Design, Synthesis, and Photophysical Investigation of Porphyrin-containing Polymer-wrapped Single-walled Carbon Nanotubes

Significant advances in understanding the fundamental photophysical behavior of single-walled carbon nanotubes (SWNTs) have been made possible by the development of ionic, conjugated aryleneethynylene polymers that helically wrap SWNTs with well-defined morphology. My contribution to this work was the design and synthesis of porphyrin-containing polymers and the photophysical investigation of the corresponding polymer-wrapped SWNTs. For these new constructs, the polymer acts as more than just a solubilization scaffold; such assemblies can provide benchmark data for evaluating spectroscopic signatures of energy and charge transfer events and lay the groundwork for further, rational development of polymers with precisely tuned redox properties and electronic coupling with the underlying SWNT. The first design to incorporate a zinc porphyrin into the polymer backbone, PNES-PZn, suffered from severe aggregation in solution and was redesigned to produce the porphyrin-containing polymer S-PBN-PZn. This polymer was utilized to helically wrap chirality-enriched (6,5) SWNTs, which resulted in significant quenching of the porphyrin-based fluorescence. Time-resolved spectroscopy revealed a simultaneous rise and decay of the porphyrin radical cation and SWNT electron polaron spectroscopic signatures indicative of photoinduced electron transfer. A new polymer, S-PBN(b)-Ph2PZn3, was then synthesized which incorporated a meso-ethyne linked zinc porphyrin trimer. By changing the absorption profile and electrochemical redox potentials of the polymer, the photophysical behavior of the corresponding polymer-wrapped (6,5)-SWNTs was dramatically changed, and the polymer-wrapped SWNTs no longer showed evidence for photoinduced electron transfer.

Geochemical composition of calcite and aragonite, and characteristics of hydrothermal fluids of ODP Leg 168 sites

During Leg 168 a transect was drilled across the eastern flank of the Juan de Fuca Ridge in an area where the volcanic basement is covered by sediments of variable thickness. Samples of basement volcanic rocks were recovered from nine locations along the transect, where the basement sediment interface is presently heated to temperatures varying from 15° to 64°C. Altered rocks with secondary calcium carbonate were common at four of the sites, where present-day temperatures range from 38° to 64°C. Fluid inclusions in aragonite suggest that the mineral precipitated from an aqueous fluid of seawater salinity at temperatures well below 100°C. The chemical compositions of secondary calcite and aragonite were determined with both an electron microprobe and a laser-ablation inductively coupled plasma-mass spectroscopy (LA-ICP-MS) microprobe. These two techniques yielded consistent analyses of the same minor elements (Mg and Sr) in the same specimens. The combined results show that secondary aragonites contain very little Mg, Mn, Fe, Co, Ni, Cu, Zn, Rb, La, Ce, Pb, or U, yet they contain significant Sr. In contrast, secondary calcites contain significant Mg, Mn, Fe, Ni, Cu, Zn, and Pb, yet very little Co, Rb, Sr, La, Ce, or U. Secondary calcium carbonates provide subseafloor reservoirs for some minor and trace elements. Replacement of aragonite by calcite should result in a release of Sr, Rb, and Zn to solution, and it provides a sink for Mg, Mn, Ni, Cu, Zn, and Pb.

Chlorophyll-a, primary production rates, carbon concentrations and cell counts of coccolithophores, diatoms and microzooplankton measured in water samples from the North Atlantic during the M87/1 cruise in April 2012

The Deep Convection cruise repeatedly sampled two locations in the North Atlantic, sited in the Iceland and Norwegian Basins, onboard the RV Meteor (19 March - 2 May 2012). Samples were collected from multiple casts of a conductivity-temperature-depth (CTD) - Niskin rosette at each station. Water samples for primary production rates, community structure, chlorophyll a [Chl a], calcite [PIC], particulate organic carbon [POC] and biogenic silicic acid [BSi] were collected from predawn casts from six light depths (55%, 20%, 14%, 7%, 5% and 1% of incident PAR). Additional samples for community structure and ancillary parameters were collected from a second cast. Carbon fixation rates were determined using the 13C stable isotope method. Water samples for diatom and micro zooplankton counts, collected from the predawn casts, were preserved with acidic Lugol's solution (2% final solution) and counted using an inverted light microscope. Water samples for coccolithophore counts were collected onto cellulose nitrate filters and counted using polarising light microscopy. Water samples for Chl a analysis were filtered onto MF300 and polycarbonate filters and extracted in 90% acetone. PIC and BSi samples were filtered onto polycarbonate filters and analysed using an inductively coupled plasma emission optical spectrometer and a SEAL QuAAtro autoanalyser respectively.

