Dynamic Internal Cavities of Dendrimers as Constrained Media. A Study of Photochemical Isomerizations of Stilbene and Azobenzene Using Poly(alkyl aryl ether) Dendrimers

Dendritic rnicroenvironments defined by dynamic internal cavities of a dendrimer were probed through geometric isomerization of stilbene and azobenzene. A third-generation poly(alkyl aryl ether) dendrimer with hydrophilic exterior and hydrophobic interior was used as a reaction cavity in aqueous medium. The dynamic inner cavity sizes were varied by utilizing alkyl linkers that connect the branch junctures from ethyl to n-pentyl moiety (C(2)G(3)-C(5)G(3)). Dendrimers constituted with n-pentyl linker were found to afford higher solubilities of stilbene and azobenzene. Direct irradiation of trans-stilbene showed that C(5)G(3) and C(4)G(3) dendrimers afforded considerable phenanthrene formation, in addition to cis-stilbene, whereas C(3)G(3) and C(2)G(3) gave only cis-stilbene. An electron-transfer sensitized trans-cis isomerization, using cresyl violet perchlorate as the sensitizer, also led to similar results. Thermal isomerization of cis-azobenzene to trans-azobenzene within dendritic microenvironments revealed that the activation energy of the cis- to trans-isomer was increasing in the series C(5)G(3) < C(4)G(3) < C(3)G(3)

Nanoindentation as a probe for mechanically-induced molecular migration in layered organic donor-acceptor complexes

Nanoindentation and scratch experiments on 1:1 donor-acceptor complexes, 1 and 2, of 1,2,4,5-tetracyanobenzene with pyrene and phenanthrene, respectively, reveal long-range molecular layer gliding and large interaction anisotropy. Due to the layered arrangements in these crystals, these experiments that apply stress in particular directions result in the breaking of interlayer interactions, thus allowing molecular sheets to glide over one another with ease. Complex 1 has a layered crystal packing wherein the layers are 68° skew under the (002) face and the interlayer space is stabilized by van der Waals interactions. Upon indenting this surface with a Berkovich tip, pile-up of material was observed on just one side of the indenter due to the close angular alignment of the layers with the half angle of the indenter tip (65.35°). The interfacial differences in the elastic modulus (21 ) and hardness (16 ) demonstrate the anisotropic nature of crystal packing. In 2, the molecular stacks are arranged in a staggered manner; there is no layer arrangement, and the interlayer stabilization involves C-H�N hydrogen bonds and ��� interactions. This results in a higher modulus (20 ) for (020) as compared to (001), although the anisotropy in hardness is minimal (4 ). The anisotropy within a face was analyzed using AFM image scans and the coefficient of friction of four orthogonal nanoscratches on the cleavage planes of 1 and 2. A higher friction coefficient was obtained for 2 as compared to 1 even in the cleavage direction due to the presence of hydrogen bonds in the interlayer region making the tip movement more hindered. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The application of metallointercalators in recognition of and charge transport in nucleic acids

Metal complexes that utilize the 9,10-phenanthrene quinone diimine (phi) moiety bind to DNA through the major groove. These metallointercalators can recognize DNA sites and perform reactions on DNA as a substrate. The site-specific metallointercalator Λ-1-Rh(MGP)_2phi^(5+) competitively disrupts the major groove binding of a transcription factor, yAP-1, from an oligonucleotide that contains a common binding site. The demonstration that metal complexes can prevent transcription factor binding to DNA site-specifically is an important step in using metallointercalators as therapeutics.

The distinctive photochemistry of metallointercalators can also be applied to promote long range charge transport in DNA. Experiments using duplexes with regions 4 to 10 nucleotides long containing strictly adenine and thymine sequences of varying order showed that radical migration is more dependent on the sequence of bases, and less dependent on the distance between the guanine doublets. This result suggests that mechanistic proposals of long range charge transport must involve all the bases.

RNA/DNA hybrids show charge migration to guanines from a remote site, thus demonstrating that nucleic acid stacking other than B-form can serve as a radical bridge. Double crossover DNA assemblies also provide a medium for charge transport at distances up to 100 Å from the site of radical introduction by a tethered metal complex. This radical migration was found to be robust to mismatches, and limited to individual, electronically distinct base stacks. In single DNA crossover assemblies, which have considerably greater flexibility, charge migration proceeds to both base stacks due to conformational isomers not present in the rigid and tightly annealed double crossovers.

Finally, a rapid, efficient, gel-based technique was developed to investigate thymine dimer repair. Two oligonucleotides, one radioactively labeled, are photoligated via the bases of a thymine-thymine interface; reversal of this ligation is easily visualized by gel electrophoresis. This assay was used to show that the repair of thymine dimers from a distance through DNA charge transport can be accomplished with different photooxidants.

