Quinoxalino[2,3-b']porphyrins behave as pi-expanded porphyrins upon one-electron reduction: broad control of the degree of delocalization through substitution at the macrocycle periphery

The synthesis and redox properties of a series of free-base and metal(II) quinoxalino[2,3-b']porphyrins and their use in an investigation of the substituent effects on the degree of communication between the porphyrin and its beta,beta'-fused quinoxalino component are reported. ESR, thin-layer spectroelectrochemistry, and quantum chemical calculations of the resultant radical anions from one-electron reduction indicate that localization of the unpaired electron across both the porphyrin and the fused quinoxalino group can be controlled, the system as a whole behaving as a highly polarizable pi-expanded porphyrin radical anion. ESR studies on the radical anions of zinc(II) quinoxalino[2,3-b']porphyrin derivatives indicate that nitrogen-atom spin distribution changes as a function of chemical substitution: 27% quinoxaline character when the porphyrin ring bears a 7-nitro substituent, 34% quinoxaline character in the unsubstituted parent, and 51-61% nitroquinoxaline character when the quinoxalino unit has one or more nitro groups. Close analogies are found between the calculated and observed nitrogen-atom spin distributions, indicating that the calculations embody the key chemical effects. The calculations also indicate that the nitrogen-atom spin distributions closely parallel the important total porphyrin, quinoxaline, and nitro spin distributions, indicating that the observed quantities realistically depict the change in the nature of the delocalization of the radical anion as a function of chemical substitution. The profound effects observed indicate long-range communication of the type that is essential in molecular electronics applications.     

Synthesis, complexation and water exchange properties of Gd(III)-TTDA-mono and bis(amide) derivatives and their binding affinity to human serum albumin

With the objective of tuning the lipophilicity of ligands and maintaining the neutrality and stability of Gd(III) chelate, we designed and synthesized two bis(amide) derivatives of TTDA, TTDA-BMA and TTDA-BBA, and a mono(amide) derivative, TTDA-N-MOBA. The ligand protonation constants and complex stability constants for various metal ions were determined in this study. The identification of the microscopic sites of protonation of the amide ligand by 1H NMR titrations show that the first protonation site occurs on the central nitrogen atom. The values of the stability constant of TTDA-mono and bis(amide) complex are significantly lower than those of TTDA and DTPA, but the selectivity constants of these ligands for Gd(III) over Zn(II) and Cu(II) are slightly higher than those of TTDA and DTPA. On the basis of the water-exchange rate values available for [Gd(TTDA-BMA)(H2O)], [Gd(TTDA-BBA)(H2O)] and [Gd(TTDA-N-MOBA)(H2O)]-, we can state that, in general, the replacement of one carboxylate group by an amide group decreases the water-exchange rate of the gadolinium(III) complexes by a factor of about three to five. The decrease in the exchange rate is explained in terms of a decreased steric crowding and charge effect around the metal ion when carboxylates are replaced by an amide group. In addition, to support the HSA protein binding studies of lipophilic [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] complexes, further protein-complex binding was studied by ultrafiltration and relaxivity studies. The binding constants (KA) of [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] are 8.6 x 10(2) and 1.0 x 10(4) dm3 mol(-1), respectively. The bound relaxivities (r1(b)) are 51.8 and 52 dm3 mmol(-1) s(-1), respectively. The KA value of [Gd(TTDA-BBA)(H2O)] is similar to that of MS-325 and indicates a stronger interaction of [Gd(TTDA-BBA)(H2O)] with HSA.     

Cytotoxic kurubasch aldehyde from Trichilia emetica

Kurubasch aldehyde, a sesquiterpenoid with an hydroxylated humulene skeleton, was isolated as free alcohol from Trichilia emetica Vahl. (Meliaceae), belonging to the order Sapindales. Related substances have been previously found in plants as esters of aromatic acids, and these plants were species belonging to the distant order Apiales. This is the first report of humulenes found in the genus Trichilia and only the second of humulenes in the order Sapindales. The aldehyde is a modest inhibitor of the growth of Plasmodium falciparum (IC50 76 microM) and slow-proliferating breast cancer cells MCF7 (78 microM), but a potent inhibitor of proliferation of S180 cancer cells (IC50 7.4 microM).     

Functionalization of corroles: the nitration reaction

The reaction of meso-triarylcorroles with AgNO2 proceeds with concomitant metalation and peripheral substitution to give the corresponding nitro-substituted silverIII corrole complex. The substitution is highly regioselective, giving only the corresponding 3-nitro derivative, among the different possible isomers. The results obtained indicate that the reaction intermediate is the pi-cation radical of the complex, which is then attacked by nitrite ion. This was proven by the reaction of the copper corrole complexes with NaNO2: in this case, the nitration reaction proceeded without the addition of an oxidant, because of the pi-cation radical character of the copper complex. The reaction is also successful in the case of 2,3,17,18-tetraethyl-8,12-diacetoxymethyl-7,13-dimethylcorrole (AMCorH3), with the formation of the meso-substituted silver corrole derivative (NO2)3AMCorAg (fully characterized by X-ray crystallography), the first of its kind to be reported. Two of the corroles are characterized by cyclic voltammetry and spectroelectrochemistry in dichloromethane, and the site of electron transfer is elucidated.     

