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71.
Dr. George Dhimba Prof. Dr. Alfred Muller Prof. Dr. Koop Lammertsma 《欧洲无机化学杂志》2023,26(25):e202300256
Cis-MoO2(nacnac)2 (nacnac=β-diketiminate) can be a viable chiral-at-metal catalyst when its two β-diketiminate (nacnac) ligands are N-substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây-Dutt, Conte-Hippler, and Dhimba-Muller-Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X-D/6-311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔGo=27.4 kcal/mol with N-substituted t-butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed. 相似文献
72.
A facile method for the copper-catalyzed synthesis of N-benzyl-N-phenyl-2-benzothiazolamines was explored. In the presence of CuI, N-phenylbenzothiazolamines was in situ generated from substituted 1-(2-iodophenyl)-3-phenylthioureas, which susequently underwent coupling with benzyl/allyl halides to give the desired N-benzyl/allyl-N-phenyl-2-benzothiazolamines fluently in a one-pot manner. The protocol features easy performance, easily available materials, good yield and broad substrates scope, showing potential synthetic value for the preparation of a variety of biologically or pharmaceutically active compounds. 相似文献
73.
Dr. Gang Wang Jiang Wu Yi Li Zicheng Huang Jing Zou Dr. Zhao-Lin He 《European journal of organic chemistry》2023,26(34):e202300450
A cross-1,3-dipolar cycloaddition reaction of α-halohydroxamates (in situ generated azaoxyallyl cations) with N,N′-cyclic azomethine imines was developed. The synthetic protocol provided facile and rapid access to pyrazolo[1,2-a][1,2,4]triazine derivatives in good yields and excellent diastereoselectivities under mild metal-free conditions. 相似文献
74.
Sonomi Arata Dr. Yuna Kim Prof. Norihisa Hoshino Dr. Keishiro Tahara Dr. Kiyonori Takahashi Dr. Tomofumi Kadoya Tomonori Inoue Prof. Takayoshi Nakamura Prof. Tomoyuki Akutagawa Prof. Jun-ichi Yamada Prof. Kazuya Kubo 《欧洲无机化学杂志》2023,26(12):e202300017
Unsymmetrical gold(III)-dithiolene complexes are potential candidates for molecular materials that exhibit thermal structural phase transitions. In this study, unsymmetrical ppy-gold(III) (ppy−=C-deprotonated-2-phenylpyridine(−)) complexes [AuC5] and [AuC6] coordinated by dithiolene ligands containing tetrathiafulvalene (TTF) skeletons with pentylthio (2-{bis(pentylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) and hexylthio groups (2-{bis(hexylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) were synthesized. Both complexes exhibited a large absorption band at approximately 508 nm, owing to intramolecular ligand-to-ligand charge transfer. One-dimensional columnar structures with head-to-tail molecular arrangements around the metal ions were constructed in the crystals. The flexible alkylthio groups were intercalated into crystalline spaces between dithiolene ligands in the columns. [AuC5] exhibits a simple phase transition at 198 °C between crystalline and isotropic phases irreversibly. The crystalline phase of [AuC6] observed at 25 °C melted at 148 °C. Another crystalline phase grew above 148 °C with a very slow crystallization rate from the liquid phase and was completely transformed into an isotropic phase at 200 °C. 相似文献
75.
76.
合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H2O)4]2(SO4)3·3.5H2O}n (1)、{[Ni(Hbpma)(H2O)4]4(SO4)6·10.75H2O}n (2)、{[Mn(Hbpma)(H2O)4](SO4)1.5·3H2O}n (3)、{[Zn(Hbpma)(H2O)4]4(SO4)6·4H2O·4CH3OH}n (4)和{[Cu(Hbpma)2(H2O)2](SO4)2·9H2O}n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。 相似文献
77.
Cuprous chloride was coordinated by diazabutadiene (DAB‐R) ligands to form Cu(I)‐(DAB‐R) complexes, most of which have a 1:1 ratio of Cu to DAB‐R as reported. In the case of a special DAB‐iPP, N,N′‐bis(2,6‐diisopropylphenyl)‐1,4‐diaza‐1,3‐butadiene, an unexpected composition of complex was found with the formula Cu(I)Cl(DAB)2. When employed as catalyst for triarylamine synthesis from the coupling of aryl halides with primary and secondary arylamines, the new Cu(I)‐(DAB‐iPP) complex displayed high efficiency. 相似文献
78.
研究了N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)溶于疏水性离子液体咪唑类离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C2mim][NTf2])中对硝酸水溶液体系中四价钍离子(Th4+)的萃取行为。详细考察了接触时间、酸度、Th4+浓度、TODGA浓度、温度对TODGA/[C2mim][NTf2]体系萃取性能的影响。作为对比,我们还考察了TODGA在传统有机溶剂异辛烷中对Th4+的萃取。结果表明:TODGA/[C2mim][NTf2]体系对Th4+的萃取是吸热反应,且在50℃下,能在5 min内达到平衡。萃取体系随着酸度对Th4+的萃取性能先降后增大;Th4+浓度的增大,TODGA浓度的降低,对Th4+的萃取性能下降。TODGA在离子液体萃取体系中比在有机体系中有更好的Th4+萃取效果,特别是在低酸条件下。通过萃取机理研究,推测出在低酸下萃取反应是离子交换且TODGA与Th4+配比为2∶1,在高酸下萃取是中性配位。 相似文献
79.
The base mediated cycloaddition reactions of 4‐dimethylamino‐1‐phenacylpyridinium bromides with two molecular 3‐phenacylideneoxindoles in methylene dichloride afforded functionalized dispirocyclopentyl‐3,3′‐bisoxindoles in good yields and with high diastereoselectivity. The similar cycloaddition reactions of 1‐(N,N‐dialkylcarbamoylmethyl) and 1‐cyanomethyl 4‐dimethylamino‐pyridinium bromide in refluxing ethanol in the presence of triethylamine also resulted in dispirocyclopentyl‐3,3′‐bisoxindoles with high diastereoselectivity. The stereochemistry of dispirocyclopentyl‐3,3′‐bisoxindoles was elucidated on the basis of 1H NMR data and single crystal structures. 相似文献
80.
通过丙烯酰胺(AM),丙烯酸(AA),烯丙醇聚氧乙烯醚(APEG)和N,N-二烯丙基苄胺(NANB)制备共聚物P(AM/AA/APEG/NANB)。确定了最佳反应条件:m(AM)∶m(AA)=6.5∶3,APEG为5 wt%,NANB加量0.2 wt%,pH为7,反应温度40℃,引发剂0.4 wt%。通过IR和1H NMR确定了聚合物的分子结构,并对其进行性能测试。结果表明:2000 mg·L-1的AM/AA/APEG/NANB溶液具有较好的流变性能(120℃,粘度保留率:38.56%;1000 s-1,粘度保留率:17.93%)和抗盐性能(20 000 mg·L-1Na Cl,2000 mg·L-1Mg Cl2或Ca Cl2,粘度保留率分别为22.14%、18.34%和15.33%),且提高采收率可达16.12%。 相似文献