Thus, nucleic acids that support long range charge transport have been shown to include A-track DNA, RNA/DNA hybrids, and single and double crossovers, and a method for thymine dimer repair detection using charge transport was developed. These observations underscore and extend the remarkable finding that DNA can serve a medium for charge transport via the heteroaromatic base stack.

Aplicações de métodos de classificação e calibração multivariada acoplados com técnicas espectroscópicas em amostras ambientais e alimentos

Este trabalho de pesquisa descreve dois estudos de caso de métodos quimiométricos empregados para a quantificação de hidrocarbonetos policíclicos aromáticos HPAs (naftaleno, fluoreno, fenantreno e fluoranteno) em água potável usando espectroscopia de fluorescência molecular e a classificação e caracterização de sucos de uva e seus parâmetros de qualidade através de espectroscopia de infravermelho próximo. O objetivo do primeiro estudo é a aplicação combinada de métodos quimiométricos de segunda ordem (N-PLS, U-PLS, U-PLS/RBL e PARAFAC) e espectrofluorimetria para determinação direta de HPAs em água potável, visando contribuir para o conhecimento do potencial destas metodologias como alternativa viável para a determinação tradicional por cromatografia univariada. O segundo estudo de caso destinado à classificação e determinação de parâmetros de qualidade de sucos de uva, densidade relativa e teor de sólidos solúveis totais, foi medida por espectroscopia de infravermelho próximo e métodos quimiométricos. Diversos métodos quimiométricos, tais como HCA, PLS-DA, SVM-DA e SIMCA foram investigados para a classificação amostras de sucos de uva ao mesmo tempo que métodos de calibração multivariada de primeira ordem, tais como PLS, iPLS e SVM-LS foram usadas para a predição dos parâmetros de qualidade. O princípio orientador para o desenvolvimento dos estudos aqui descritos foi a necessidade de metodologias analíticas com custo, tempo de execução e facilidade de operação melhores e menor produção de resíduos do que os métodos atualmente utilizados para a quantificação de HPAs, em água de torneira, e classificação e caracterização das amostras de suco de uva e seus parâmetros de qualidade

Desenvolvimento e produção de metabólitos de arruda (Ruta graveolens L.) exposta a substratos contaminados por hidrocarbonetos de petróleo

A indução da síntese de moléculas biologicamente ativas é conhecida como uma estratégia de defesa do organismo vegetal às condições adversas, onde plantas medicinais e/ou aromáticas são foco de pesquisa na terapêutica médica, na indústria farmacêutica, de cosméticos e de alimentos. A possibilidade de que os hidrocarbonetos de petróleo presentes no solo possam agir como agentes elicitores do metabolismo vegetal tem despertado interesse científico. O presente trabalho teve como objetivo avaliar o desenvolvimento in vivo e in vitro de Ruta graveolens L. (Rutaceae), considerando as respostas morfológicas e metabólicas na presença de petróleo e derivados. Além disso, verificar o potencial de desenvolvimento dessa espécie em áreas contaminadas, com base na hipótese de que tais substâncias podem influenciar na produção de substâncias de interesse, sem que haja redução significativa da biomassa vegetal. Foram realizados experimentos de (i) germinação in vivo em solo contaminado e parcialmente biorremediado, assim como solo com contaminação recente com óleo cru (0,8 % e 2,8 %) e diesel comercial S50 (0 % a 6,0 %), sendo que neste último foi avaliado o desenvolvimento e a produção de biomassa das plântulas; (ii) germinação in vitro em meio MS contaminado com fenantreno (1,0; 5,0 e 10,0 mg/L de meio) ou benzo[a]pireno (0,001; 0,010 e 0,100 mg/L de meio), sendo avaliado o desenvolvimento e a produção de biomassa; e (iii) resposta fisiológica de plantas oriundas do estoque in vitro à exposição de fenantreno ou benzo[a]pireno. R. graveolens teve redução significativa da germinação em solos contaminados, principalmente os solos parcialmente biorremediados pelo do processo de bioestímulo; não teve redução significativa da germinação in vivo nos solos contaminados com óleo cru, biorremediado e contaminado com diesel, porém o desenvolvimento pósgerminação foi afetado. Na exposição in vitro aos hidrocarbonetos, não houve alteração significativa na germinação nem na capacidade de desenvolvimento e produção de biomassa nas concentrações testadas de até 10 mg/L de fenantreno e até 0,1 mg/L de benzo[a]pireno. Em relação à propagação in vitro, foi possível a multiplicação de plantas em meio de cultura sem suplementação hormonal, na presença dos contaminantes. A presença de fenantreno e benzo[a]pireno in vitro não promoveu mudanças significativas nos níveis de compostos fenólicos e flavonoides totais produzidos, não havendo também alteração no perfil fitoquímico da espécie, quanto à presença de rutina. Pelo exposto, conclui-se que a espécie tem potencial para uso em biomonitoramento de solos contaminados , considerando a sua capacidade de produzir metabólitos e tolerar a presença dos hidrocarbonetos selecionados, sendo indicada ao cultivo em áreas contaminadas nos níveis investigados

Determination of PAH, PCB, and OCP in water from the Three Gorges Reservoir accumulated by semipermeable membrane devices (SPMD)

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 m s(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ng L-1, with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ng L-1, with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ng L-1 and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR. (C) 2009 Elsevier Ltd. All rights reserved.

