Oxidative coupling of porphyrins using copper(II) salts

A method for radical coupling of porphyrins using copper(II) salts as one-electron oxidants was developed. A Zn(II)-porphyrin bearing an aminophenyl group yielded porphyrin oligomers, and two tri-arylporphyrins were oxidized to form doubly and triply linked dimers. Bromination of doubly linked dimers gave macrocycles with twisted skeletons.     

Photoinduced electron transfer in a hexaphenylbenzene-based self-assembled porphyrin-fullerene triad

A hexaphenylbenzene-based zinc porphyrin dyad forms a 1:1 complex with a fullerene bearing two pyridyl groups via coordination of the pyridyl nitrogens with the zinc atoms. The fullerene is symmetrically located between the two zinc porphyrins. The binding constant for the complex is 7.3 x 10(4) M(-1) in 1,2-difluorobenzene. Photoinduced electron transfer from a porphyrin first excited singlet state to the fullerene occurs with a time constant of 3 ps, and the resulting charge-separated state has a lifetime of 230 ps. This self-assembled construct should form a basis for the construction of more elaborate model photosynthetic antenna-reaction center systems.     

基于箭形累积损伤的裂纹尖端力学:奇异性分级和多尺度分段

在适度的空间和时间尺度组合下,裂纹既可在几个月中蠕变几个纳米,也能在几秒钟内扩展10km.虽然裂纹的尖端没有实际的质量,但是它能通过激活周围的物质而处于高能量状态.依赖于材料的损伤方向,激活质量的减少和增加可发生在尺度转变之前或之后.每个尺度区的分段阈值被假定为与裂纹尖端速度的平方a~2和激活质量密度M的乘积有关:W=M_(↓↑)a_(↑↓)~2和D=M~(↓↑)a_(↑↓)~2.W和D分别被称为直接吸收和自耗散能量密度.正如下标/上标符号所示,激活的质量密度M_(↓↑)和M~(↓↑)与裂纹尖端速度a变化趋势相反,既可增加也可减少.a~2和M的互补效应隐含着常用于宇宙物理学建模的膨胀和/或收缩的物理过程.在用于尺度敏感的裂纹尖端的行为时,激活的质量密度有相同的解释.分段时的多尺度可以由…皮观、纳观、微观和宏观…组成.因此,形象地说,材料损伤过程可以通过裂纹扩展过程中非均匀的总体和局部能量的传递来模拟.疲劳裂纹扩展引起的材料损伤被用来阐释由大到小和由慢到快的尺度/时间序,热力学中的冷→热和有序→无序转换.这一过程正巧与宇宙演化的箭形方向相反,宇宙演化遵循小→大和快→慢,而热力学相反,遵循热→冷和无序→有序.为了表示由损伤萌生所造成的类裂缝型缺陷的不均匀性,提出了一个被称为裂纹尖端力学(crack tip mechanics,CTM)的新模式.涉及的范围是模拟原子列之间的界面裂纹或连续体中分叉的切口.假如需要的话,尺寸和时间的范围可以复盖从皮观到宏观甚至更大.虽然采用疲劳裂纹来说明CTM的基本原理,在宇宙物理学背景中与直接吸收和自耗散相关的膨胀和收缩的情况可以描述裂纹周围激活质量的行为,它们可看为能量的汇或源.奇异性被用来捕获能量的源或汇的特性,物理上,两者作为界面的一部分,从数学上看则是不连续的线的一部分.能量从一种形式变为另一种形式取决于能量吸收或耗散的箭形损伤时间,这之中牵涉到尺度分段和奇异性强度的联合应用.材料组分随时间的劣化是根据指定的设计寿命导出的,从而使材料的响应与加载率的时间历史匹配.2024-T3铝板的皮观/纳观/微观/宏观开裂模型用来说明什么地方可以增加结构的寿命部分.皮观/纳观/微观/宏观/结构系统的性能随时间劣化可以用9个尺度转变物理参数来描述:纳观/微观区有3个(μ_(na/mi)~*,σ_(na/mi)~*,d_(na/mi)~*),微观/宏观区有3个(μ_(mi/ma)~*,σ_(mi/ma)~*,d_(mi/ma)~*),皮观/纳观区有3个(μ_(pi/na)~*,σ_(pi/na)~*,d_(pi/na)~*).下标pi,na,mi,ma和struc分别表示皮观、纳观、微观、宏观和结构.只要知道两个相连的尺度敏感参数,在较低尺度的时间相关的局部物理参数就完成了分析连续体的形式论,虽然它们并不需要用实验来知道.更具体地说,根据皮观→纳观→微观→宏观分别有1.25/1.00/0.75/0.50的λ奇异性强度,皮观裂纹、纳观裂纹、微观裂纹和宏观裂纹的转变特征是从时间箭形的指定的寿命预期来确定的.附加的0.25强度的奇异性可用于结构元件.回想起来,λ=0.5相应于断裂力学中的应力分量与r~(0.5)成反比,r是与宏观裂纹尖端的距离.微观裂纹、纳观裂纹和皮观裂纹分别赋予r~(-0.75),r~(-1.0),r~(-1.25)的奇异性.箭形时间(以年为单位)取决于问题的定义.设备的关键部件可用1.5~±/2.5~±/3.5~±/5.5~±寿命分布和总寿命为13~±年(a)的皮观/纳观/微观/宏观尺度来设计运行.上标±表示多于或少于实际运行的时间.累进损伤被假定为发生在皮观→纳观→微观→宏观方向.同样的方案用于20年总寿命的2024-T3铝板的疲劳损伤,按照1.5~±/2.5~±/3.5~±/5.5~±/7.0~±的方式将它的寿命分布在皮观、纳观、微观、宏观和结构的尺度上,这样的指定只是满足在每个尺度范围内损伤内部材料结构所用的能量匹配,因此可以强制执行在总寿命的跨度内精确的时间相关的材料性能劣化过程.     

