全文获取类型
收费全文 | 34176篇 |
免费 | 4949篇 |
国内免费 | 3959篇 |
专业分类
化学 | 24497篇 |
晶体学 | 363篇 |
力学 | 2203篇 |
综合类 | 403篇 |
数学 | 3953篇 |
物理学 | 11665篇 |
出版年
2024年 | 40篇 |
2023年 | 688篇 |
2022年 | 688篇 |
2021年 | 1037篇 |
2020年 | 1355篇 |
2019年 | 1312篇 |
2018年 | 1060篇 |
2017年 | 997篇 |
2016年 | 1512篇 |
2015年 | 1466篇 |
2014年 | 1811篇 |
2013年 | 2405篇 |
2012年 | 3028篇 |
2011年 | 3171篇 |
2010年 | 1983篇 |
2009年 | 2005篇 |
2008年 | 2116篇 |
2007年 | 1969篇 |
2006年 | 1791篇 |
2005年 | 1508篇 |
2004年 | 1154篇 |
2003年 | 1021篇 |
2002年 | 1013篇 |
2001年 | 786篇 |
2000年 | 709篇 |
1999年 | 786篇 |
1998年 | 639篇 |
1997年 | 603篇 |
1996年 | 665篇 |
1995年 | 556篇 |
1994年 | 511篇 |
1993年 | 426篇 |
1992年 | 386篇 |
1991年 | 333篇 |
1990年 | 271篇 |
1989年 | 214篇 |
1988年 | 165篇 |
1987年 | 151篇 |
1986年 | 144篇 |
1985年 | 122篇 |
1984年 | 92篇 |
1983年 | 67篇 |
1982年 | 44篇 |
1981年 | 39篇 |
1979年 | 18篇 |
1978年 | 19篇 |
1977年 | 23篇 |
1976年 | 21篇 |
1975年 | 29篇 |
1974年 | 27篇 |
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
991.
合成了三(三苯基氧膦)合硝酸镧络合物, 经鉴定确定络合物化学式为La(NO_3)_3·3ph_3PO·C_2H_5OH·CHCl_3。其中C_2H_5OH和CHCl_3为溶剂化分子。经X射线单晶衍射, 测定了该络合物属单斜晶系P2_1/n空间群, 晶体学参数如下a=1.3111(5) nm Z=4b=2.5075(10) nm F(000)=2687.65c=1.8725(6) nm μ吸收系数=9.83(cm~(-1))β=98.53(3)° d计算=1.45 gcm~(-3)V=6.088 nm d实验=1.43 gcm~(-3)La与9个氧直接配位, 其中六个氧来自三个双卤配位硝酸根, 另三个氧分别由三个苯基氧膦上的膦酰基所提供。La-O平均键长0.2549 nm。 相似文献
992.
表面活性剂混合物水溶液中的囊泡形成 总被引:1,自引:0,他引:1
1:1烷基羧酸钠-溴化烷基三甲铵混合水溶液的浓度在cmc以上时, 能自发或超声分散形成一类新型混合表面活性剂囊泡(单层膜), 正负离子表面活性剂的突出囊泡形成能力以及不同表面活性剂结构组合变化所显现的多样特性, 皆预示出混合功能有序组合体研究的广阔前景。 相似文献
993.
994.
Ji‐Jiang Wang Meng‐Lin Yang Huai‐Ming Hu Prof. Dr. Gang‐Lin Xue Dong‐Sheng Li Qi‐Zhen Shi 《无机化学与普通化学杂志》2007,633(2):341-345
To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)0.5(phen)]·H2O ( 2 ) (H4btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd2 units are linked by bridging btc4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd2 units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature. 相似文献
995.
Ultrafine nylon fibers were prepared by electrospinning of nylon-6,66,1010 terpolymer solution in 2,2,2-trifluoroethanol (TFE). The morphology, crystallinity and mechanical properties of the electrospun nylon-6,66,1010 fibers were investigated by scanning electron microscope (SEM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and tensile test. The effects of electrospun process parameters such as solution concentration, voltage and tip-to-collector distance on the morphology and the average size of the electrospun fibers were also studied. The results show that the spinnable concentration of nylon-6,66,1010/TFE solution is in the range of 6-14 wt%, and higher solution concentration favors the formation of uniform fibers without beads. The diameters of the electrospun fibers increase with increasing the solution concentration and decrease slightly with increasing the voltage and needle tip-to-collector distance. But no obvious morphology changes were found with the increase of the voltage and collection distance. DSC and WAXD results suggest that the electrospun nylon-6,66,1010 membranes have lower crystallinity than those of the corresponding casting films. The electrospun nylon-6,66,1010 membrane obtained from the 14 wt% concentration exhibits the largest tensile strength and elongation at break. 相似文献
996.
