全文获取类型
收费全文 | 7827篇 |
免费 | 1105篇 |
国内免费 | 446篇 |
专业分类
化学 | 4076篇 |
晶体学 | 34篇 |
力学 | 797篇 |
综合类 | 189篇 |
数学 | 1942篇 |
物理学 | 2340篇 |
出版年
2024年 | 11篇 |
2023年 | 101篇 |
2022年 | 287篇 |
2021年 | 310篇 |
2020年 | 388篇 |
2019年 | 265篇 |
2018年 | 240篇 |
2017年 | 344篇 |
2016年 | 405篇 |
2015年 | 345篇 |
2014年 | 465篇 |
2013年 | 464篇 |
2012年 | 492篇 |
2011年 | 457篇 |
2010年 | 386篇 |
2009年 | 472篇 |
2008年 | 433篇 |
2007年 | 450篇 |
2006年 | 423篇 |
2005年 | 363篇 |
2004年 | 328篇 |
2003年 | 280篇 |
2002年 | 231篇 |
2001年 | 185篇 |
2000年 | 188篇 |
1999年 | 148篇 |
1998年 | 160篇 |
1997年 | 112篇 |
1996年 | 96篇 |
1995年 | 104篇 |
1994年 | 82篇 |
1993年 | 70篇 |
1992年 | 60篇 |
1991年 | 34篇 |
1990年 | 31篇 |
1989年 | 25篇 |
1988年 | 14篇 |
1987年 | 16篇 |
1986年 | 16篇 |
1985年 | 26篇 |
1984年 | 16篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1980年 | 6篇 |
1979年 | 14篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1971年 | 2篇 |
排序方式: 共有9378条查询结果,搜索用时 796 毫秒
151.
Molecularly imprinted polymers (MIPs) are tailor-made polymers with high selectivity for the template molecule. This selectivity arises from the synthetic procedure followed to prepare the MIP. In this work, the influence of process parameters on the preparation of vinblastine (VLB) imprinted polymers was presented. In the procedure of polymerization, VLB (0.1 mmol) was used as the template molecule and a commonly used initiator, azobisisobutyronitrile (AIBN), was employed to initiate the reaction at 60 °C. The influence of the following parameters was investigated: the moles of functional monomer (MAA, 0.3-1.0 mmol), the moles of cross-linker (EDMA, 1.5-5.0 mmol) and the porogenic solvent (toluene or acetonitrile). A mathematical method of uniform design was applied to optimize these selected parameters in order to increase the selectivity of MIP for template molecule. The experimental data were analyzed to obtain the regression model and the optimal conditions were achieved by optimization with uniform design software. The MIP was synthesized under the optimal conditions that 1.0 mmol of MAA and 5.0 mmol of EDMA copolymerized in toluene in the presence of 0.1 mmol of VLB. After removal of the template molecule, the obtained MIP was then employed as the sorbents of solid-phase extraction (SPE) to separate VLB from Catharanthus roseus extract. The results showed that the polymer exhibited high affinity to the template molecule and could separate and enrich VLB from C. roseus extract effectively. The recovery of VLB on the optimal MIP was 89.00%, which agreed closely with the predicted recovery. Therefore it is possible to further improve the nature of the polymer by optimizing the polymerization parameters with the method of uniform design. 相似文献
152.
153.
Regulations for pesticide residue analysis in food require very low detection limits; thus requiring maximum sensitivity in
the gas chromatographic determination. This is accomplished by an overall method optimisation, which includes optimisation
of injector parameters. Here we study the effect of the inlet liner design on the optimisation by comparing five liner designs
in splitless and pulsed splitless injection modes, using a test mixture of fifteen pesticides analyzed by GC-ECD. Possible
links between the injection parameters and liner types were evaluated, with the result that, accurate choice of inlet liner
and injection parameters can reduce detection limits by up to 300%.
Revised: 25 October 2005 and 9 January 2006 相似文献
154.
S. Kumagai 《Journal of Optimization Theory and Applications》1980,31(2):285-288
In Ref. 1, Jittorntrum proposed an implicit function theorem for a continuous mappingF:R
n ×R
m R
n, withF(x
0,y
0)=0, that requires neither differentiability ofF nor nonsingularity of
x
F(x
0,y
0). In the proof, the local one-to-one condition forF(·,y):A R
n R
n for ally B is consciously or unconsciously treated as implying thatF(·,y) mapsA one-to-one ontoF(A, y) for ally B, and the proof is not perfect. A proof can be given directly, and the theorem is shown to be the strongest, in the sense that the condition is truly if and only if. 相似文献
155.
L. G. Chalmet R. L. Francis J. F. Lawrence 《Journal of Optimization Theory and Applications》1980,32(2):135-149
An example of design might be a warehouse floor (represented by a setS) of areaA, with unspecified shape. Givenm warehouse users, we suppose that useri has a known disutility functionf
isuch thatH
i(S), the integral off
iover the setS (for example, total travel distance), defines the disutility of the designS to useri. For the vectorH(S) with entriesH
i(S), we study the vector minimization problem over the set {H(S) :S a design} and call a design efficient if and only if it solves this problem. Assuming a mild regularity condition, we give necessary and sufficient conditions for a design to be efficient, as well as verifiable conditions for the regularity condition to hold. For the case wheref
iis thel
p-distance from warehouse docki, with 1<p<, a design is efficient if and only if it is essentially the same as a contour set of some Steiner-Weber functionf
=1
f
1++
m
f
m
,when the
i
are nonnegative constants, not all zero.This research was supported in part by the Interuniversity College for PhD Studies in Management Sciences (CIM), Brussels, Belgium; by the Army Research Office, Triangle Park, North Carolina; by a National Academy of Sciences-National Research Council Postdoctorate Associateship; and by the Operations Research Division, National Bureau of Standards, Washington, D.C. The authors would like to thank R. E. Wendell for calling Ref. 16 to their attention. 相似文献
156.
