全文获取类型
收费全文 | 1063篇 |
免费 | 52篇 |
专业分类
化学 | 690篇 |
晶体学 | 4篇 |
力学 | 27篇 |
数学 | 158篇 |
物理学 | 236篇 |
出版年
2023年 | 5篇 |
2022年 | 56篇 |
2021年 | 60篇 |
2020年 | 17篇 |
2019年 | 28篇 |
2018年 | 22篇 |
2017年 | 19篇 |
2016年 | 80篇 |
2015年 | 49篇 |
2014年 | 55篇 |
2013年 | 107篇 |
2012年 | 58篇 |
2011年 | 57篇 |
2010年 | 46篇 |
2009年 | 51篇 |
2008年 | 49篇 |
2007年 | 26篇 |
2006年 | 41篇 |
2005年 | 19篇 |
2004年 | 23篇 |
2003年 | 11篇 |
2002年 | 10篇 |
2001年 | 7篇 |
2000年 | 9篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1997年 | 10篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1992年 | 3篇 |
1991年 | 9篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 20篇 |
1983年 | 7篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 9篇 |
1977年 | 10篇 |
1975年 | 8篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1972年 | 5篇 |
排序方式: 共有1115条查询结果,搜索用时 15 毫秒
181.
Depleted uranium (DU) is a by-product of the uranium enrichment process for nuclear fuel. According to the Commission Decision 2002/657/EC, a confirmatory method for the quantification of DU in freeze-dried fish was developed by isotope ratio dynamic reaction cell inductively coupled plasma-mass spectrometry (IR-DRC-ICP-MS). A preliminary study was performed to determine the following parameters: instrumental detection limit (IDL), isotopic ratio measurement limit (IRML), percentage of DU (P(DU)) in presence of natural uranium (NU) and limit of quantification (LoQ(DU)). The analyses were carried out by means of IR-DRC-ICP-MS. Ammonia was the reaction gas used for the dynamic reaction cell. In addition, a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) was employed to calculate the within-laboratory reproducibility. For the confirmatory method the following parameters were determined: (a) trueness; (b) precision; (c) critical concentrations alpha and beta (CC(alpha), CC(beta)); (d) specificity; (e) stability. Trueness was assessed by using the recovery tests. The recovery and within-laboratory reproducibility were determined by fortifying the blank digested solution of dogfish tissue: six aliquots were fortified at 1, 1.5 and 2 times the LOQ(DU) with 25.0, 37.5 and 50.0 ng L(-1) or 4.16, 6.24, 8.32 microg kg(-1) with a recovery of -8.2, +9.5 and +9.6%, respectively and a within-laboratory reproducibility (three analytical run) of 15.5, 8.0 and 11.0%, respectively. The results for the decision limit and the detection capability were: CC(alpha) = 11.69 ng L(-1) and CC(beta) = 19.8 ng L(-1). The digested solutions resulted to be stable during testing time (60 days) and the method can be considered highly specific as well. 相似文献
182.
Nonlinear Dynamics - Spatial relations between neurons in the network with time delays play a crucial role in determining dynamics of the system. During the development of the nervous system,... 相似文献
183.
ukasz Orze Maria Oszajca Justyna Polaczek Dominika Porbska Rudi van Eldik Grayna Stochel 《Molecules (Basel, Switzerland)》2021,26(16)
Pressure is one of the most important parameters controlling the kinetics of chemical reactions. The ability to combine high-pressure techniques with time-resolved spectroscopy has provided a powerful tool in the study of reaction mechanisms. This review is focused on the supporting role of high-pressure kinetic and spectroscopic methods in the exploration of nitric oxide bioinorganic chemistry. Nitric oxide and other reactive nitrogen species (RNS) are important biological mediators involved in both physiological and pathological processes. Understanding molecular mechanisms of their interactions with redox-active metal/non-metal centers in biological targets, such as cofactors, prosthetic groups, and proteins, is crucial for the improved therapy of various diseases. The present review is an attempt to demonstrate how the application of high-pressure kinetic and spectroscopic methods can add additional information, thus enabling the mechanistic interpretation of various NO bioinorganic reactions. 相似文献
184.