Hong FE Chang YC Chang CP Huang YL 《Dalton transactions (Cambridge, England : 2003)》2004,(1):157-165
Treatment of a cobalt-containing diphosphine ligand, [[mu-P,P-PPh2CH2PPh2]Co2(CO)4[mu-PPh2C[triple bond]CPPh2]] 1 with metal complexes W(CO)6, Ru3(CO)12, AuCl(tht)(tht = tetrahydrothiophene) and (COD)PdCl2(COD = 1,5-cycloctadiene) gave 1-chelated metal complexes [(1)W(CO)4], [(mu-1)Ru3(CO)10] 4, [(1)(AuCl)2] 5 and [(1)PdCl2] 6, respectively. All these compounds were characterized by spectroscopic means whereas 3, 4 and 6 were also studied by X-ray diffraction. These compounds display chelating and bridging modes of metal-phosphine complexation. Variable-temperature 1H and 31P NMR experiments were carried out for 3-6 and revealed that the fluxional behavior of each individual bridging dppm fragment was affected greatly by the bite angle of 1 in each metal complex. Suzuki cross-coupling reactions were satisfactorily catalyzed by under mild conditions. The reactions of aryl halides or iodothiophenes with chloroform and alkali in biphasic solution utilizing a catalytic amount of result into the formation of benzoic and thiophenic acids, respectively. 相似文献
997.
Alan P. Marchand Anna Hazlewood Zilin Huang Satish Kumar Vadlakonda John-David R. Rocha Trevor D. Power Kata Mlinarić-Majerski Lada Klaić Goran Kragol Jeffrey C. Bryan 《Structural chemistry》2003,14(3):279-288
Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K+ and Rb+. A stable host–guest complex was prepared by slow evaporation of a CH2Cl2–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K+ complex and picrate anion was calculated to be ca. –64.9 kcal mol–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10. 相似文献
998.
离子浮选石墨炉原子吸收光谱法测定水中痕量Cr(Ⅵ)/Cr(Ⅲ) 总被引:10,自引:0,他引:10
本文以二苯卡巴肼(DPCI)和十二烷基硫酸钠(SLS)为浮选剂研究了分离浓缩(Cr(Ⅵ)的最佳条件,建立了水中痕量络的形态分析方法。该方法简单、快速、检测限0.03μgL^-1,变异系九小于4%,200mL水样中含NO350,Na^+,Mg^2+40,Cl28,D,Ca^2+,SO410,CO39,Al^2+,Co^2+,Ni62+5,Mn^2,Pb^2+2.5,Fe^3+0.2mg不影响测定。方 相似文献
999.
For chiral primary amino compounds not separable by cyclodextrins alone, chiral recognition was successfully achieved by the formation of a sandwiched complex of the non-chiral 18-crown-6, the chiral amine and cyclodextrin (CD) [18-crown-6+amino compound+CD]. The separation of 1-methyl-3-phenylpropylamine and 1,2,3,4-tetrahydro-1-naphthylamine racemates showed the special function of the non-chiral 18-crown-6 on chiral recognition. By formation of the sandwiched complex, the chiral center of 1-methyl-3-phenylpropylamine was successfully recognized, and resolution of 1,2,3,4-tetrahydro-1-naphthylamine dramatically increased. In these studies, the mobility differences of the enantiomers were evaluated as a function of the concentration of cyclodextrins with and without the 18-crown-6, and as a function of the concentration of the 18-crown-6. In addition, the separations by this method were compared to those by the chiral 18-crown-6 reagent. 相似文献
1000.
STUDY ON PREPARATION OF INORGANIC COMPOSITE MEMBRANE AND ITS PROPERTIES FOR HYDROGEN PERMEATION 下载免费PDF全文
IntroductionDevclopmcntoftcchniqucsforthcscparationofgascousmixturesisofgrcatimportancetochemicalindustries.Rccentadvanccsinceramicmaterialprocessinghavcstimulatedtheeffortstodcvclopccramicormctallicmcmbrancsforgasseparation.Suchmembraneswouldbesuitableforthescparationsathightemperatureatx`hichthcx`ellcstablishedorganicpol}mermcmbranescannotfunctionButmostcommercialceramicmembranesxvhichcanbcobtainedinmarkctaremicroporous(porediamcterfromO.ItoloPm)whereseparationmcchanismisgovcrncdbyKnudscnd… 相似文献