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21.
Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes 下载免费PDF全文
Dominique Miesel Dr. Alexander Hildebrandt Marcus Korb Prof. Dr. Heinrich Lang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11545-11559
2,5‐Diferrocenyl‐1‐Ar‐1H‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐tert‐butylphenyl ( e )) have been prepared by reactions of ArPH2 ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐tert‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [NnBu4][B(C6F5)4]; these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ]+–[ 3 e ]+ show intervalence charge‐transfer absorptions between 4650 and 5050 cm?1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b . 相似文献
22.
Dr. Christiane Lang Sebastian Bestgen Dr. Alexander Welle Rouven Müller Prof. Peter W. Roesky Prof. Christopher Barner‐Kowollik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14728-14731
A platform technology for the creation of spatially resolved surfaces encoded with a monolayer consisting of different metal complexes was developed. The concept entails the light‐triggered activation of a self‐ assembled monolayer (SAM) of UV‐labile anchors, that is, phenacylsulfides, and the subsequent cycloaddition of selected diene‐functionalized metal complexes at defined areas on the surface. The synthesis and characterization of the metal complexes for the UV‐light assisted anchoring on the surface and a detailed study of a short‐chain oligomer model system in solution confirm the high efficiency of the photoreaction. The hybrid materials obtained by this concept can potentially be utilized for the design of highly valuable catalytic or (opto‐)electronic devices. 相似文献
23.
Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells 下载免费PDF全文
Yunyi Gao Fadi Haso Jennifer E. S. Szymanowski Jing Zhou Lang Hu Prof. Dr. Peter C. Burns Prof. Dr. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(51):18785-18790
The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion‐transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm‐sized, fullerene‐shaped molecular cluster Li48+mK12(OH)m[UO2(O2)(OH)]60?(H2O)n (m≈20 and n≈310) ( U60 ) shows selective permeability to different alkali ions. The subnanometer pores on the water–ligand‐rich surface of U60 are able to block Rb+ and Cs+ ions from passing through, while allowing Na+ and K+ ions, which possess larger hydrated sizes, to enter the interior space of U60 . An interestingly high entropy gain during the binding process between U60 and alkali ions suggests that the hydration shells of Na+/K+ and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells. 相似文献
24.
分别用稀土醋酸盐和稀土高氯酸盐与希弗碱配体和巯基烟酸配体反应得到了两例镝配合物[Dy2(OAc)6H2O]n(1)和{[DyL(H2O)4]ClO4·H2O}n(2)(L=2,2'-二硫代-二(3-吡啶甲酸)),并通过单晶X-射线衍射、元素分析、红外光谱和磁性测试对其进行了表征。结构研究和磁性测试表明:化合物1是羧基桥连的一维链结构,该化合物表现出慢磁弛豫性质,有效能垒为2 K;化合物2是通过原位生成的二硫键桥连的二维网状结构,表现出明显的铁磁相互作用和慢磁弛豫行为。 相似文献
25.
Sonja Kracht Dr. Matthias Messerer Dr. Matthieu Lang Dr. Sonja Eckhardt Dr. Miriam Lauz Prof. Bernard Grobéty Prof. Katharina M. Fromm Prof. Bernd Giese 《Angewandte Chemie (International ed. in English)》2015,54(10):2912-2916
Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag+ ions bound by peptides with histidine as the Ag+‐binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time‐resolved UV/Vis spectra which exhibit an isosbestic point. 相似文献
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27.
Yongbing Song Run Jiang Zheng Wang Lang Wang Yuhua Yin Baohui Li An‐Chang Shi 《Macromolecular theory and simulations》2016,25(6):559-570
The self‐assembled morphologies of cyclic amphiphiles, which are composed of a long hydrophobic block and a short hydrophilic block, in selective solutions are studied by using a simulated annealing method. The morphological dependence of the aggregates on solvent quality is investigated. The topology effects are studied by comparing results from linear counterparts of the amphiphiles. It is observed that, in addition to spherical micelles, cylindrical micelles, disklike micelles, vesicles, and large compound micelles, muticompartment vesicles with several fluidic cores can be formed by the cyclic systems. The morphologies are regulated by the interaction parameter εAS between the hydrophobic block and solvents. Furthermore, it is revealed that the differences of characteristics of the self‐assembled aggregates originate from the difference in architectural constraint. The wide region of forming multicompartment vesicles suggests that cyclic amphiphilic macromolecules could be a suitable candidate for applications to deliver multiple functional components by compartmentalizing different components in different confined space of vesicles. 相似文献
28.
目的 了解亚胺培南耐药鲍曼不动杆菌(CRAB)医院感染的危险因素,并探讨Ⅰ类整合子在鲍曼不动杆菌亚胺培南耐药中的作用。方法 选取确诊为CRAB 医院感染患者54 例作为病例组,按1:3 配对选择162 例亚胺培南敏感鲍曼不动杆菌(CSAB)医院感染患者作为对照组,采用单因素分析及多因素logistic 回归分析其危险因素,PCR 检测Ⅰ类整合酶基因。结果 单因素分析发现,与CRAB 医院感染相关的危险因素有病情危重、入住ICU 时间、住院时间≥14d、机械通气/ 人工气道、留置尿管、中心静脉置管、免疫抑制剂的使用、抗生素使用时间≥7d、抗生素药物种类≥3 种。多因素logistic回归分析发现,病情危重(OR:8.47;95% CI:1.56~46.0)、入住ICU 时间(OR:9.32; 95% CI:1.83~47.43)、住院天数≥14d(OR:13.89;95% CI:3.07~62.85)、机械通气/ 人工气道(OR:18.86; 95% CI:4.38~81.31)、抗生素使用种类≥3 种(OR:6.16;95% CI:1.85~20.51)、抗生素使用时间≥7d(OR:5.41; 95% CI: 1.36~21.58)是CRAB 医院感染的独立危险因素;CRAB 组中Ⅰ类整合酶基因检出率(59.3%)显著高于CSAB 组(34.6%),差异有统计学意义(P<0.001)。结论 病情危重、入住ICU 时间、住院时间、机械通气/ 人工气道、抗生素使用种类≥3种、抗生素使用时间≥7d 是CRAB 医院感染的独立危险因素,Ⅰ类整合子在CRAB 中普遍存在,需加强对相关危险因素的控制及耐药机制的研究,早期防治CRAB 医院感染的发生。 相似文献
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在高功率固体激光器的终端光学组件内, 大口径薄型KDP (KH2PO4)晶体的精密装配和校准是实现惯性约束核聚变的关键技术之一. 为了达到晶体在线安装高效高精度的要求, 需要测量高功率激光三次谐波转换效率达到最高时的晶体相位匹配角分布. 本文针对Ⅰ/Ⅱ类大口径薄型KDP晶体三次谐波转换的方式, 根据晶体的非线性光学属性获得了晶体不同位置相位匹配角之间的关系; 根据激光束在晶体内的传输路径分析得到了晶体面形、相位匹配角与激光三次谐波转换效率达到最高时 晶体最佳偏转角之间的相互关系. 在此基础上, 建立了Ⅰ/Ⅱ类KDP晶体相位匹配角的理论预测模型, 并利用实验进行了验证和分析. 实验结果表明, 晶体相位匹配角的预测值与实验值之差在10.0 μrad以内, 验证了Ⅰ/Ⅱ类KDP晶体相位匹配角理论预测模型的正确性, 为获得晶体全口径相位匹配角分布提供了简单、高效的预测方法. 相似文献