Muhammad Modassar A. N. Ranjha Rabia Kanwal Bakhtawar Shafique Rai Naveed Arshad Shafeeqa Irfan Marek Kieliszek Przemysaw ukasz Kowalczewski Muhammad Irfan Muhammad Zubair Khalid Ume Roobab Rana Muhammad Aadil 《Molecules (Basel, Switzerland)》2021,26(16)
Different parts of a plant (seeds, fruits, flower, leaves, stem, and roots) contain numerous biologically active compounds called “phytoconstituents” that consist of phenolics, minerals, amino acids, and vitamins. The conventional techniques applied to extract these phytoconstituents have several drawbacks including poor performance, low yields, more solvent use, long processing time, and thermally degrading by-products. In contrast, modern and advanced extraction nonthermal technologies such as pulsed electric field (PEF) assist in easier and efficient identification, characterization, and analysis of bioactive ingredients. Other advantages of PEF include cost-efficacy, less time, and solvent consumption with improved yields. This review covers the applications of PEF to obtain bioactive components, essential oils, proteins, pectin, and other important materials from various parts of the plant. Numerous studies compiled in the current evaluation concluded PEF as the best solution to extract phytoconstituents used in the food and pharmaceutical industries. PEF-assisted extraction leads to a higher yield, utilizes less solvents and energy, and it saves a lot of time compared to traditional extraction methods. PEF extraction design should be safe and efficient enough to prevent the degradation of phytoconstituents and oils. 相似文献
185.
Maciej Saktura Anna Skrzyska Sebastian Frankowski Sylwia Wdka ukasz Albrecht 《Molecules (Basel, Switzerland)》2021,26(16)
In our studies, the organocatalytic 1,3-dipolar cycloaddition between 2-nitrobenzofurans or 2-nitrobenzothiophene and N-2,2,2-trifluoroethyl-substituted isatin imines has been developed. The reaction has been realized by employing bifunctional organocatalysis, with the use of squaramide derivative being crucial for the stereochemical efficiency of the process. The usefulness of the cycloadducts obtained has been confirmed in selected transformations, including aromative and non-aromative removal of the nitro group. 相似文献
186.
A comparative study of dynamic response including damage and rupture processes of thin metallic plates subjected to shock-wave impulses – explosions is presented. The results of the finite element numerical analysis are related to experiments. Due to high strain rate during explosions the elasto-viscoplastic Chaboche's constitutive law including damage effects has been applied. For the assumed model proper material parameters identification has been done. In the dynamic, geometrically non-linear analysis the MSC.Marc system has been used. A good correlation between numerical and experimental results has been observed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
187.
Chromium(III)-lutidinato complexes of general formula [Cr(lutH)
n
(H2O)6−2n
]3−n (where lutH− is N,O-bonded lutidinic acid anion) were obtained and characterized in solution. Acid-catalysed aquation of [Cr(lutH)3]0 leads to only one ligand dissociation, whereas base hydrolysis produces chromates(III) as a result of subsequent ligand liberation
steps. The kinetics of the first ligand dissociation were studied spectrophotometrically, within the 0.1–1.0 M HClO4 and 0.4–1.0 M NaOH range. In acidic media, two reaction stages, the chelate-ring opening and the ligand dissociation, were
characterized. The dependencies of pseudo-first-order rate constants on [H+] are as follows: k
obs1 = k
1 + k
−1/K
1[H+] and k
obs2 = k
2
K
2[H+]/(1 + K
2[H+]), where k
1 and k
2 are the rate constants for the chelate-ring opening and the ligand dissociation, respectively, k
−1 is the rate constant for the chelate-ring closure, and K
1 and K
2 are the protonation constants of the pyridine nitrogen atom and coordinated 2-carboxylate group in the one-end bonded intermediate,
respectively. In alkaline media, the rate constant for the first ligand dissociation depends on [OH−]: k
obs1 = k
OH(1) + k
O[OH−], where k
OH(1) and k
O are rate constants of the first ligand liberation from the hydroxo- and oxo-forms of the intermediate, respectively, and
K
2 is an equilibrium constant between these two protolytic forms. Kinetic parameters were determined and a mechanism for the
first ligand dissociation is proposed. The kinetics of the ligand liberation from [Cr(lut)(OH)4]3− were also studied and the values of the pseudo-first-order rate constants are [OH−] independent. 相似文献
188.
