全文获取类型
收费全文 | 3192篇 |
免费 | 479篇 |
国内免费 | 432篇 |
专业分类
化学 | 2327篇 |
晶体学 | 30篇 |
力学 | 225篇 |
综合类 | 46篇 |
数学 | 314篇 |
物理学 | 1161篇 |
出版年
2024年 | 8篇 |
2023年 | 57篇 |
2022年 | 110篇 |
2021年 | 115篇 |
2020年 | 144篇 |
2019年 | 109篇 |
2018年 | 118篇 |
2017年 | 117篇 |
2016年 | 149篇 |
2015年 | 130篇 |
2014年 | 177篇 |
2013年 | 219篇 |
2012年 | 214篇 |
2011年 | 292篇 |
2010年 | 201篇 |
2009年 | 196篇 |
2008年 | 208篇 |
2007年 | 192篇 |
2006年 | 158篇 |
2005年 | 121篇 |
2004年 | 95篇 |
2003年 | 75篇 |
2002年 | 75篇 |
2001年 | 69篇 |
2000年 | 60篇 |
1999年 | 73篇 |
1998年 | 60篇 |
1997年 | 50篇 |
1996年 | 48篇 |
1995年 | 51篇 |
1994年 | 51篇 |
1993年 | 48篇 |
1992年 | 47篇 |
1991年 | 37篇 |
1990年 | 40篇 |
1989年 | 32篇 |
1988年 | 25篇 |
1987年 | 31篇 |
1986年 | 24篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有4103条查询结果,搜索用时 15 毫秒
211.
Wenling Zhang Jinlin He Zhuang Liu Peihong Ni Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2010,48(5):1079-1091
A series of well‐defined amphiphilic triblock copolymers [polyethylene glycol monomethyl ether]‐block‐poly(ε‐caprolactone)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] (mPEG‐b‐PCL‐b‐PDMAEMA or abbreviated as mPEG‐b‐PCL‐b‐PDMA) were prepared by a combination of ring‐opening polymerization and atom transfer radical polymerization. The chemical structures and compositions of these copolymers have been characterized by Fourier transform infrared spectroscopy, 1H NMR, and thermogravimetric analysis. The molecular weights of the triblock copolymers were obtained by calculating from 1H NMR spectra and gel permeation chromatography measurements. Subsequently, the self‐assembly behavior of these copolymers was investigated by fluorescence probe method and transmission electron microscopy, which indicated that these amphiphilic triblock copolymers possess distinct pH‐dependent critical aggregation concentrations and can self‐assemble into micelles or vesicles in PBS buffer solution, depending on the length of PDMA in the copolymer. Agarose gel retardation assays demonstrated that these cationic nanoparticles can effectively condense plasmid DNA. Cell toxicity tests indicated that these triblock copolymers displayed lower cytotoxicity than that of branched polyethylenimine with molecular weight of 25 kDa. In addition, in vitro release of Naproxen from these nanoparticles in pH buffer solutions was conducted, demonstrating that higher PCL content would result in the higher drug loading content and lower release rate. These biodegradable and biocompatible cationic copolymers have potential applications in drug and gene delivery. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1079–1091, 2010 相似文献
212.
Two new coordination polymers, [Na(H2L)(H2O)2]n ( 1 ) and [Ba(H2L)2(H2O)]n ( 2 ) (H3L = 3‐formyl‐4‐hydroxybenzenesulfonic acid) were synthesized and structurally characterized. The H2L– ligand shows three different bridging modes, μ3 in 1 , μ3 and μ4 in 2 . Compound 1 presents a 2D pillared structure, whereas 2 forms a 3D framework. Both 1 and 2 show blue luminescence at 380 nm in aqueous solution, however, their solid state emissions are at 406 and 446 nm, respectively. 相似文献
213.
Ni C Fettinger JC Long GJ Power PP 《Dalton transactions (Cambridge, England : 2003)》2010,39(44):10664-10670
Reaction of {Li(THF)Ar'MnI(2)}(2) (Ar' = C(6)H(3)-2,6-(C(6)H(2)-2,6-(i)Pr(3))(2)) with LiAr', LiC≡CR (R = (t)Bu or Ph), or (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) afforded the diaryl MnAr'(2) (1), the alkynyl salts Ar'Mn(C≡C(t)Bu)(4){Li(THF)}(3) (2) and Ar'Mn(C≡CPh)(3)Li(3)(THF)(Et(2)O)(2)(μ(3)-I) (3), and the manganate salt {Li(THF)}Ar'Mn(μ-I)(C(6)H(2)-2,4,6-(i)Pr(3)) (4), respectively. Complex 4 reacted with one equivalent of (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) to afford the homoleptic dimer {Mn(C(6)H(2)-2,4,6-(i)Pr(3))(μ-C(6)H(2)-2,4,6-(i)Pr(3))}(2) (5), which resulted from the displacement of the bulkier Ar' ligand in preference to the halogen. The reaction of the more crowded {Li(THF)Ar*MnI(2)}(2) (Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) with Li(t)Bu gave complex Ar*Mn(t)Bu (6). Complex 1 is a rare monomeric homoleptic two-coordinate diaryl Mn(II) complex; while 6 displays no tendency to eliminate β-hydrogens from the (t)Bu group because of the stabilization supplied by Ar*. Compounds 2 and 3 have cubane frameworks, which are constructed from a manganese, three carbons from three acetylide ligands, three lithiums, each coordinated by a donor, plus either a carbon from a further acetylide ligand (2) or an iodide (3). The Mn(II) atom in 4 has an unusual distorted T-shaped geometry while the dimeric 5 features trigonal planar manganese coordination. The chloride substituted complex Li(2)(THF)(3){Ar'MnCl(2)}(2) (7), which has a structure very similar to that of {Li(THF)Ar'MnI(2)}(2), was also prepared for use as a possible starting material. However, its generally lower solubility rendered it less useful than the iodo salt. Complexes 1-7 were characterized by X-ray crystallography and UV-vis spectroscopy. Magnetic studies of 2-4 and 6 showed that they have 3d(5) high-spin configurations. 相似文献
214.