Effect of axial ligands and macrocyclic structure on redox potentials and electron-transfer mechanisms of SnIV porphyrins

The electrochemical properties of dichloro- and dihydroxo-SnIV porphyrins with three different macrocycles were examined in CH2Cl2 containing 0.1 or 0.2 M tetra-n-butylammonium perchlorate as supporting electrolyte. The investigated compounds are represented as (TPP)SnX2, (P)Sn(X)2, and (PQ)Sn(X)2, where TPP = 5,10,15,20-tetraphenylporphyrin, P = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin, PQ = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b']porphyrin, and X = Cl or OH. Each porphyrin can be electroreduced in two one-electron-transfer steps with the half-wave potentials and stability of the eletroreduced compounds being dependent upon the type of coordinated axial ligand and specific macrocyclic structure. All reductions of (TPP)Sn(OH)2, (P)Sn(OH)2, and (PQ)Sn(OH)2 are reversible under the given experimental conditions and lead to the expected porphyrin pi-anion radicals and dianions, which were characterized by thin-layer UV-vis spectroelectrochemistry. This contrasts with what occurs upon the reduction of (PQ)SnCl2, which undergoes a chemical reaction with trace H2O in solution, leading to the formation of (PQ)Sn(OH)2 as well as to a protonated form of the quinoxalinoporphyrin, (PQH)Sn(OH)2, under the application of an applied potential. A protonation of the Q group breaks the conjugation between the fused quinoxaline unit and the porphyrin macrocycle, thus effectively giving a compound whose reduction properties resemble that of the metalloporphyrin in the absence of the fused ring. The electrooxidation of each neutral SnIV porphyrin was also investigated, and the effect of axial ligand and fused quinoxaline ring on the redox potentials and products of electron transfer are discussed.     

Fourier transform infrared investigation on the state of water in reverse micelles of quaternary ammonium gemini surfactants C12-s-C(12).2Br in n-heptane

The state of water in the reverse micelles of C12-s-C(12).2Br homologues has been investigated by Fourier transform infrared spectroscopy. The results showed that the solubilized water had four states: the quaternary ammonium head-group-bound, the Br--bound, the bulklike, and the free water. With increasing W0, the number of bulklike water per surfactant (nb) rapidly increased, which indicated swelling of the reverse micelle. The number of the head-bound water per surfactant (nN+) gradually increased. This was attributed to a reduction of the interfacial curvature, which permitted more water molecules to associate with the ionic heads of surfactants and also led to a part of n-hexanol being expelled from the interface and thus water filled up. Owing to the existence of n-hexanol in the interface, the head-bound water of the present system was smaller than that of AOT system at the same W0. The number of counterion-bound water per surfactant (nBr-) remained unchanged with W0. This was due to much smaller dissociation of the head of C12-2-C(12).2Br than that of AOT. With increasing s, unchanged nN+ is attributed to the comprehensive effects of enlarged head, which promotes the hydration, increased ionization degree, and reduced size of the water pool. Owing to increased ionization degree, nBr- increases with s.     

Analysis and implementation of new fractional-order multi-scroll hidden attractors

To improve the complexity of chaotic signals,in this paper we first put forward a new three-dimensional quadratic fractional-order multi-scroll hidden chaotic system,then we use the Adomian decomposition algorithm to solve the proposed fractional-order chaotic system and obtain the chaotic phase diagrams of different orders,as well as the Lyaponov exponent spectrum,bifurcation diagram,and SE complexity of the 0.99-order system.In the process of analyzing the system,we find that the system possesses the dynamic behaviors of hidden attractors and hidden bifurcations.Next,we also propose a method of using the Lyapunov exponents to describe the basins of attraction of the chaotic system in the matlab environment for the first time,and obtain the basins of attraction under different order conditions.Finally,we construct an analog circuit system of the fractional-order chaotic system by using an equivalent circuit module of the fractional-order integral operators,thus realizing the 0.9-order multi-scroll hidden chaotic attractors.     

多层非线性抗震钢结构的损失估计与优化设计

本文通过结构的动力可靠性分析和损失估计建立了以动力可靠性为约束的非线性抗震结构双目标(造价与损失期望)优化设计模型,提出了具体实现这种优化设计思想的实际可行的方法。文中将地震地面运动模拟为平稳过滤有色噪声,建立了以破坏指数刻划的结构体系的模糊震害等级,提出了结构模糊动力可靠性分析和损失估计的具体方法,从而使优化设计模型中各有关量的分析和计算得以具体地实现。     

Parameter identification in offshore platform using arma moded and technology of extracting free vibration signal

A procedure for identifying the dynamic parameter of offshore platform is presented. The present procedure consists of two key features. First uses random decrement (RD) technology to extract free vibration signal in strong noise environment in which it may not white noise. Second technology which called autoregressive moving average (ARMA) was used to model the data treated by the random decrement method. In order to get rid of the color noise in the output signal response from the offshore platform an imaginary system is added in RD system and make the course of extracting performed under the state of color input by choosing the breakover condition and lead time. For eliminating multi-values of parameters identified, an updating moving average method is used. The dynamic parameters of structure under arbitrary input are identified. Example of the method as applied to a scale-model offshore platform was used to evaluate the technology of efficiency and the value of on-line. Foundation items: the National Outstanding Youth Science Foundation of China (59625815); the Applied Development Foundation of National High Technology Biography: OU Jin-ping (1959-), Professor, Vice-President, Doctor