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31.
32.
Cao C Dahal S Shang M Beatty AM Hibbs W Schulz CE Scheidt WR 《Inorganic chemistry》2003,42(17):5202-5210
The effect of a sixth ligand in a series of low-spin thiocarbonyl-ligated iron(II)octaethylporphyrinates has been investigated. Six-coordinate complexes have been synthesized and characterized by M?ssbauer and infrared spectroscopy and single-crystal X-ray structure determinations. The results are compared with the five-coordinate parent complex. The crystal structures of [Fe(OEP)(CS)(1-MeIm)] and [Fe(OEP)(CS)(Py)] are reported and discussed. The 1-methylimidazole and pyridine derivatives exhibit Fe-C(CS) bond distances of 1.703(4) and 1.706(2) A that are significantly longer than the 1.662(3) A reported for five-coordinate [Fe(OEP)(CS)] (Scheidt, W. R.; Geiger, D. K. Inorg. Chem. 1982, 21, 1208). The trans Fe-N(ligand) distances of 2.112(3) and 2.1550(15) A observed for the 1-methylimidazole and pyridine complex are approximately 0.13 A longer than those observed for analogous bis-ligated complexes and are consistent with a significant structural trans effect for the CS ligand. M?ssbauer investigations carried out for five- and six-coordinate thiocarbonyl derivatives with several different sixth axial ligands reveal interesting features. All derivatives exhibit very small isomer shift values, consistent with a very strong interaction between iron and CS. The five-coordinate derivative has delta(Fe) = 0.08 mm/s, and the six-coordinate complexes exhibit delta(Fe) = 0.14 to 0.19 mm/s at 4.2 K. The five-coordinate complex shows a large quadrupole splitting (DeltaE(q) = 1.93 mm/s at 4.2 K) which is reduced on coordination of the sixth ligand (DeltaE(q) = 0.42-0.80 mm/s at 4.2 K). Addition of a sixth ligand also leads to a small decrease in the value of nu(CS). Correlations in structural, IR, and M?ssbauer results suggest that the sixth ligand effect is primarily induced by changes in sigma-bonding. The structure of [Fe(OEP)(CS)(CH(3)OH)] is briefly reported. Crystal data: [Fe(OEP)(CS)(1-MeIm)] crystallizes in the monoclinic system, space group P2(1)/n, Z = 4, a = 9.5906(5) A, b = 16.704(4) A, c = 23.1417(6) A, beta = 100.453(7) degrees. [Fe(OEP)(CS)(Py)] crystallizes in the triclinic system, space group P1, Z = 5, a = 13.9073(6) A, b = 16.2624(7) A, c = 22.0709(9) A, alpha = 70.586(1) degrees, beta = 77.242(1) degrees, gamma = 77.959(1) degrees. [Fe(OEP)(CS)(CH(3)OH)] crystallizes in the triclinic system, space group P1, Z = 1, a = 9.0599(5) A, b = 9.4389(5) A, c = 11.0676(6) A, alpha = 90.261(1) degrees, beta = 100.362(1) degrees, gamma = 114.664(1) degrees. 相似文献
33.
Jie Shao Hai Lin Xue-Fang Shang Hua-Mei Chen Hua-Kuan Lin 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(3-4):371-375
A new urea-based receptor was designed to selectively recognize H2PO4− among other anions (such as F-, Cl-, Br-, I-, OH-, AcO-) in organic solvent (DMSO) through intermolecular hydrogen bonding. Addition of anions to the receptor caused changes in
UV–vis spectrum which provided the first indication of its anion binding ability.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
34.
Shang Chen Chenyan Ren Yuan Ji Dongke Liu Xinke Zhang Fengshan Wang 《Molecules (Basel, Switzerland)》2022,27(13)
Thymus immunosuppressive pentapeptide (TIPP) is a novel anti-inflammatory peptide with high efficacy and low toxicity. This study aims to establish a selective LC-MS/MS method for analyzing the analyte TIPP in biological samples, laying the foundation for further PK and PD studies of TIPP. Protein precipitation was conducted in acetonitrile supplemented with 2% formic acid and 25 mg/mL dithiothreitol as a stabilizer, which was followed by backwashing the organic phase using dichloromethane. The chromatographic separation of TIPP was achieved on a C18 column with a gradient elution method. During positive electrospray ionization, TIPP was analyzed via multiple-reaction monitoring. The linear relationships between the concentration of TIPP and peak area in murine plasma cell lysates, supernatants, and the final cell rinse PBS were established within the ranges of 20–5000 ng/mL, 1–200 ng/mL, 10–200 μg/mL, and 0.1–20 ng/mL, respectively (r2 > 0.99). Validated according to U.S. FDA guidelines, the proposed method was proved to be acceptable. Such a method had been successfully applied to investigate the pharmacokinetics of TIPP in mice via subcutaneous injection. The plasma half-life in mice was 5.987 ± 1.824 min, suggesting that TIPP is swiftly eliminated in vivo. The amount of TIPP uptake by RBL-2H3 cells was determined using this method, which was also visually verified by confocal. Furthermore, the effective intracellular concentration of TIPP was deduced by comparing the intracellular concentration of TIPP and degrees of inflammation, enlightening further investigation on the intracellular target and mechanism of TIPP. 相似文献
35.