微生物的固定化及其降解土壤中菲、芘的研究

该论文是在综合分析中国典型土壤的污染特性与土壤环境背景的基础上，研制开发出适合中国国情的有机污染土壤的污染特性与土壤环境背景的基础上，研制开发出适合中国国情的有机污染土壤清洁技术.采用固定化进行有机物降解试验，目的是以期开发出一条提高有机污染土壤降解效率的新途径.该论文首先通过菌种的筛选与鉴定后，进行微生物的固定化包埋，挑选出最佳的固定化载体.最合理的载体配比是：聚乙烯醇100（p/gL<'-1>），活性炭50（p/gL<'-1>）.同时确定细菌采用化学方法进行固定化包埋，载体形状为球形;真菌采用物理方法进行固定化包埋，载体形状为莲藕型.并将固定化微生物应用于有机污染土壤菲、芘的降解.通过不同接种量的固定化微生物对菲、芘的降解、固定化微生物对不同系列浓度菲和芘的降解以及固定化微生物在自然土壤中对菲、芘降解的各参数测定，说明固定化微生物用于降解土壤中有机污染物具有一定的应用前景.该研究首次将固定化微生物用于降解土壤中有机污染物，为将来的实际应用奠定了一定的理论基础.同时首次采用了新的载体形状——莲藕型，具有一定的创新性.

表面活性剂与菲的复合生态效应

利用表面活性剂去除土壤中难降解的多环芳烃，近年来得到了较多的应用.但对其去污机理及两者共存时的复合毒性，国内外研究甚少.该篇论文以六种不同离子类型、分子结构的表面活性剂和以菲为多环芳烃的代表，研究了表面活性剂对菲降解的影响，和与菲共存时的复合毒性，以及表面活性剂对菲在模拟生态系统中的迁移转化规律的影响.

LAS对菲在土壤(柱)中的迁移影响

The migration of phenanthrene and factors affecting its migration in soil in presence of LAS are studied through the simulation of soil column. Results show that:① Through 180 days of leaching, when the LAS concentration is 0.5 or 5mg·L *.1, the phenanthrene residual rate is less than 10 percent and the residue distributes mainly in surface soil(0-5cm);② When LAS concentration is 0.5mg·L *.1, the phenanthrene residual rate in soil is 3-8 times that of LAS concentration being 5mg·L *.1;③ The phenanthrene residual rate in soil is 2.5-6 times that of soil that with organic matter removed.It's shown that the LAS concentration has obvious effect for the phenanthrene residual rate in soil and the organic matter in soil has good cap ability in keeping phenanthrene.

An electroosmotic pump for packed capillary liquid chromatography

An electroosmotic pump (EOP) capable of generating pressure above 3 MPa and mul/min flow rate with reverse phase mobile phases of HPLC was constructed and evaluated. The pump consisted of three parallel connected fused silica capillary columns (25 cm x 320 mum I.D.) packed with 2 mum silica materials, hollow electrodes, a high voltage DC power supply, and. a liquid pressure transducer. The EOP was applied in a capillary liquid chromatographic system for mobile phase delivery instead of a mechanical pump. Standard samples containing thiourea, naphthalene, anthracene, phenanthrene and acetonitrile were separated on a 15 cm x 320 mum I.D. 5 mum Chromasil C-18 packed capillary column with acetonitrile/water as mobile phase. (C) 2003 Elsevier Science B.V. All rights reserved.

固定化微生物降解土壤中菲和芘的研究

Immobilized with PVA,sodium alginate and activated carbon,both Zoogloea sp. and Fusarium sp.strains could degrade phenanthrene and pyrene efficiently.The optimal carrier was made of 100ρ·g -1 L PVA,5 sodium alginateρ·g -1 L and 50 activated carbon ρ·g -1 L.The degradation rates of phenanthrene and pyrene in 10 days were 87.48% and 75.34% by the immobilized bacterium,37.04% and 20.85% higher than those by the free bacterium,and the rates in 15 days were 84.36% and 74.87% by the immobilized fungus,5.35% and 11.23% higher than those by the free fungus.

Ambipolar organic heterojunction transistors with various p-type semiconductors

Ambipolar transport has been realized in organic heterojunction transistors with metal phthalocyanines, phenanthrene-based conjugated oligomers as the first semiconductors and copper-hexadecafluoro-phthalocyanine as the second semiconductor. The electron and hole mobilities of ambipolar devices with rod-like molecules were comparable to the corresponding single component devices, while the carrier mobility of ambipolar devices with disk-like molecules was much lower than the corresponding single component devices.