Influence of ionic interactions on the photoinduced Birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1 2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxypheny-lazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged PAH or PAZO.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Irradiance stress responses of gas exchange and antioxidant enzyme contents in pariparoba [Pothomorphe umbellata (L.) Miq.] plants

We evaluated the growth and development of the medicinal species Pothomorphe umbellata ( L.) Miq. under different shade levels ( full sun and 30, 50, and 70 % shade, marked as I(100), I(70), I(50), and I(30), respectively) and their effects on gas exchange and activities of antioxidant enzymes. Photosynthetically active radiation varied from 1 254 mu mol m(-2) s(-1) at I(100) to 285 mu mol m(-2) s(-1) at I(30). Stomatal conductance, net photosynthetic rate, and relative chlorophyll (Chl) content were maximal in I(70) plants. Plants grown under I(100) produced leaves with lower Chl content and signs of chlorosis and necrosis. These symptoms indicated Chl degradation induced by the generation of reactive oxygen species. Stress related antioxidant enzyme activities ( Mn-SOD, Fe-SOD, and Cu/Zn-SOD) were highest in I(100) plants, whereas catalase activity was the lowest. Hence P. umbellata is a shade species ( sciophyte), a feature that should be considered in reforestation programs or in field plantings for production of medicinal constituents.

Influence of light curing source on microhardness of composite resins of different shades

Introduction: The evolution of light curing units can be noticed by the different systems recently introduced. The technology of LED units promises longer lifetime, without heating and with production of specific light for activation of camphorquinone. However, further studies are still required to check the real curing effectiveness of these units. Purpose: This study evaluated the microhardness of 4 shades (B-0.5, B-1, B-2 and B-3) of composite resin Filtek Z-250 (3M ESPE) after light curing with 4 light sources, being one halogen (Ultralux - Dabi Atlante) and three LED (Ultraled - Dabi Atlante, Ultrablue - DMC and Elipar Freelight - 3M ESPE). Methods: 192 specimens were distributed into 16 groups, and materials were inserted in a single increment in cylindrical templates measuring 4mm x 4mm and light cured as recommended by the manufacturer. Then, they were submitted to microhardness test on the top and bottom aspects of the cylinders. Results: The hardness values achieved were submitted to analysis of variance and to Tukey test at 5% confidence level. It was observed that microhardness of specimens varied according to the shade of the material and light sources employed. The LED appliance emitting greater light intensity provided the highest hardness values with shade B-0.5, allowing the best curing. On the other hand, appliances with low light intensity were the least effective. It was also observed that the bottom of specimens was more sensitive to changes in shade. Conclusion: Light intensity of LED light curing units is fundamental for their good functioning, especially when applied in resins with darker shades.

Effect of ionic strength solution on the stability of chitosan-DNA nanoparticles

Chitosan-DNA nanoparticles employed in gene therapy protocols consist of a neutralised, stoichiometric core and a shell of the excess of chitosan which stabilises the particles against further coagulation. At low ionic strength, these nanoparticles possess a high stability; however, as the ionic strength increases, it weakens the electrostatic repulsion which can play a decisive part in the formation of highly aggregated particles. In this study, new results about the effect of ionic strength on the colloidal stability of chitosan-DNA nanoparticles were obtained by studying the interaction between chitosans of increasing molecular weights (5, 10, 16, 29, 57 and 150 kDa) and calf thymus DNA. The physicochemical properties of polyplexes were investigated by means of dynamic light scattering, static fluorescence spectroscopy, optic microscopy, transmission electronic microscopy and gel electrophoresis. After subsequent addition of salt to the nanoparticles solution, secondary aggregation increased the size of the polyplexes. The nanoparticles stability decreased drastically at the ionic strengths 150 and 500 mM, which caused the corresponding decrease in the thickness of the stabilising shell. The morphologies of chitosan/DNA nanoparticles at those ionic strengths were a mixture of large spherical aggregates, toroids and rods. The results indicated that to obtain stable chitosan-DNA nanoparticles, besides molecular weight and N/P ratio, it is quite important to control the ionic strength of the solution. �� 2013 Copyright Taylor and Francis Group, LLC.

