全文获取类型
收费全文 | 2077篇 |
免费 | 78篇 |
国内免费 | 7篇 |
专业分类
化学 | 1485篇 |
晶体学 | 26篇 |
力学 | 17篇 |
数学 | 304篇 |
物理学 | 330篇 |
出版年
2023年 | 14篇 |
2022年 | 31篇 |
2021年 | 83篇 |
2020年 | 67篇 |
2019年 | 51篇 |
2018年 | 48篇 |
2017年 | 40篇 |
2016年 | 89篇 |
2015年 | 76篇 |
2014年 | 80篇 |
2013年 | 128篇 |
2012年 | 128篇 |
2011年 | 139篇 |
2010年 | 103篇 |
2009年 | 97篇 |
2008年 | 135篇 |
2007年 | 110篇 |
2006年 | 90篇 |
2005年 | 81篇 |
2004年 | 74篇 |
2003年 | 59篇 |
2002年 | 65篇 |
2001年 | 36篇 |
2000年 | 38篇 |
1999年 | 24篇 |
1998年 | 18篇 |
1997年 | 13篇 |
1996年 | 23篇 |
1995年 | 18篇 |
1994年 | 24篇 |
1993年 | 20篇 |
1992年 | 26篇 |
1991年 | 22篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 5篇 |
1985年 | 11篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 4篇 |
1979年 | 5篇 |
1977年 | 2篇 |
1968年 | 1篇 |
1936年 | 2篇 |
1927年 | 2篇 |
1924年 | 2篇 |
1923年 | 1篇 |
排序方式: 共有2162条查询结果,搜索用时 62 毫秒
71.
Gabriela M. M. Calabria Adilson R. Gonçalves 《Applied biochemistry and biotechnology》2006,129(1-3):320-325
Oxidation of lignin obtained from acetosolv and ethanol/water pulping of sugarcane bagasse was performed by phenol oxidases:
tyrosinase (TYR) and laccase (LAC), to increase the number of carbonyl and hydroxyl groups in lignin, and to improve its chelating
capacity. The chelating properties of the original and oxidized lignins were compared by monitoring the amount of Cu2+ bound to lignin by gel permeation chromatography. The Acetosolv lignin oxidized with TYR was 16.8% and with LAC 21% higher
than that of the original lignin. For ethanol/water lignin oxidized with TYR was 17.2% and with LAC 18% higher than that of
the original lignin. 相似文献
72.
Soft PVC is employed for the manufacturing of a wide range of products with different properties and a relatively low cost. The utilization of soft PVC is restricted by the poor thermal, chemical and mechanical resistance properties. Also, plasticizer migration can modify the properties or can make useless the materials for some applications because of toxicity or a general loss of properties. PVC crosslinking is the most effective way to improve mechanical and transport properties of rigid or flexible PVC at high temperatures, but at the same time the thermal stability of PVC may be significantly reduced. In this work, the crosslinking reaction of plasticized poly(vinyl chloride) (PVC) through difunctional amines was studied. The mechanisms involved in the crosslinking reaction were explained by Fourier transform infrared (FTIR) analysis. The thermal activated crosslinking reaction was studied by cone and plate rheometry, analyzing the evolution of viscoelastic properties of the suspension as a function of time and temperature. The effect of the addition of crosslinking agents on the thermal stability of the polymer was studied by thermogravimetric analysis (TGA), which revealed that crosslinking reactions promote thermal degradation phenomena in the polymer matrix. This is attributed to the formation of HCl and other species promoting polymer degradation during crosslinking, thus leading to higher weight loss during thermal treatment with respect to unmodified PVC plastisols. This was also confirmed by an evident yellowing after crosslinking, especially at higher temperatures. 相似文献
73.
Alam MS Kim IJ Nemati B O'Neill JJ Romero V Severini H Sun CR Wang P Zoeller MM Crawford G Fulton R Gan KK Kagan H Kass R Lee J Malchow R Morrow F Sung M White C Whitmore J Wilson P Butler F Fu X Kalbfleisch G Lambrecht M Skubic P Snow J Bortoletto D Brown DN Dominick J McIlwain RL Miao T Miller DH Modesitt M Schaffner SF Shibata EI Shipsey IP Battle M Ernst J Kroha H Roberts S Sparks K Thorndike EH Wang C Artuso M Goldberg M Haupt T Horwitz N Kennett R Moneti GC Playfer S Rozen Y Rubin P 《Physical review D: Particles and fields》1992,46(11):4822-4827
74.
