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51.
Ewa Oledzka Marcelina Dyrka Marcin Sobczak Anna Zgadzaj Grzegorz Nalecz-Jawecki 《高分子科学杂志,A辑:纯化学与应用化学》2016,53(3):169-176
This paper describes the development of covalent star-shaped poly(L-lactide/?-caprolactone) random copolymer-oxprenolol (OXP) conjugates as a potential approach to controlling drug release from implantable delivery systems. We prepared synthesized materials containing 14–17 mol% OXP, which were conjugated via an ester bond. The conjugates, which were composed of biodegradable copolyester chains, natural genistein as a central core and drug, were characterized by hydrogen nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FTIR) and viscosity methods. We evaluated the cyto- and genotoxicity of the synthesized copolymeric matrices, followed by the conjugates, with bacterial luminescence, protozoan and Salmonella typhimurium TA1535 assays. Furthermore, we performed in vitro mammalian assays of the obtained products with V79 cells. We found that the in vitro release of OXP from the obtained star-shaped conjugates was dependent on the structure of the synthesized biodegradable matrices. 相似文献
52.
Marta Zalewska Agnieszka Gawin Milena Ściskalska Marcin Moczulski Halina Milnerowicz 《International journal of environmental analytical chemistry》2013,93(14-15):1422-1434
Metallurgy processes are associated with many hazardous and toxic factors, including heavy metals. Exposure to heavy metals can cause damage to different organs, which can be observed through variation in the concentration of proteins in serum. The aim of this study was to evaluate the changes in a serum protein profile of copper smelters exposed to As, Cd and Pb ions, and xenobiotics present in tobacco smoke. A 2.3-fold higher Pb concentration in the blood and a 2.8-fold greater As concentration have been observed in the urine of non-smoking smelters compared to a control group. In the blood of smoking smelters, Cd concentration was 2-fold higher than in non-smoking ones. Serum proteins were separated by capillary electrophoresis, and in the group of non-smoking smelters, a higher amount of α1-globulins was observed. In the group of smoking smelters, fewer α1-globulins were noted. Furthermore, a greater amount of α2-globulins in the serum of smoking and non-smoking workers in relation to the control group was revealed. A positive correlation between the concentration of Cd in the blood and the content of a fraction containing α1- and α2-globulins was revealed. Urine Cd concentration was found to be negatively associated with the α1- and α2-globulins fraction. Observed abnormalities in the proteins profiles of smelters can be important markers when assessing exposure to heavy metals and in the early diagnosis of diseases caused by them. 相似文献
53.
Grzegorz Zi?ba Marcin Rojkiewicz Violetta Kozik Krystyna Jarzembek Anna Jarczyk Aleksander Sochanik Piotr Ku? 《Monatshefte für Chemie / Chemical Monthly》2012,58(4):153-159
Abstract
A series of mono-alkylcarboxylic acid derivatives of tetraphenylporphyrin have been prepared. All the porphyrins were completely characterized by use of mass, 1H NMR, UV–visible, and fluorescence spectroscopy. Experimental log P were determined by use of reversed-phase thin-layer chromatography with use of log P Rekker. These porphyrins are potential photosensitizers in photodynamic therapy. 相似文献54.
We apply the B3LYP and QCISD theoretical methods with the 6-311++G(d,p) basis set and the LANL2DZ effective core potentials to investigate the reaction paths leading to the preparation of the HAuF6, HAu2F11, and HAu3F16 superacids. The Gibbs free energies of deprotonation of these systems are calculated to estimate their acid strength. The thermodynamic stability of the corresponding anionic precursors ((AuF6)–, (Au2F11)–, and (Au3F16)–) and their vertical excess electron detachment energies are evaluated and discussed. The suggested route of the HAu2F11 preparation involves the F– attachment to the Au2F10 reactant which results in the formation of the (Au2F11)– anion whose protonation yields the HAu2F11 superacid. The suggested HAuF6 superacid preparation route is based on a qualitatively similar scheme and involves the conversion of the AuF5 reactant into the (AuF6)– anion followed by its protonation. The proposed path for the HAu3F16 superacid preparation involves the attachment of AuF5 to HAu2F11. 相似文献
55.
Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene. 相似文献
56.