采用多拷贝同时搜寻法(MCSS), 并结合现有微管抑制剂的SAR及3D-QSAR对β微管蛋白中Taxol(紫杉醇)结合腔的性质进行了分析. 结构研究结果表明, Taxol结合腔以疏水性质为主, 并指出官能团分布的具体位置: 在Phe270上方(Leu361-Pro272-Leu273-Leu228之间)的弧形区域、Asp26羧基下方及其与Glu22羧基之间、M-loop的中部, 以及Asp224内侧且靠近Arg276的胍基的位置. 而Asp224的内侧又是新提出的结合位点. 研究结果符合现有微管抑制剂的SAR, 为现有抗肿瘤药物的结构改造以及小分子微管抑制剂设计提供了理论依据. 相似文献
157.
J. Hernández-Borges M. A. Rodríguez-Delgado F. J. García-Montelongo 《Chromatographia》2006,63(3-4):155-160
Several improvements in sample pretreatment for the determination of organic pollutants (i.e. n-alkanes, polycyclic aromatic hydrocarbons, PAHs) in marine biota (mussels) are presented. The use of liquid nitrogen and
homogenization of the samples are shown to be an alternative to the time consuming liophilization step required for the analysis
of biota samples. Microwave-assisted hydrolysis and extraction are combined to isolate organic pollutants (19 n-alkanes and 27 PAHs) from biota matrices. Experimental design (ED) and artificial neural networks (ANNs) were used to optimize
the experimental conditions. NIST-CRM 2978 was used to test the validity of the developed method which shows a good agreement
with certified values. 相似文献
158.
159.
《Arabian Journal of Chemistry》2022,15(12):104329
To reduce the amount of hazardous chemical bottle waste in the environment, we report the optimization research of silica extraction in chemical bottle waste into silica gel. Alkali fusion and sol–gel process were utilised to prepare silica gel effectively. The alkali fusion process was carried out by adding sodium hydroxide to produce sodium silicate. Afterwards, silica gel was prepared by the sol–gel method using hydrochloric acid. Box-Behnken Design (BBD) was applied to Optimisation factors the poptimiseactors affecting the silica recovery. The factors that optimised mass ratio, particle size, and temperature. The optimum recovery of silica gel was obtained by SiO2: NaOH mass ratio of 1:3, the particle size of 63–74 µm, and a temperature of 800 °C. The purity of silica gel optimum is 63.74% characterised using X-ray fluorescence. The structure of silica gel is the appearance of amorphous peaks at 2θ 20-30° characterised using an x-ray diffractogram. The silica gel surface was characterises using scanning electron microscopy-energy dispersive x-ray. It showed an irregular surface and characteristic showed that silica gel had a radius of 15.74 nm and a specific surface area of 297.08 m2. 相似文献
160.
Aromí G Ribas J Gamez P Roubeau O Kooijman H Spek AL Teat S MacLean E Stoeckli-Evans H Reedijk J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6476-6488
Coordination complexes of the ligand H3L [1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene] with Cu(II) are reported. Clusters showing various nuclearities or modes of supramolecular organization have been prepared by slightly changing the reaction conditions and have been crystallographically characterized. The reaction of H3L with one equivalent of Cu(OAc)2 in DMF yields the dinuclear complex [Cu2(HL)2(dmf)2] (1). Reaction in MeOH of H3L with an increased amount of metal, in the form of Cu(NO3)2, and excess strong base (nBu4NOH) affords the cluster [Cu8(L)2(OMe)8(NO3)2] (2). Complex 2 is a dimer of two linear [Cu4] arrays bridged by methoxide ligands, where the polynucleating ligand is fully deprotonated. The [Cu4]2 clusters are linked to each other by NO3- bridges to form one-dimensional coordination polymers. The link between [Cu8] units and their relative spatial positioning can be modified by changing the anion of the Cu(II) salt, as demonstrated by the synthesis of the cluster polymers [Cu8(L)2(OMe)8Cl2] (3) and [Cu8(L)(OMe)7.86Br2.14] (4), where only NO3- has been replaced by Cl- or Br-, respectively. Similarly, when ClO4- is used, compound [Cu8(L)2(OMe)8(ClO4)2(MeOH)4] (5) can be isolated. It contains independent [Cu8] units. A slight change in the stoichiometry of the reaction leading to 2 affords the related complex catena-[Cu4(L)(OMe)3(NO3)2(H2O)0.36] (6). This polymer contains essentially the same [Cu4] moiety as 2, albeit organized in a completely different arrangement. Each [Cu4] unit in 6 is linked by OMe- ligands to two such equivalent groups to form an infinite chain. Magnetic susceptibility measurements reveal weak antiferromagnetic exchange between Cu(II) centers in 1 (J = -0.73 cm(-1)) and strong antiferromagnetic coupling within [Cu4] chains in 2, 5, and 6 (most negative J values of -113.8 and -177.3 cm(-1) for 2 and 6, respectively). 相似文献