首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1722篇
  免费   99篇
  国内免费   258篇
化学   1935篇
晶体学   13篇
综合类   11篇
物理学   120篇
  2024年   4篇
  2023年   13篇
  2022年   40篇
  2021年   52篇
  2020年   50篇
  2019年   39篇
  2018年   29篇
  2017年   41篇
  2016年   48篇
  2015年   58篇
  2014年   64篇
  2013年   152篇
  2012年   78篇
  2011年   76篇
  2010年   50篇
  2009年   69篇
  2008年   89篇
  2007年   121篇
  2006年   75篇
  2005年   97篇
  2004年   93篇
  2003年   100篇
  2002年   86篇
  2001年   69篇
  2000年   58篇
  1999年   63篇
  1998年   60篇
  1997年   44篇
  1996年   47篇
  1995年   39篇
  1994年   43篇
  1993年   30篇
  1992年   17篇
  1991年   20篇
  1990年   13篇
  1989年   14篇
  1988年   8篇
  1987年   8篇
  1986年   4篇
  1985年   5篇
  1984年   1篇
  1982年   6篇
  1981年   2篇
  1980年   2篇
  1978年   1篇
  1976年   1篇
排序方式: 共有2079条查询结果,搜索用时 328 毫秒
51.
Aspen wood substrates with varying degrees of deacetylation, xylan, and lignin removal have been prepared and submitted to enzymatic hydrolysis with a cellulase/hemicellulase preparation for an extended constant period of hydrolysis. Controlled deacetylation has been achieved by treating wood with various alkali metal hydroxide solutions, at various alkali/wood ratios. It has been found that samples with the same extent of deacetylation produce the same sugar yields upon enzymatic hydrolysis. Increased degree of deacetylation increases the yield of sugars obtained from enzymatic hydrolysis, all other compositional parameters held constant. The acetyl group removal is proportional to the stoichiometric relation between added base and wood acetyl content, i.e., the same number of milliequivalents of base/weight of wood remove the same extent of acetyl groups, regardless of the concentration of the base solution. No cation effects are found among Li, Na, and K alkali hydroxide solutions, suggesting that swelling is not as important a parameter as is the removal of the acetyl groups from the xylan backbone in determining the extent of hydrolyzability of the resulting sample.  相似文献   
52.
The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques.  相似文献   
53.
Dioscoreae (Chinese name Shanyao), the rhizome of various species of genus Dioscorea opposita Thunb.(Dioscoreaceae), has been used as an important invigorant in traditional Chinese medicine (TCM) for many years1. Starch, the most abundant carbohydrate in …  相似文献   
54.
The hydrolysis of solutions, containing either LiMo2O4(OPr i )5( i PrOH) and “La(OPr i )3” or LiOPr i and La2Mo4O8(OPr i )14 in 1∶1 ratio, in toluene or i PrOH, by water solutions in isopropanol, leads to formation of monolythic gels. The latter can be converted by drying and heat treatment at 600°C into a fine powder of pure α-LiLaMo2O8 phase, which is transformed into β-LiLaMo2O8 powder by annealing at 800°C. The sintering of the pellets pressed under 4 bar pressure of α-LiLaMo2O8 powder at 800°C for 2 h converts them into pieces of β-LiLaMo2O8 transparent ceramics, thus providing a route to LiLnMo2O8 laser waveguide materials.  相似文献   
55.
前驱体水解对纳米铂形状控制合成的影响   总被引:5,自引:1,他引:5  
于迎涛  徐柏庆 《化学学报》2003,61(11):1758-1764
以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂,对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性,揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定,避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言,避光静墨的 K_2PtCl_6水溶液很稳定,以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后,以聚丙烯酸钠为保护剂 ,通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。  相似文献   
56.
He D  Bao L  Long Y  Wei W  Yao S 《Talanta》2000,50(6):525-1273
A new bulk acoustic wave (BAW) cellulase sensing technique, which is based on the enzymatic hydrolysis process of sodium carboxymethylcellulose (CMC) by cellulase, was established. The frequency shift curves of BAW sensor indicated that the viscosity of the tested solutions decreased during the hydrolysis process. The hydrolysis rate of CMC by cellulase was calculated from the frequency shift curves. The hydrolysis rate of CMC under different pH conditions at 30°C showed that cellulase had high hydrolysis ability approximately at pH 5.0. Kinetic parameters (the Michaelis constant Km and the maximum rate Vmax) of the process were estimated by using a linear method of Lineweaver–Burk plot. Km is 1.95±0.25 mg ml−1 and Vmax is −(4.25±0.58)×10−3 g1/2 cm−3/2 cP1/2 min−1. Also the activation energy (Ea) of the enzymatic hydrolysis, with a value of 51.99±1.26 kJ mol−1, was estimated in this work.  相似文献   
57.
The hydrolysis reaction of 2-nitro-4-carboxyphenyl acetate was studied in dichloromethane in the presence of an added electrolyte (NaOH) and cationic surfactants systems with varying quantities of added water at 25°C. The kinetic and conductivity data were correlated.  相似文献   
58.
Reactions of naphthaleneeuropium and naphthaleneytterbium, C10H8Ln(DME) (Ln = Eu or Yb), with phenylacetylene are accompanied by the formation of the C-C bond and yield the complexes of composition Ph2C4H2Ln(DME)2. Hydrolysis of the Ph2C4H2Ln(DME)2 complexes affords a mixture of isomers of 1,4-diphenyl-1,3-butadiene. Reactions of C10H8[LnI(DME)2]2 with PhCCH yield mixed iodine-ethynyl complexes [ILn(-CCPh)(DME)2]2. According to the data of X-ray diffraction analysis, the ytterbium complex consists of two YbI(DME)2 units bonded through two bridging CCPh groups. The crystals of this complex belong to the space groupP21/c. The central cyclic Yb-C-Yb-C fragment is planar; the C(I)-Yb(I)-C(I) angle is 86.4(3)°. The Yb-C bond lengths are 2.584(8) and 2.603(9) Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2101–2104, August, 1996.  相似文献   
59.
The reaction of 2,6-dibenzylidenecyclohexanone with PCl5 occursvia the sequential stages of desoxychlorination and substitutional phosphorylation to form (after oxidation, methoxylation, and hydrolysis on the surface of the chromatographic SiO2 adsorbent) organophosphorus products of the 1-(a-chloro-, a-hydroxy-, or -alkoxy)benzyl-2-chloro-3-(-(dimethylphosphoryl)benzylidene)cyclobex-1-ene series.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 441–443, February, 1996.  相似文献   
60.
Stable colloidal suspensions of cellulose microcrystallites may be prepared from filter paper by sulfuric acid hydrolysis. Above a critical concentration, the suspensions form a chiral nematic ordered phase, or colloid crystal. The preparation conditions govern the properties of the individual cellulose microcrystallites, and hence the liquid crystalline phase separation of the cellulose suspensions. The particle properties and the phase separation of the suspensions were strongly dependent on the hydrolysis temperature and time, and on the intensity of the ultrasonic irradiation used to disperse the particles. The particle size of the microcrystallites was characterized with transmission electron microscopy and photon correlation spectroscopy. The surface charge was determined by conductometric titration. It was possible to fractionate the microcrystallites by size using the partitioning between isotropic and liquid crystalline phases; the longer microcrystallites migrate to the liquid crystalline phase  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号