全文获取类型
收费全文 | 7228篇 |
免费 | 299篇 |
国内免费 | 36篇 |
专业分类
化学 | 6103篇 |
晶体学 | 49篇 |
力学 | 80篇 |
数学 | 685篇 |
物理学 | 646篇 |
出版年
2024年 | 4篇 |
2023年 | 63篇 |
2022年 | 257篇 |
2021年 | 284篇 |
2020年 | 184篇 |
2019年 | 167篇 |
2018年 | 107篇 |
2017年 | 127篇 |
2016年 | 252篇 |
2015年 | 264篇 |
2014年 | 264篇 |
2013年 | 424篇 |
2012年 | 582篇 |
2011年 | 611篇 |
2010年 | 415篇 |
2009年 | 392篇 |
2008年 | 477篇 |
2007年 | 481篇 |
2006年 | 405篇 |
2005年 | 386篇 |
2004年 | 315篇 |
2003年 | 259篇 |
2002年 | 220篇 |
2001年 | 69篇 |
2000年 | 63篇 |
1999年 | 60篇 |
1998年 | 42篇 |
1997年 | 48篇 |
1996年 | 36篇 |
1995年 | 49篇 |
1994年 | 22篇 |
1993年 | 26篇 |
1992年 | 20篇 |
1991年 | 22篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 17篇 |
1986年 | 12篇 |
1985年 | 18篇 |
1984年 | 15篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1978年 | 6篇 |
1975年 | 4篇 |
1970年 | 2篇 |
1968年 | 2篇 |
1965年 | 2篇 |
排序方式: 共有7563条查询结果,搜索用时 15 毫秒
91.
Carla M. Bossu Edilene C. Ferreira Fernanda S. Chaves Eveline A. Menezes Ana Rita A. Nogueira 《Microchemical Journal》2006,84(1-2):88-92
A flow injection system was proposed to evaluate the transient product of a colorimetric reaction between hydrolysable tannin and potassium iodate (KIO3) solution. The system optimization was accomplished by using statistical methods based on experimental design. Flow rate of KIO3 solution, sample volume, carrier flow rate, and reaction coil were the selected factors for evaluation. On screening step, complete factorial 24 was used and two levels for each selected factor were studied. For the optimization phase, a centered face composite design 22 + star was employed to evaluate sample volume and flow rate of KIO3 solution, which were the factors identified in the screening phase as having more influence on the absorbance signal. After optimization, the proposed system was compared with batch determination. Some characteristics, such as analytical frequency, reagent consumption and chemical residues generation presented better results by the use of the proposed system if compared with batch method. The system presented good repeatability with standard deviation lower than 3%, for n = 10, linearity (R2 = 0.9974) for tannic acid standard, analytical frequency of 15 injections h− 1 and limit of quantification of 24 mg L− 1 of tannic acid. Good results were obtained when the proposed system was applied to hydrolysable tannin determination in Stryphnodendron barbatimão, Eucalyptus citriodora and Phyllanthus niruri, samples of plants commonly used in popular medicine. 相似文献
92.
Michelle Bitencourt Matheus P. Freitas Roberto Rittner 《Journal of Molecular Structure》2007,840(1-3):133-136
The effect of attaching an additional fluorine atom at C-2 in 1-fluoropropane (FP), giving 1,2-difluoropropane (DFP), on its conformational equilibrium, is theoretically evaluated. This substitution causes critical implications on the conformer stabilities of DFP (TG, GT and GG conformations) and the steric and electrostatic interactions should favor the conformer with fluorine atoms trans. However, the gauche effect plays a major role in describing the energies balance in DFP, shifting the equilibrium towards the conformation in which the two fluorine atoms are gauche. The origin of this effect is discussed through an NBO analysis, which allows the evaluation of both classical and non-classical (hyperconjugation and bent bonds) interactions as the prevailing factors governing the conformational equilibrium of molecules containing the 1,2-difluoroethane fragment. 相似文献
93.
94.