Data fusion in multivariate calibration transfer 总被引:1,自引:0,他引:1
We report the use of stacked partial least-squares regression and stacked dual-domain regression analysis with four commonly used techniques for calibration transfer to improve predictive performance from transferred multivariate calibration models. The predictive performance from three conventional calibration transfer methods, piecewise direct standardization (PDS), orthogonal signal correction (OSC) and model updating (MUP), requiring standards measured on both instruments, was significantly improved from data fusion either by stacking of wavelet scales or by stacking of spectral intervals, as demonstrated by transfer of calibrations developed on near-infrared spectra of synthetic gasoline. Stacking did not produce as significant an improvement for calibration transfer using a finite impulse response (FIR) filter, but application of SPLS regression to FIR-transferred spectra improves predictive performance of the transferred model. 相似文献
215.
Paul Tanui Martin Kullberg Ni Song Yashodhan Chivate Eriks Rozners 《Tetrahedron》2010,66(27-28):4961-4964
Amides as neutral and hydrophobic internucleoside linkages in RNA are highly interesting modifications for RNA interference. However, testing amides in siRNAs is hampered by the shortage of efficient methods to synthesize the monomeric building blocks, the nucleoside amino acid equivalents. This paper reports an efficient synthesis of protected ribonucleoside 5′-amino 3′-carboxylic acids from d-xylose in 14 steps 7% overall yield. The key features that ensure efficiency and ease of operations are chemoselective reduction of the ester and minimization of protecting group manipulation. 相似文献
216.
Zhongyue Zhou Mingfeng Xie Tang Tang Yijun Zhang Tao Yuan Fei Qi Tom Ni Xueyu Qian 《Plasma Chemistry and Plasma Processing》2010,30(3):391-400
Capacitive radio frequency (RF) discharge of c-C4F8 (octafluorocyclobutane) has been studied with synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry (PIMS)
at 4 Torr and 33.33 kHz. Various free radicals and reactive intermediates have been identified through measurement of photoionization
mass spectra and photoionization efficiency (PIE) spectra. CF2=CF2 is main product in the plasma, indicating that the dissociation of c-C4F8 into CF2=CF2 is one of prominent reactions in the present experimental conditions. The observation of large species including C5F8, C5F10 and C6F10 is presented in our work. Besides, the dependences of the signals of neutral species in the discharge of c-C4F8 on RF power are presented in this paper. 相似文献
217.
Amphiphilic hyperbranched poly(amino ester)s with hydrophilic multi‐ethoxylated triacrylate backbone and hydrophobic long alkyl side chain were firstly synthesized via one pot Michael addition polymerization. The poly‐(amino ester) could dissolve in cold water and self‐assemble into loose micelle. Under 50–1000 ms bubble, the dynamic surface tension (DST) of the poly(amino ester) aqueous solution (0.5 wt%) still maintained in the range of 32–28 mN/m. The aqueous solutions of poly(amino ester)s with different molecular weights showed the lower critical solution temperature (LCST) in the range of 8–50°C, which could also be tuned by its pH. Capped with hydrophobic groups on the terminal units and partially neutralized with acid, the poly(amino ester)s still kept their stable dynamic surfactant behaviors, indicating promising application. 相似文献
218.
Polymerization of n‐octylallene was successfully carried out using a conventional binary rare earth catalytic system composed of rare earth tris(2‐ethylhexylphosphonate) (Ln(P204)3) and tri‐isobutyl aluminum (Al(i‐Bu)3) for the first time. The effects of catalyst, solvent, reaction time and temperature on the polymerization of n‐octylallene were studied. The resulting poly(n‐octylallene) has weight‐average molecular weight of 11000, molecular weight distribution of 1.4 and 96% yield under the moderate reaction conditions: [Al]/[Y] =50 (molar ratio), [n‐octylallene]/[Y] =100 (molar ratio), polymerized at 80°C for 20 h in bulk. The poly(n‐octylallene) obtained consisted of 1,2‐ and 2,3‐polymerized units, and was characterized by FT‐IR, 1H NMR and GPC. Further investigation shows that the polymerization of n‐octylallene has some living polymerization characteristics, preparing the polymer with controlled molecular weight and narrower molecular weight distribution. 相似文献
219.
220.
采用不同合成方法制备了4种组成为Ce0.5Zr0.5O2的铈锆固溶体.通过XRD,BET,H2-TPR,HREM以及SEAD等表征手段,研究了微观晶相结构对铈锆固溶体还原性能的影响规律,以及对固溶体储放氧能力的影响.分析结果表明,在同一组成下,不同制备方法得到截然不同的晶相组成,4种固溶体包含4种不同的晶相组合.通过对微观晶相结构的定量分析,发现立方相的形成对促进固溶体的还原性能起到重要作用.其中,反相微乳法制得的铈锆固溶体能够形成完整的立方相结构,在H2-TPR还原过程中耗氢量最大,表明其具有优良的可还原性及储放氧能力,适合作为TWC,POX等催化剂载体. 相似文献