Evaluation of ionic degradation and slot corrosion of metallic brackets by the action of different dentifrices

OBJETIVO: avaliar in vitro a degrada����o i��nica e corros��o do fundo do slot de braquetes met��licos submetidos �� escova����o com dentifr��cios, realizando an��lises da composi����o qu��mica por Espectroscopia de Energia Dispersiva (EDS) e qualitativa por Microscopia Eletr��nica de Varredura (MEV). M��TODOS: foram selecionados 38 braquetes divididos aleatoriamente em quatro grupos experimentais (n = 7). Dois grupos (n = 5) funcionaram como controles positivo e negativo. Aparelhos ortod��nticos simulados foram confeccionados com fios de a��o inoxid��vel 0,019" x 0,025" e an��is elastom��ricos. Os grupos foram divididos de acordo com o tratamento de superf��cie: G1 (M��xima Prote����o Antic��ries��); G2 (Total 12��); G3 (Sensitive��); G4 (Branqueador��); Controle Positivo (saliva artificial) e Controle Negativo (sem tratamento). Foram realizados 28 ciclos de escova����o e avalia����es antes (T0) e ap��s (T1) o experimento. RESULTADOS: o teste de Wilcoxon indicou n��o existir diferen��a nas concentra����es i��nicas de tit��nio (Ti), cromo (Cr), ferro (Fe) e n��quel (Ni) entre os grupos. O grupo G2 apresentou redu����o significativa (p < 0,05) na concentra����o do ��on alum��nio (Al) e os grupos G3 e G4 apresentaram aumento significativo (p < 0,05) nas concentra����es do ��on alum��nio. A an��lise em MEV mostrou aumento nas caracter��sticas indicativas de corros��o dos grupos G2, G3 e G4. CONCLUS��O: a an��lise por EDS revelou que os grupos controle e G1 n��o sofreram altera����es na composi����o qu��mica. O grupo G2 apresentou degrada����o na quantidade de ��ons Al, e G3 e G4 sofreram aumento na concentra����o de Al. A imers��o em saliva artificial e o dentifr��cio M��xima Prote����o Antic��ries�� n��o alteraram o polimento de superf��cie. Os dentifr��cios Total 12��, Sensitive�� e Branqueador�� alteraram o polimento de superf��cie.

Effect of Water Exchange and Mechanical Aeration on Grow-out of the Amazon River Prawn in Ponds

Conselho Nacional de Desenvolvimento Cient��fico e Tecnol��gico (CNPq)

Controlling the formation of ionic-liquid-based aqueous biphasic systems by changing the hydrogen-bonding ability of polyethylene glycol end groups

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

Chromatic stability of acrylic resins of artificial eyes submitted to the accelerated aging and polishing

Esthetics and durability of materials used to fabricate artificial eyes has been an important issue since artificial eyes are essential to restore esthetics and function, protect the remaining tissues and help with patients' psychological therapy. However, these materials are submitted to degrading effects of environmental agents on the physical properties of the acrylic resin. OBJECTIVE: This study assessed the color stability of acrylic resins used to fabricate sclera in three basic shades (N1, N2 and N3) when subjected to accelerated aging, mechanical and chemical polishing. MATERIAL AND METHODS: Specimens of each resin were fabricated and submitted to mechanical and chemical polishing. Chromatic analysis was performed before and after accelerated aging through ultraviolet reflection spectrophotometry. RESULTS: All specimens revealed color alteration following polishing and accelerated aging. The resins presented statistically significant chromatic alteration (p<0.01) between the periods of 252 and 1008 h. CONCLUSIONS: Both polishing methods presented no significant difference between the values of color derivatives of resins.

The social construction of cooperation: exchange, identification and collective intentions within the organization

My aim is to develop a theory of cooperation within the organization and empirically test it. Drawing upon social exchange theory, social identity theory, the idea of collective intentions, and social constructivism, the main assumption of my work implies that both cooperation and the organization itself are continually shaped and restructured by actions, judgments, and symbolic interpretations of the parties involved. Therefore, I propose that the decision to cooperate, expressed say as an intention to cooperate, reflects and depends on a three step social process shaped by the interpretations of the actors involved. The first step entails an instrumental evaluation of cooperation in terms of social exchange. In the second step, this ���social calculus��� is translated into cognitive, emotional and evaluative reactions directed toward the organization. Finally, once the identification process is completed and membership awareness is established, I propose that individuals will start to think largely in terms of ���We��� instead of ���I���. Self-goals are redefined at the collective level, and the outcomes for self, others, and the organization become practically interchangeable. I decided to apply my theory to an important cooperative problem in management research: knowledge exchange within organizations. Hence, I conducted a quantitative survey among the members of the virtual community, ���www.borse.it��� (n=108). Within this community, members freely decide to exchange their knowledge about the stock market among themselves. Because of the confirmatory requirements and the structural complexity of the theory proposed (i.e., the proposal that instrumental evaluations will induce social identity and this in turn will causes collective intentions), I use Structural Equation Modeling to test all hypotheses in this dissertation. The empirical survey-based study found support for the theory of cooperation proposed in this dissertation. The findings suggest that an appropriate conceptualization of the decision to exchange knowledge is one where collective intentions depend proximally on social identity (i.e., cognitive identification, affective commitment, and evaluative engagement) with the organization, and this identity depends on instrumental evaluations of cooperators (i.e., perceived value of the knowledge received, assessment of past reciprocity, expected reciprocity, and expected social outcomes of the exchange). Furthermore, I find that social identity fully mediates the effects of instrumental motives on collective intentions.

