全文获取类型
收费全文 | 3919篇 |
免费 | 218篇 |
国内免费 | 19篇 |
专业分类
化学 | 3040篇 |
晶体学 | 40篇 |
力学 | 112篇 |
数学 | 197篇 |
物理学 | 767篇 |
出版年
2024年 | 4篇 |
2023年 | 25篇 |
2022年 | 22篇 |
2021年 | 115篇 |
2020年 | 81篇 |
2019年 | 92篇 |
2018年 | 75篇 |
2017年 | 84篇 |
2016年 | 140篇 |
2015年 | 135篇 |
2014年 | 187篇 |
2013年 | 252篇 |
2012年 | 408篇 |
2011年 | 398篇 |
2010年 | 223篇 |
2009年 | 192篇 |
2008年 | 286篇 |
2007年 | 253篇 |
2006年 | 228篇 |
2005年 | 222篇 |
2004年 | 166篇 |
2003年 | 155篇 |
2002年 | 125篇 |
2001年 | 64篇 |
2000年 | 34篇 |
1999年 | 29篇 |
1998年 | 13篇 |
1997年 | 19篇 |
1996年 | 10篇 |
1995年 | 12篇 |
1994年 | 5篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 10篇 |
1990年 | 5篇 |
1989年 | 8篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1964年 | 2篇 |
1961年 | 2篇 |
排序方式: 共有4156条查询结果,搜索用时 293 毫秒
1.
Elsye Agustina Jeungchoon Goak Suntae Lee Youngho Seo Jun-Young Park Naesung Lee 《ChemistryOpen》2015,4(5):613-619
Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red–orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO4/HNO3 and H2SO4/HNO3 mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs. 相似文献
2.
3.
A (w,r) cover‐free family is a family of subsets of a finite set such that no intersection of w members of the family is covered by a union of r others. A (w,r) superimposed code is the incidence matrix of such a family. Such a family also arises in cryptography as the concept of key distribution pattern. In the present paper, we give some new results on superimposed codes. First we construct superimposed codes from super‐simple designs which give us results better than superimposed codes constructed by other known methods. Next we prove the uniqueness of the (1,2) superimposed code of size 9 × 12, the (2,2) superimposed code of size 14 × 8, and the (2,3) superimposed code of size 30 × 10. Finally, we improve numerical values of upper bounds for the asymptotic rate of some (w,r) superimposed codes. © 2004 Wiley Periodicals, Inc. 相似文献
4.
Hyun Joo Rhee 《Tetrahedron letters》2004,45(43):8019-8022
Stereoselective synthesis of (+)-lauthisan has been accomplished starting from d-glyceraldehyde acetonide by combination of diastereoselective alkylation and ring-closing metathesis. High degree of 1,3-asymmetric induction has been realized in ether system. 相似文献
5.
Do W. Lee Eun Y. Seo Sung I. Cho Chae S. Yi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2747-2755
Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [kobs = (1.19 vs 0.56) × 10?4 s?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]o/[ 1d ]o/[ethyl 2‐bromoisobutyrate]o/[MMA]o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr2. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004 相似文献
6.
Yusong Wu Toshihiro Seo Shiro Maeda Takashi Sasaki Satoshi Irie Kensuke Sakurai 《Journal of Polymer Science.Polymer Physics》2004,42(22):4107-4115
Two benzoyl substituted chitosan derivatives, 3,6‐O‐dibenzoylchitosan (DBC) and 2‐N‐3,6‐O‐tribenzoylchitosan (TBC), were prepared, and their optical activities in organic solvent were investigated by circular dichroism (CD). For TBC, two splitting bands (a negative one at 288 nm and a positive one at 274 nm) corresponding to the 1Lb transition of the benzoyl group were observed in chloroform and dichloromethane, while only a negative CD band was recorded in N, N‐dimethylformamide (DMF). These results indicated that the transition moments of benzoyl groups were orderly arranged along the helical polymer chain when TBC was dissolved in a solvent with low polarity, but the same ordered structure did not appear in a polar solvent of DMF. For DBC, only negative CD signals corresponding to the 1Lb transition of the benzoyl group were observed, regardless of the solvent property, which indicated that the chromophores were not arranged in an ordered fashion with appropriate geometry to interact with one another to induce bi‐signate CD signals. Adding methanol or DMF to the solution of TBC/chloroform resulted in a progressive decrease of the intensity of the positive split band at 274 nm. The intensity of the positive band was weakened upon heating a solution of TBC/chloroform from 20 to 60 °C. The results suggested that the ordered arrangement of the chromophores in the TBC system was dependent on solvent and sensitive to temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4107–4115, 2004 相似文献
7.