Dr. Srijit Biswas Dr. Christian Dahlstrand Rahul A. Watile Dr. Marcin Kalek Prof. Dr. Fahmi Himo Prof. Dr. Joseph S. M. Samec 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17939-17950
Gold(I)‐chloride‐catalyzed synthesis of α‐sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α‐sulfenylated aldehydes and ketones in 60–97 % yield. Secondary aliphatic propargylic alcohols generated α‐sulfenylated ketones in yields of 47–71 %. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3‐position, and that the hydride from the alcohol was transferred to the 2‐position of the product. Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2‐position of propargylic alcohol was determined by a low‐energy, five‐membered cyclic protodeauration transition state instead of the strained, four‐membered cyclic transition state found for attack at the 3‐position. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2‐hydride shift, generating the final product of the reaction. 相似文献
57.
Pawel J. Kulesza Silvia Zamponi Marcin A. Malik Krzysztof Miecznikowski Mario Berrettoni Roberto Marassi 《Journal of Solid State Electrochemistry》1997,1(1):88-93
Using Prussian blue (PB) electrodeposited on gold-covered foil as a model system, we have demonstrated the usefulness of
the time-derivative measurements of absorbance versus potential (linear potential-scan voltabsorptometry) for spectroelectrochemical
characterization of thin electrochromic films. The time-derivative signals were monitored for PB at 680 and 420 nm in potassium,
sodium and lithium electrolytes. Information obtained from cyclic voltabsorptometry is equivalent or complementary to that
from conventional cyclic voltammetry. In the case of PB films investigated in lithium electrolyte, the voltabsorptometric
time-derivative peaks are better defined than the respective voltammetric peaks. The combination of voltabsorptometry with
voltammetry enables molar absorptivity and/or film loading to be determined. Also, concentration changes of differently colored
mixed-valence redox centers can be monitored as a function of applied potential.
Received: 16 January 1997 / Accepted: 11 March 1997 相似文献
58.
Mikko Keränen Marcin Gnyba Paavo Raerinne Terho Kololuoma Arto Maaninen Juha T. Rantala 《Journal of Sol-Gel Science and Technology》2004,31(1-3):369-372
Sol–gel adhesive material for isostatic hotpressing lamination process was synthesized using 3-aminopropyltrimethoxysilane (APTES), 3-glycidyloxypropyltrimethoxysilane (GPTS) and methacryloxypropyltrimethoxysilane (MPTS) as precursors. Reaction dynamics between APTES and GPTS was followed on-line with Raman spectroscopy. The lamination process was optimized by varying hotpressing times and pressures at the constant temperature. Mechanical shear strength properties were found to be excellent for studied composition, 25–30 kg/cm2 at its best. One possible application of laminated polycarbonate (PC) structure is a soldier helmet visor. Therefore, the ballistic protection properties were tested by shooting with 1.1 gram standard fragment, and determining the v50 velocity value, which corresponds to 50% perforation. The laminated structure gave 5.7% better protection compared with the solid polycarbonate. The laminated components were found to have high optical transparency at the visible wavelengths as well as high environmental stability. 相似文献
59.
Bonding analysis in β-diketiminate boron and related systems has been performed. For the optimized geometries (MP2/aug-cc-pVTZ),
the post-SCF electron density function has been produced and its topological parameters have been analyzed according to Atoms in Molecules
Quantum Theory approach. The B–N bond has characteristics similar to those found for TM–ligand bonding. The symmetric character
of the B–N interaction found for the β-diketiminate boron results from the fully π-electron delocalized character of the β-diketiminate moiety. If the π-electron system in NCCCN sequence of bonds is localized, the asymmetric B–N bonding is enforced.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
相似文献
Marcin PalusiakEmail: |
60.
Marcin Kubisiak Karolina Zelga Wojciech Bury Iwona Justyniak Krzysztof Budny-Godlewski Zbigniew Ochal Janusz Lewiński 《Chemical science》2015,6(5):3102-3108
This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by RnM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn4(μ3-OOtBu)3(μ4-O)(O2CEt)3]2, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn4(μ4-O)(μ3-2-O–THF)(O2CEt)5]2, provide clear mechanistic signatures for the mode of function of the RZn(O2CR′)/air system. 相似文献