Structure and dynamics of ionic liquid,electrode interfaces

In the early 20th century, Gouy, Chapman, and Stern developed a theory to describe the capacitance and the spatial ion distribution of diluted electrolytes near an electrode. After a century of research, considerable progress has been made in the understanding of the electrolyte/electrode interface. However, its molecular-scale structure and its variation with an applied potential is still under debate. In particular for room-temperature ionic liquids, a new class of solventless electrolytes, the classical theories for the electrical double layer are not applicable. Recently, molecular dynamics simulations and phenomenological theories have attempted to explain the capacitance of the ionic liquid/electrode interface with the molecular-scale structure and dynamics of the ionic liquid near the electrode. rnHowever, experimental evidence is very limited. rnrnIn the presented study, the ion distribution of an ionic liquid near an electrode and its response to applied potentials was examined with sub-molecular resolution. For this purpose, a new sample chamber was constructed, allowing in situ high energy X-ray reflectivity experiments under potential control, as well as impedance spectroscopy measurements. The combination of structural information and electrochmical data provided a comprehensive picture of the electric double layer in ionic liquids. Oscillatory charge density profiles were found, consisting of alternating anion- and cation-enriched layers at both, cathodic and anodic, potentials. This structure was shown to arise from the same ion-ion correlations dominating the liquid bulk structure that were observed as a distinct X-ray diffraction peak. Therefore, existing physically motivated models were refined and verified by comparison with independent measurements. rnrnThe relaxation dynamics of the interfacial structure upon potential variation were studied by time resolved X-ray reflectivity experiments with sub-millisecond resolution. The observed relaxation times during charging/discharging are consistent with the impedance spectroscopy data revealing three processes of vastly different characteristic time-scales. Initially, the ion transport normal to the interface happens on a millisecond-scale. Another 100-millisecond-scale process is associated with molecular reorientation of electrode-adsorbed cations. Further, a minute-scale relaxation was observed, which is tentatively assigned to lateral ordering within the first layer.

Tuning of magnetic exchange interactions between organic radicals through bond and space

The dissertation entitled "Tuning of magnetic exchange interactions between organic radicals through bond and space" comprises eight chapters. In the initial part of chapter 1, an overview of organic radicals and their applications were discussed and in the latter part motivation and objective of thesis was described. As the EPR spectroscopy is a necessary tool to study organic radicals, the basic principles of EPR spectroscopy were discussed in chapter 2. rnAntiferromagnetically coupled species can be considered as a source of interacting bosons. Consequently, such biradicals can serve as molecular models of a gas of magnetic excitations which can be used for quantum computing or quantum information processing. Notably, initial small triplet state population in weakly AF coupled biradicals can be switched into larger in the presence of applied magnetic field. Such biradical systems are promising molecular models for studying the phenomena of magnetic field-induced Bose-Einstein condensation in the solid state. To observe such phenomena it is very important to control the intra- as well as inter-molecular magnetic exchange interactions. Chapters 3 to 5 deals with the tuning of intra- and inter-molecular exchange interactions utilizing different approaches. Some of which include changing the length of ��-spacer, introduction of functional groups, metal complex formation with diamagnetic metal ion, variation of radical moieties etc. During this study I came across two very interesting molecules 2,7-TMPNO and BPNO, which exist in semi-quinoid form and exhibits characteristic of the biradical and quinoid form simultaneously. The 2,7-TMPNO possesses the singlet-triplet energy gap of ��EST = ���1185 K. So it is nearly unrealistic to observe the magnetic field induced spin switching. So we studied the spin switching of this molecule by photo-excitation which was discussed in chapter 6. The structural similarity of BPNO with Tschitschibabin���s HC allowed us to dig the discrepancies related to ground state of Tschitschibabin���s hydrocarbon(Discussed in chapter 7). Finally, in chapter 8 the synthesis and characterization of a neutral paramagnetic HBC derivative (HBCNO) is discussed. The magneto liquid crystalline properties of HBCNO were studied by DSC and EPR spectroscopy.rn