On the electric current from electrodes in a magnetized semiconductor film

The problem on the electric current from electrodes in a magnetizedsemiconductor film is reduced to the skew derivative problemfor the Laplace equation outside cuts in a plane. The problemfor the Laplace equation is studied under different conditionsat infinity, which have a certain physical meaning. With thehelp of potential theory, the skew derivative problem is reducedto a Fredholm integral equation of the second kind, which isuniquely solvable. The Neumann problem for the Laplace equationin the exterior of cuts in a plane is a particular case of ourproblem.     

阻抗谱法确定扩散系数

给出了阻抗谱法确定扩散系数的理论和方法;以钒酸盐阴极材料Na_(1+x)V_3O_(?)(L.T.)为例,应用本方法计算给出了Li~+在阴极中的扩散系数为10~(?)-10~(-9)cm~2·s~(-1);最后还对误差来源进行了讨论. 关键词：     

NMR spectra of carotenoporphyrins. Computer-assisted conformational analysis

A computer-assisted method of conformational analysis for porphyrin molecules bearing flexible side-chains has been developed. The method utilizes the ring current-induced chemical shift changes of the side-chain protons which arise from the porphyrin macrocycle and any attached aryl rings. The treatment has been applied to a series of carotenoporphyrin molecules, which are important as models for a variety of photophysical processes in biological systems. Chemical shift data of sufficient accuracy for the conformational analysis were obtained from 500 MHz NMR experiments. The conformations of the carotenoporphyrins varied from extended ones with the carotenoid well away from the porphyrin ring to tightly folded species, depending on molecular constitution. The analytical method can be extended to other porphyrin-based systems.     

Energy transfer and spin polarization of the carotenoid triplet state in synthetic carotenoporphyrin dyads and in natural antenna complexes

A series of carotenoporphyrin dyads, in which the carotenoid is covalently linked to a tetraarylporphyrin at the ortho, meta or para position of one of the meso aromatic rings, has been studied using Time-Resolved Electron Paramagnetic Resonance (TREPR) spectroscopy. In parallel, an investigation has been carried, on two different photosynthetic antenna systems, the B800–B850 complex ofR. acidophila and the LHCII complex of higher organisms. The initial spin polarization of the carotenoid triplet-state, populated indirectly by laser excitation, has been detected. It has been demonstrated that the initial polarization is not a characteristic property of the carotenoid triplet-state, as previously stated, but depends on the donor-acceptor mutual orientation. The triplet energy transfer to the carotenoid from a chlorophyll or porphyrin triplet state is discussed on the basis of the observed spin polarization.     

Driving force and electronic coupling effects on photoinduced electron transfer in a fullerene-based molecular triad

Tuning thermodynamic driving force and electronic coupling through structural modifications of a carotene (C) porphyrin (P) fullerene (C60) molecular triad has permitted control of five electron and energy transfer rate constants and two excited state lifetimes in order to prepare a high-energy charge-separated state by photoinduced electron transfer with a quantum yield of essentially unity (> or = 96%). Excitation of the porphyrin moiety of C-P-C60 is followed by a combination of photoinduced electron transfer to give C-P(.+)-C60.- and singlet-singlet energy transfer to yield C-P-1C60. The fullerene excited state accepts an electron from the porphyrin to also generate C-P(.+)-C60.-. Overall, this initial state is formed with a quantum yield of 0.97. Charge shift from the carotenoid to yield C(.+)-P-C60.- is at least 60 times faster than recombination of C-P(.+)-C60.-, leading to the overall quantum yield near unity for the final state. Formation of a similar charge-separate species from the zinc analog of the triad with a yield of 40% is also observed. Charge recombination of C(.+)-P-C60.- in 2-methyltetrahydrofuran yields the carotenoid triplet state, rather than the ground state. Comparison of the results for this triad with those for related triads with different structural features provides information concerning the effects of driving force and electronic coupling on each of the electron transfer steps.     

Photonic switching of photoinduced electron transfer in a dithienylethene-porphyrin-fullerene triad molecule

A dithienylethene (DTE)-porphyrin (P)-fullerene (C(60)) triad molecule in which intramolecular photoinduced electron transfer is controlled by the photochromic DTE moiety has been prepared. Irradiation of the molecule with visible light gives the open form of the dithienylethene (DTEo). Excitation of the porphyrin gives DTEo-(1)P-C(60), which undergoes photoinduced electron transfer with a time constant of 25 ps to generate DTEo-P(.+)-C(60)(.-). Irradiation with ultraviolet light produces the closed form of the dithienylethene (DTEc). Excitation of DTEc-P-C(60) yields DTEc-(1)P-C(60), whose porphyrin first excited singlet state is quenched in 2.3 ps by singlet-singlet energy transfer to DTEc, generating (1)DTEc-P-C(60) and precluding significant photoinduced electron transfer. Such highly reversible photonically controlled intramolecular photoinduced electron transfer may eventually be useful in the design of photonic or optoelectronic devices.