Fulton R Jensen T Johnson DR Kagan H Kass R Morrow F Whitmore J Wilson P Bortoletto D Chen W Dominick J McIlwain RL Miller DH Ng CR Schaffner SF Shibata EI Shipsey IP Yao W Battle M Sparks K Thorndike EH Wang C Alam MS Kim IJ Li WC Romero V Sun CR Wang P Zoeller MM Goldberg M Haupt T Horwitz N Jain V Mestayer MD Moneti GC Rozen Y Rubin P Sharma V Skwarnicki T Thulasidas M Zhu G Csorna SE Letson T Alexander J Artuso M Bebek C Berkelman K Browder T Cassel DG Cheu E Coffman DM Crawford G DeWire JW 《Physical review D: Particles and fields》1991,43(3):651-663
75.
Kubota Y Nelson JK Perticone D Poling R Schrenk S Crawford G Fulton R Jensen T Johnson DR Kagan H Kass R Malchow R Morrow F Whitmore J Wilson P Bortoletto D Brown D Dominick J McIlwain RL Miller DH Modesitt M Ng CR Schaffner SF Shibata EI Shipsey IP Battle M Kroha H Sparks K Thorndike EH Wang C Alam MS Kim IJ Li WC Nemati B Romero V Sun CR Wang P Zoeller MM Goldberg M Haupt T Horwitz N Jain V Mestayer MD Moneti GC Rozen Y Rubin P Skwarnicki T Stone S Thusalidas M Yao W Zhu G Barnes AV Bartelt J 《Physical review D: Particles and fields》1991,44(3):593-600
76.
In a sodium dodecyl sulphate (SDS) micellar solution, the rate of coupling of a diazonium ion with N-(1- naphthyl)ethylenediamine (NED) increases greatly, the protonation of the resulting azo dyes takes place at higher pH values and the dyes are more soluble. These favourable features were applied to the development of a simple flow-injection spectrophotometric procedure for the determination of diazotizable substances of pharmaceutical interest. Limits of detection in the range 0.2–0.5 μg ml?1 (signal-to-noise ratio=3), with relative standard deviation of 0.7–3% (n=3) for 5 μg ml?1 standards, were obtained. 相似文献
77.
Jandera P Skeifíková V Rehová L Hájek T Baldriánová L Skopová G Kellner V Horna A 《Journal of separation science》2005,28(9-10):1005-1022
Methods were developed for the analysis of natural antioxidants including phenolic compounds and flavonoids in beverages and plant extracts using gradient HPLC with multi-channel electrochemical coulometric detection. Suitability of various reversed-phase columns for this purpose was compared; pH and mobile phase gradients were optimized with respect to the separation selectivity and sensitivity of detection. Because of different target compounds in various sample types, the overlapping resolution maps and the normalized resolution product approaches described earlier were used to select optimum columns and gradients to suit the analysis of the individual sample types. The methods were applied to the analysis of phenolic compounds and flavonoids in beer, wine, tea, and yacon extracts. 32 phenolic compounds were identified and determined, including derivatives of benzoic and cinnamic acids, flavones, and a few related glycosides. Eight-channel CoulArray detection offers high selectivity and sensitivity with limits of detection in the low microg L(-1) range, at least an order of magnitude lower than single-channel coulometric detection using the Coulochem detector. No special sample pretreatment is necessary and, because of the compatibility of the CoulArray detector with gradient elution, phenolic antioxidants of different polarities can be determined in a single run. In addition to the retention times, the ratios of the areas of the pre-dominant and post-dominant peaks to the area of the dominant peak can be used for improved identification of natural antioxidants. 相似文献
78.