A signal registration strategy from micropatterned immunosensors that converts antigen-antibody binding reactions into electrochemical signals was demonstrated. An array-type micropatterned gold electrode on a silicon wafer was fabricated, containing two electrode geometries of rectangular (100 microm x 500 microm) and circular (r. 50 microm) types, exhibiting electrochemical characteristics of bulk and micro-electrodes, respectively. Ferritin was employed as a model analyte for immunosensing because it has an advantageous molecular structure for functionalization to the sensing interface, and is regarded as a general marker protein for tumors and cancer recurrence. With the fabricated and ferritin-functionalized immunosensors, biospecific interactions were performed with antiferritin antiserum and secondary antibody samples, followed by electrochemical signaling via an immunoprecipitation reaction by the label enzyme. Under the optimized affinity-surface construction steps and reaction conditions, both types of microfabricated electrodes exhibited well-defined calibration results as a function of the protein concentration in antiserum samples. Furthermore, circular-type micropatterned immunoelectrodes exhibited voltammetric characteristics of microelectrodes, which is advantageous in terms of sensor operation under a fixed potential and low signal drift during the signaling reaction compared with the bulk-type electrodes. The results support that the employed signaling method with the proposed immunosensor configuration is fit for sensor miniaturization and integration to future biomicrosystems. 相似文献
8.
Sang Hyun Kwon Yoshio Okamoto Chiyo Yamamoto Wonjo Cheong Myeonghee Moon Jung Hag Park 《Analytical sciences》2006,22(12):1525-1529
Porous zirconia particles are very robust material and have received considerable attention as a stationary phase support for HPLC. We prepared cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia (CDMPCCZ) as a chiral stationary phase (CSP) for separation of enantiomers of a set of 14 racemic compounds in normal phase (NP) and reversed-phase (RP) liquid chromatography. Retention and enantioselectivity on CDMPCCZ were compared to those on CDMPC-coated zirconia (CDMPCZ) to see how the change in immobilization method of the chiral selector affects the retention and chiral selectivity. In NPLC, retention was longer and the number of resolved racemates was smaller on CDMPCCZ than on CDMPCZ. However, chiral selectivity factors for some resolved racemates were better on CDMPCCZ than on CDMPCZ. The longer retention on CDMPCCZ is likely due to strong, non-chiral discriminating interactions with the carbon layer on CDMPCZ. In RPLC only two racemates were resolved on CDMPCCZ, but retention times were shorter than, and resolutions were comparable to, those in NPLC, indicating a potential for improving chromatographic performance of the CDMPCCZ column in RPLC with optimized column preparation and separation conditions. 相似文献
9.
10.
Jin-Mok Hur Chung-Seok Seo Sun-Seok Hong Dae-Seung Kang Seong-Won Park 《Reaction Kinetics and Catalysis Letters》2003,80(2):217-222
The concept of a novel electrochemical reduction process for the treatment of spent nuclear fuels in Li2O-LiCl molten salt was proposed and fresh tests using U3O8 powder were carried out to elucidate the reaction mechanism and verify the feasibility of the process. Electrolysis of Li2O and reduction of U3O8 powder took place simultaneously at the cathode part of the electrolysis cell via a catalytic EC mechanism and the conversion of U3O8 to U metal was more than 99%.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献