Conformation and internal mobility of 5H-dibenzo[a,d]cycloheptene derivatives in solution. Conformational analysis of highly flexible structures,part II

Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.

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Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2

Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.

     

原子力显微镜针尖诱导聚氧乙烯熔体结晶的研究

原子力显微镜(AFM)是研究高分子结晶行为的一种重要实验手段.在使用AFM原位观察高分子结晶时,为保证能真实地反映结晶过程,一个必须注意的问题是要避免AFM针尖的影响.与此同时,人们考察了在AFM扫描时针尖诱导高分子结晶成核的情况.若使用AFM接触模式(contactmode),扫描时容易造     

利用AFM和SNOM对淋巴细胞膜表面超微结构及其光学性质的初步研究

利用原子力显微镜(Atomic Force Microscopy，AFM)对淋巴细胞表面形貌进行了形态学的初步研究，观察到了其膜表面其他显微技术所不能发现的超微结构．同时也运用扫描近场光学显微镜(Scanning Near field Optical Microscopy，SNOM)对淋巴细胞进行成像，观察了其对光的透射、吸收等光学性质，并对两种成像方法进行了比较．研究发现：淋巴细胞膜表面凹凸不平，分布着大量直径几十到几百纳米不等的小颗粒；淋巴细胞中央部位有自发荧光现象．结果表明，AFM和SNOM可作为进一步探讨淋巴细胞的结构与功能关系的有力工具．     

New perylene polyimides containing p‐n diblocks for sensitization in TiO2 solar cells

Three novel perylene polyimides (PPIs) containing p‐n diblock units were designed and synthesized for use in dye‐sensitized mesoporous TiO₂ solar cells. They all dissolve in m‐cresol and N‐methyl‐2‐pyrrolidone (NMP). Their visible light absorption, electrochemical and photoelectrochemical properties were systematically studied. The polyimides have band gap energies of 2.16, 2.19 and 2.25 eV deduced from ultraviolet–visible absorption spectra, and electron affinity (E_a) and ionization potential (IP) of ?3.93 and 6.10 eV for PPI1, ?3.94 and 6.13 eV for PPI2, ?3.93 and 6.59 eV for PPI3, respectively, deduced from cyclic voltammogram. Experimental data show that introduction of 4,4′‐bisaminetriphenylamine cannot only greatly enhance optic‐electro conversion efficiency, but also enhance the dissolubility which in favorable for making the devices. The relationship of structure and properties of PPI is discussed and the mechanism of photocurrent generation is explained. Copyright © 2004 John Wiley & Sons, Ltd.     

Phipps's lagrangian and hamiltonian

In this work it is derived Phipps's Lagrangian function and Phipps's Hamiltonian function. This allows the utilization of Phipps's interaction in the Lagrangian and Hamiltonian frameworks.Dedicated to Thomas E. Phipps, Jr. on the occasion of his 70th birthday (1995).     

The difference between Newtonian and relativistic forces

This paper discusses a new turn in the 148-year old electrodynamic force law controversy between the 1822 Ampère force law of the Newtonian electrodynamics and Grassmann's 1845 law which has become the electrodynamic force law of relativistic electromagnetism. Faced with the infallibility of Ampère's empirical law, defenders of relativity theory now argue that Ampère's law is equivalent to the relativistic law. This paper demonstrates that, far from being equivalent, the laws require two different mechanics of solid bodies, disagree on internally generated stresses, and predict different force distributions.     

RECENT PROGRESS OF NANO-MECHANICAL MAPPING

 Nano-mechanical mapping by atomic force microscopy has been developed as an useful application to measure mechanical properties of soft materials at nanometer scale. To date, the Hertzian theory was used for analyzing force-distance curves as the simplest model among several contact mechanics between elastic bodies. However, the preexisting methods based on this theory do not consider the adhesive interaction in principle, which cannot be neglected in the ambient condition. A new analytical method was introduced to estimate the elasticity and the adhesive energy simultaneously by means of the JKR theory, describing adhesive contact between elastic materials. Poly(dimethylsiloxane) (PDMS) and isobutylene-co-isoprene rubber (IIR) were analyzed to verify the applicable limit of the JKR analysis. For elastic samples such as PDMS, the force-deformation plots obtained experimentally were consistent with JKR theoretical curves. Meanwhile, for viscoelastic samples, especially for IIR, the experimental plots revealed large deviations from JKR curves depending on scanning velocity and maximum loading force. Some nano-rheological arguments were employed based on the difference between these specimens.     

Surface structures of adsorption layers of sodium hyaluronate and bovine serum albumin complexes on poly(γ-methyl-l-glutamate) film and their surface properties

Two-dimensional structures and characteristics of the complexes between sodium hyaluronate (NaHA) and bovine serum albumin (BSA) were studied by using a quartz crystal microbalance method and an atomic force microscope (AFM). NaHA did not adsorb on poly(-methyl-l-glutamate) (PMLG) film. On the other hand, the complexes adsorbed on it and the adsorption behaviors were found to be Langmuir types. With increasing weight ratio of BSA to NaHA, W _BSA, the adsorption constants K decreased and the saturated adsorption masses increased. The adsorbed complexes were spherical particles and at saturated adsorption states they covered compactly on the PMLG film. The mean diameters d _AFM estimated from the topographic images decreased from 70 to 54 nm with increasing W _BSA. The adhesion force F _ad and the frictional force F _f between the complex layers and the AFM tip were obtained by using the contact mode of the AFM. With increasing W _BSA, the values of F _ad decreased and the values of F _f increased. Compared with the frictional coefficient of the NaHA adsorption layer on the BSA monolayer, the values for the NaHA–BSA complex layer were found to be much higher.     

Electron radiation effects on the structure of ultradisperse polytetrafluoroethylene

Electron radiation effects (40 mrad, 70 mrad, and 100 mrad) on the molecular and supramolecular structure and morphology of ultradisperse polytetrafluoroethylene obtained by the thermogas dynamic (TGD) method were studied by IR and EPR spectroscopy, X-ray phase analysis, and atomic force microscopy. Irradiation of ultradisperse powder in air leads to oxidized polymer forms due to the terminal carbonyl groups and stable peroxide radicals that appear in the structure. Fast electron radiation in doses of up to 100 mrad did not change the polymer crystallinity and particle entity, while thin films on the surface of ultradisperse polytetrafluoroethylene powder decomposed.     

单核锌双卟啉配合物构象平衡的理论研究及光谱分析

合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果: 利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。