Maria G. Babashkina Damir A. Safin Dr. Łukasz Szyrwiel Maria Kubiak Felix D. Sokolov Yuri V. Starikov Henryk Kozlowski 《无机化学与普通化学杂志》2009,635(3):554-557
Reaction of the potassium salt of N‐thiophosphorylated thiourea α‐naphthylNHC(S)NHP(S)(OiPr)2 ( HL ) with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to the mononuclear complex [Cu(PPh3)2L–S,S′]. By using copper(I) iodide instead ofCu(PPh3)3I, the polynuclear complex [Cun(L–S,S′)n] was obtained. The structures of these compounds were investigated by elemental analysis, 1H and 31P{1H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh3)2L were determined by single‐crystal X‐ray diffraction. 相似文献
189.
Stanis?aw Le?niak Anna Chrostowska Dawid Kuc Saïd Khayar ?ukasz Urbaniak 《Tetrahedron》2009,65(51):10581-6916
The synthesis of [(E)-arylimino]-acetonitriles 3 has been described. It was found that the title compounds can be obtained on the three ways, namely by: (i) dehydrogenation of arylaminoacetonitriles 1, (ii) thermal fragmentation of 1-aryl-4-cyano-β-lactams 4 and (iii) retro-ene reaction of (allyl-p-methoxyphenyl-amino)-acetonitrile (7a) under FVT conditions. 1H and 13C NMR spectra of compounds 3, 5 and 6, and all their precursors 1 and 4, were recorded and analysed in detail using chemical shifts δH and δC [from GIAO DFT B3LYP/6-31(d) calculations] and J-couplings predicted at the DFT B3LYP/IGLO-II level. Also, UV-photoelectron spectra of 4a,d and 3a,d were measured and analysed considering the theoretical evaluation of their ionisation potentials. 相似文献
190.
In this work, complexes of Zr(IV) and Al(III) cations with 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraazaporphine (TAP) were tested as ionophores in plasticized PVC membranes of ion-selective electrodes. It was found that both tested ionophores show enhanced affinity towards fluoride anion. High fluoride selectivity was observed in the presence of anionic or cationic additives in the membrane, which indicates that proposed compounds work according to charged or neutral carrier mechanism, depending on membrane composition and pretreatment.tert-Butyl substituents, present in the structure of tested compounds, were supposed to prevent formation of ionophore dimers within the membrane phase. This process was found to be responsible for some unfavorable potentiometric properties of electrodes based on complexes of Zr(IV) and Al(III) cations with porphyrins (compounds closely related to tetra-tert-butyl-5,10,15,20-tetraazaporphine). As it was shown using spectrophotometrical measurements, Al(III)-TAP was not susceptible to dimerization, while dimer formation was observed for Zr(IV)-TAP. In full agreement with these observations, electrodes with membranes containing Al(III)-TAP responded in near-Nernstian and fast manner towards fluoride anion, while the employment of Zr(IV)-TAP as ionophore resulted in super-Nernstian and sluggish response. Plasticized PVC membranes doped with Al(III)-TAP and 20 mol% of lipophilic anionic additives shown remarkable F− selectivity, with selectivity coefficients, , as follows: −4.4 (Y−Br−), −4.3 (Cl−), −4.2 (NO3−), −3.6 (SCN−), −2.9 (ClO4−). 相似文献