Jörg Fridgen Georg Eickerling Ana M. Santos 《Journal of organometallic chemistry》2004,689(17):2752-2761
Novel chiral 2′-pyridinyl alcohols derived from isopropylidene-protected carbohydrates are reported. They show different characteristics at the hydroxy group, but are all suitable ligands for chiral molybdenum(VI) complexes of the type MoO2L2 (L = chiral 2′-pyridinyl alcoholate). MoO2(acac)2 served as starting material in the complex syntheses. The structure of one ligand and one dioxo complex were exemplary established by X-ray crystallography. For catalytic runs in the enantioselective epoxidation catalysis trans-methylstyrene was used as model substrate, tert-butylhydroperoxide and cumolhydroperoxide, resp., as the oxidant. 相似文献
95.
Vukadin M. Leovac Vladimir Divjaković Ana F. Petrović Nikolai V. Gerbeleu 《Monatshefte für Chemie / Chemical Monthly》1989,120(3):181-186
Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H2
L) and piperidine (Pip) yielded the paramagnetic (eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H2
L, formed as a result of deprotonation of the phenolic hydroxyl and NH2 group. Crystal data of the complex are: monoclinic P21,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)Å3,M=400.9,Z=2,d
0=1.60 gcm–3,d
c
=1.58 gcm–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.
Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)
Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H2 L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH2- und Phenolhydroxyl-Gruppe) als dianionische Form von H2 L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P21,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20Å3,M=400.9,Z=2,d 0=1.60 gcm–3,d c =1.58 gcm–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.相似文献
96.
97.
Santiago MB Vélez MM Borrero S Díaz A Casillas CA Hofmann C Guadalupe AR Colón JL 《Electroanalysis》2006,18(6):559-572
We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)2bpy]2+) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)2bpy]2+ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)2bpy]2+. The UV‐vis spectrophotometric results indicate that the [Ru(phend)2bpy]2+ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)2bpy]2+ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented. 相似文献
98.
Hair color changes and protein damage caused by ultraviolet radiation 总被引:12,自引:0,他引:12
Santos Nogueira AC Joekes I 《Journal of photochemistry and photobiology. B, Biology》2004,74(2-3):109-117
Ultraviolet and visible radiations are known to damage hair. However, quantitative data relating damage to hair type, proteins and color to the radiation wavelength are missing. We studied the effect of UV plus visible, UVA plus visible, visible mercury-vapor lamp radiation and sunlight on (blended) virgin dark-brown, blond and red hair and (one head) virgin black and curly dark-brown hair. All hair types showed a substantial increase in protein loss in water after lamp and sun irradiation. The damaging effect of UVB was about 2-5 times higher than that of UVA plus visible radiation, depending on the hair type. Significant color changes were also observed in every hair type, after lamp and sun irradiation, being more pronounced for the light colored hairs. The luminosity difference parameter was the major contributor to the hair color changes, but significant changes in the red-green and yellow-blue parameters of every hair were observed. In this case, the damaging effect is ascribable mainly to UVA radiation. No significant changes in the mechanical properties or topography were observed in any case. We discuss these results in terms of hair type and composition and melanin types. 相似文献
99.
Esteso Ana Alemany M. M. E. Ortiz Angel Liu Shaofeng 《Central European Journal of Operations Research》2022,30(3):1101-1127
Central European Journal of Operations Research - Agri-food production must increase while food waste needs to be reduced for improving the position of farmers. To do so it is necessary to... 相似文献
100.
Ana M. Vargas 《Rendiconti del Circolo Matematico di Palermo》1995,44(2):273-282
LetM
e
0
be the maximal operator over segments of length 1 with directions belonging to a Cantor set. It has been conjectured that
this operator is bounded onL
2. We consider a sequence of operators over finite sets of directions converging toM
e
0
. We improve the previous estimate for the (L
2,L
2)-norm of these particular operators. We also prove thatM
e
0
is bounded from some subsets ofL
2 toL
2. These subsets are composed of positive functions whose Fourier transforms have a very weak decay or are supported in a vertical
strip.
Partially supported by Spanish DGICYT grant no. PB90-0187. 相似文献