辉光等离子体辅助化学气相沉积低温合成金刚石薄膜的研究 总被引:5,自引:0,他引:5
采用辉光放电等离子体增强化学气相沉积 (GP CVD)技术在低温条件下合成了高品质的亚微米金刚石薄膜 ,并通过对合成过程的实时发射光谱诊断确定了 [CH4 H2 ]系统参与金刚石合成反应的主要荷能粒子。对合成过程的研究表明 :采用这种技术能使电子增强热丝化学气相沉积 (EACVD)合成高品质金刚石薄膜的温度从 85 0℃降至 (340± 5 )℃ ;薄膜低温合成中的主要荷能粒子为CH3 、CH ,CH+ 、H 等 ,其中过饱和原子氢保证了高品质金刚石薄膜的合成 ;根据光诊断和探针测量的结果推断近表面辉光放电可在基片表面形成电偶极层 ,该偶极层是进行超常态反应的必要环境 ,并在低温合成中起重要作用 相似文献
36.
Theoretical analysis on double Rayleigh backscattering noise in optical fibreRaman amplifiers and its suppression 下载免费PDF全文
In this paper, amplified double Rayleigh backscattering noise (DRB) in the optical fibre Raman amplifier is analysed. Expressions are presented for both forward pumping and backward pumping schemes. Calculation is performed to show the effective suppression of DRB noise by employing an optical isolator. The optimal position for the isolator is determined and is found to be insensitive to the power levels of the signals and pumps. The results show that a reduction of the DRB noise by almost 2 to 3 orders can be reached. 相似文献
37.
高温扫描隧道显微镜(HT-STM)可以实时原位地捕捉到表面原子的熔化相变过程.在这一原位变温实验中,快速可靠地识别出每帧STM图像中的熔融相十分关键.传统的手工统计方法存在效率低下、随意性大等问题.我们发展出一套基于数学形态学的算法,来自动快速地识别.与人工方法相比,该算法消除了人为主观误差,使确定的边界更加准确、光滑,处理效率提高了266倍. 相似文献
38.
炸药颗粒的点火燃烧过程一直是人们关注的热点问题。近年来,三维离散元技术在中尺度观测颗粒材料的动力学过程中拥有显著优势。炸药燃烧属于颗粒材料的反应动力学,运用三维离散元技术(DM3)可以有效地观测炸药燃烧传播的过程。以奥克托今(HMX)颗粒为例,本文成功模拟并观测到了HMX颗粒的燃烧反应程度,确定了颗粒开始燃烧反应的时间,以及燃烧反应传播的时间。同时,结合落锤冲击颗粒的三维图像以及其表观压强和放热功率,得到了HMX颗粒燃烧反应、燃烧传播的整个反应动力学过程,包括颗粒在冲击加载下碎化塑性变形的过程,颗粒燃烧反应放热的过程,落锤回弹颗粒喷射的过程等。同时,进一步说明了尖顶颗粒更利于颗粒点火,平顶颗粒有抑制颗粒点火的能力。 相似文献
39.
β-胡萝卜素具有光采集、光防护功能, 又是重要的光电材料, 它在外场下的分子结构和性能变化既有理论意义也有应用价值。测量了β-胡萝卜素在环己醇中68~26 ℃温度范围内的紫外-可见吸收、拉曼光谱。实验结果表明随着温度的降低, 黄琨因子和碳碳键每个振动模的电子-声子耦合常数减小, 紫外-可见吸收光谱红移, 碳碳键拉曼散射截面增加。用线性链状多烯分子的“相干弱阻尼电子-晶格振动模型”、“有效共轭长度模型”等理论给予了解释。随着温度的降低,β-胡萝卜素分子的热无序减小,分子结构有序性增加,π电子离域扩展,有效共轭长度增加,导致紫外-可见吸收光谱红移和强的拉曼活性。相干弱阻尼电子-晶格振动增强,使碳碳键拉曼散射截面增加。引用带有量纲的电子-声子相互作用常数,既可以与黄昆因子建立关系式,计算出碳碳键每个振动模的数值,也可以表征分子的有效共轭长度,π电子离域程度及拉曼散射截面的大小等。 相似文献
40.
负氢离子源的研究对于响应国家散裂中子源建设和国际热核聚变实验堆计划的开展都具有十分重要的意义. 由于离子源本身的物理特性导致数值模拟成为不可或缺的研究手段, 基于此, 首先对自主研发的全三维粒子模拟/蒙特卡罗碰撞算法进行阐述, 然后对负氢离子体积过程进行描述, 并在此基础上对中国原子能研究中心的多峰质子源进行了系统仿真, 在引出磁体极性相同和相反两种情形下, 分别对多峰质子源放电特性进行了讨论和分析. 结果显示: 在相反极性下, 两引出磁体附近的磁漂移方向相同且数值较大, 即磁漂移剧烈, 导致电子总数较大且高能电子在特定区域活跃, 进而负氢离子体积产率较高, 即负氢离子在空间呈现Y漂移; 反之, 在相同极性下, 电子约束效果相对较差且负氢离子体积产率较低, 但其空间分布均匀. 相似文献