Robert R Hudgins Fang Huang Gabriela Gramlich Werner M Nau 《Journal of the American Chemical Society》2002,124(4):556-564
A fluorescent amino acid derivative (Fmoc-DBO) has been synthesized, which contains 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as a small, hydrophilic fluorophore with an extremely long fluorescence lifetime (325 ns in H2O and 505 ns in D2O under air). Polypeptides containing both the DBO residue and an efficient fluorescence quencher allow the measurement of rate constants for intramolecular end-to-end contact formation. Bimolecular quenching experiments indicated that Trp, Cys, Met, and Tyr are efficient quenchers of DBO (k(q) = 20, 5.1, 4.5, and 3.6 x 10(8) M(-1) x s(-1) in D2O), while the other amino acids are inefficient. The quenching by Trp, which was selected as an intrinsic quencher, is presumed to involve exciplex-induced deactivation. Flexible, structureless polypeptides, Trp-(Gly-Ser)n-DBO-NH2, were prepared by standard solid-phase synthesis, and the rates of contact formation were measured through the intramolecular fluorescence quenching of DBO by Trp with time-correlated single-photon counting, laser flash photolysis, and steady-state fluorometry. Rate constants of 4.1, 6.8, 4.9, 3.1, 2.0, and 1.1 x 10(7) s(-1) for n = 0, 1, 2, 4, 6, and 10 were obtained. Noteworthy was the relatively slow quenching for the shortest peptide (n = 0). The kinetic data are in agreement with recent transient absorption studies of triplet probes for related peptides, but the rate constants are significantly larger. In contrast to the flexible structureless Gly-Ser polypeptides, the polyproline Trp-Pro4-DBO-NH2 showed insignificant fluorescence quenching, suggesting that a high polypeptide flexibility and the possibility of probe-quencher contact is essential to induce quenching. Advantages of the new fluorescence-based method for measuring contact formation rates in biopolymers include high accuracy, fast time range (100 ps-1 micros), and the possibility to perform measurements in water under air. 相似文献
79.
Coronado E Gómez-García CJ Nuez A Romero FM Rusanov E Stoeckli-Evans H 《Inorganic chemistry》2002,41(18):4615-4617
The combination of hexacyanoferrate(III) anions, [Fe(CN)(6)](3)(-), with nickel(II) complexes derived from the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) affords the enantiopure layered compounds [Ni(trans-(1S,2S)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (1) and [Ni(trans-(1R,2R)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (2). These chiral systems behave as ferromagnets (T(c) = 13.8 K) with a relatively high coercive field (H(c) = 0.17 T) at 2 K. They also exhibit an unusual magnetic behavior at low temperatures that has been attributed to the dynamics of the magnetic domains in the ordered phase. 相似文献
80.
The bicyclic and tricyclic meso-N-(methylsulfonyl)dicarboximides 1a–f are converted enantioselectively to isopropyl [(sulfonamido)carbonyl]-carboxylates 2a–f by diisopropoxytitanium TADDOLate (75–92% yield; see Scheme 3). The enantiomer ratios of the products are between 86:14 and 97:3, and recrystallization from CH2Cl2/hexane leads to enantiomerically pure sulfonamido esters 2 (Scheme 3). The enantioselectivity shows a linear relationship with the enantiomer excess of the TADDOL employed (Fig.3). Reduction of the ester and carboxamide groups (LiAlH4) and additional reductive cleavage of the sulfonamido group (Red-Al) in the products 2 of imide-ring opening gives hydroxy-sulfonamides 3 and amino alcohols 4 , respectively (Scheme 4). The absolute configuration of the sulfonamido esters 2 is determined by chemical correlation (with 2a,b ; Scheme 6), by the X-ray analysis of the camphanate of 3e (Fig. 1), and by comparative 19F-NMR analysis of the Mosher esters of the hydroxy-sulfonamides 3 (Table 1). A general proposal for the assignment of the absolute configuration of primary alcohols and amines of Formula HXCH2CHR1R2, X = O, NH, is suggested (see 11 in Table 1). It follows from the assignment of configuration of 2 that the Re carbonyl group of the original imide 1 is converted to an isopropyl ester group. This result is compatible with a rule previously put forward for the stereochemical course of reactions involving titanium TADDOLate activated chelating electrophiles ( 12 in Scheme 7). A tentative mechanistic model is proposed ( 13 and 14 in Scheme 7). 相似文献