes. However, more detailed studies are needed to understand the molecular nature of interactions established in gelatin biofilms impregnated with bioactive compounds. Because of this, we used computational methods to evaluate how the major compounds of Piper divaricatum essential oil can interact with the gelatin biofilm structure. For this, we used as inspiration the paper published, where various properties of the essential oil impregnated gelatin biofilm P. divaricatum are reported. After our computer simulations, we related our molecular observations to biofilm’s structural and mechanical properties. Our results suggest that the major compounds of the essential oil were able to interrupt intermolecular interactions between the chains of the biofilm matrix. However, the compounds also established interactions with the amino acid residues of these chains. Our molecular analyses also explain changes in the structural and mechanical properties of the essential oil-impregnated biofilm. These results can support the planning of functional packaging impregnated with bioactive compounds that can protect food against microorganisms harmful to human health. 相似文献
37.
Thierry Wesley de Albuquerque Aguiar Jos Josenildo Batista Silvio Assis de Oliveira Ferreira Maíra de Vasconcelos Lima Sampaio Dewson Rocha Pereira Magda Rhayanny Assuno Ferreira Luiz Alberto Lira Soares Ana Maria Mendona de Albuquerque Melo Mnica Camelo Pessoa de Azevedo Albuquerque Andr de Lima Aires Hallysson Douglas Andrade de Araújo Luana Cassandra Breitenbach Barroso Coelho 《Molecules (Basel, Switzerland)》2022,27(15)
Biomphalaria glabrata snails constitute the main vector of schistosomiasis in Brazil, and Bauhinia monandra Kurz, the leaves of which contain BmoLL lectin with biocidal action, is a plant widely found on continents in which the disease is endemic. This work describes the composition of B. monandra preparations and the effect on embryos and adult snails, their reproduction parameters and hemocytes. We also describe the results of a comet assay after B. glabrata exposure to sublethal concentrations of the preparations. Additionally, the effects of the preparations on S. mansoni cercariae and environmental monitoring with Artemia salina are described. In the chemical evaluation, cinnamic, flavonoid and saponin derivatives were detected in the two preparations assessed, namely the saline extract and the fraction. Both preparations were toxic to embryos in the blastula, gastrula, trochophore, veliger and hippo stages (LC50 of 0.042 and 0.0478; 0.0417 and 0.0419; 0.0897 and 0.1582; 0.3734 and 0.0974; 0.397 and 0.0970 mg/mL, respectively) and to adult snails (LC50 of 6.6 and 0.87 mg/mL, respectively), which were reproductively affected with decreased egg deposition. In blood cell analysis, characteristic cells for apoptosis, micronucleus and binucleation were detected, while for comet analysis, different degrees of nuclear damage were detected. The fraction was able to cause total mortality of the cercariae and did not present environmental toxicity. Therefore, B. monandra preparations are promising in combating schistosomiasis since they can control both the intermediate host and eliminate the infectious agent, besides being safe to the environment. 相似文献
38.
Ana Luiza Coeli Cruz Ramos Laiza Andrade Nogueira Mauro Ramalho Silva Ana Carolina do Carmo Mazzinghy Ana Paula Xavier Mariano Tssia Nunes de Albuquerque Rodrigues Ana Cardoso Clemente Filha Ferreira de Paula Angelita Cristine de Melo Rodinei Augusti Raquel Linhares Bello de Araújo Inayara Cristina Alves Lacerda Júlio Onsio Ferreira Melo 《Molecules (Basel, Switzerland)》2022,27(15)
Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min. 相似文献
39.
Jos S. Cmara Rosa Perestrelo Cristina V. Berenguer Carolina F. P. Andrade Telma M. Gomes Basit Olayanju Abuzar Kabir Cristina M. R. Rocha Jos Antnio Teixeira Jorge A. M. Pereira 《Molecules (Basel, Switzerland)》2022,27(9)
Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted. 相似文献
40.
J. B. De Andrade H. L. C. Pinheiro M. V. Andrade 《International journal of environmental analytical chemistry》2013,93(1-4):49-56
Abstract A rapid new analytical protocol was developed for the determination of formaldehyde and acetaldehyde associated to atmospheric particulate matter, at ng/m3 levels. The aerosols were collected on glass fiber filters (8″×10″) at face velocities ranging from 15 m/min to 23 m/min. Aliquots of 15.4 cm2 were sonicated, for 20 min, with 5.0 mL of 0,01% 2,4-dinitrophenylhydrazine (DNPH), 1 % phosphoric acid. The liquid phase was then filtered and the separation and quantification of the corresponding 2,4-dinitrophenylhidrazone (DNPHo) derivatives carried out by reverse phase HPLC. Acetonitrile:water (57:43, v/v) as mobile phase at 1.0 mL/min and absorbance detection at 350 nm and 365 nm for, respectively, formaldehyde-DNPHo (0.04 AUFS) and acetaldehyde-DNPHo (0.01 AUFS) were used. The precision for four different aliquots, from a 8″×10″ glass fiber filter, were under 0.04% for formaldehyde and 14.16 % for acetaldehyde. In Salvador, Bahia, Brazil, formaldehyde and acetaldehyde were determined, respectively, in the range of 6.8 ng/m3 to 27.3 ng/m3 and 9.1 ng/m3 to 54.6 ng/m3. 相似文献