Seawater carbonate chemistry, growth rate and morphology of Calcidiscus leptoporus (RCC1135) during experiments, 2011

The coccolithophore Calcidiscus leptoporus (strain RCC1135) was grown in dilute batch culture at CO2 levels ranging from ~200 to ~1600 µatm. Increasing CO2 concentration led to an increased percentage of malformed coccoliths and eventually (at ~1500 µatm CO2) to aggregation of cells. Carbonate chemistry of natural seawater was manipulated in three ways: first, addition of acid; second, addition of a HCO3/CO3 solution; and third, addition of both acid and HCO3/CO3 solution. The data set allowed the disentangling of putative effects of the different parameters of the carbonate system. It is concluded that CO2 is the parameter of the carbonate system which causes both aberrant coccolithogenesis and aggregation of cells.

Crack propagation in non-homogenous materials: Evaluation of mixed-mode SIFs, T-stress and kinking angle using a variant EFG method

A new variant of the Element-Free Galerkin (EFG) method, that combines the diffraction method, to characterize the crack tip solution, and the Heaviside enrichment function for representing discontinuity due to a crack, has been used to model crack propagation through non-homogenous materials. In the case of interface crack propagation, the kink angle is predicted by applying the maximum tangential principal stress (MTPS) criterion in conjunction with consideration of the energy release rate (ERR). The MTPS criterion is applied to the crack tip stress field described by both the stress intensity factor (SIF) and the T-stress, which are extracted using the interaction integral method. The proposed EFG method has been developed and applied for 2D case studies involving a crack in an orthotropic material, crack along an interface and a crack terminating at a bi-material interface, under mechanical or thermal loading; this is done to demonstrate the advantages and efficiency of the proposed methodology. The computed SIFs, T-stress and the predicted interface crack kink angles are compared with existing results in the literature and are found to be in good agreement. An example of crack growth through a particle-reinforced composite materials, which may involve crack meandering around the particle, is reported.

Reversibility Iteration Method to Understand Reaction Networks and to Solve Micro-Kinetics in Heterogeneous Catalysis

Solving microkinetics of catalytic systems, which bridges microscopic processes and macroscopic reaction rates, is currently vital for understanding catalysis in silico. However, traditional microkinetic solvers possess several drawbacks that make the process slow and unreliable for complicated catalytic systems. In this paper, a new approach, the so-called reversibility iteration method (RIM), is developed to solve microkinetics for catalytic systems. Using the chemical potential notation we previously proposed to simplify the kinetic framework, the catalytic systems can be analytically illustrated to be logically equivalent to the electric circuit, and the reaction rate and coverage can be calculated by updating the values of reversibilities. Compared to the traditional modified Newton iteration method (NIM), our method is not sensitive to the initial guess of the solution and typically requires fewer iteration steps. Moreover, the method does not require arbitrary-precision arithmetic and has a higher probability of successfully solving the system. These features make it ∼1000 times faster than the modified Newton iteration method for the systems we tested. Moreover, the derived concept and the mathematical framework presented in this work may provide new insight into catalytic reaction networks.

Effects of the basic fibroblast growth factor and its anti-factor in the healing and collagen maturation of infected skin wound

PURPOSE: The infection is one of the main factors that affect the physiological evolution of the surgical wounds. The aim of this work is to evaluate the effects of fibroblast growth factor (FGFâ) and anti-FGFâ in the healing, synthesis and maturation of collagen when topically used on infected skin wounds of rats. METHODS: An experimental study was perfomed in 60 male Wistar rats. All animals were divided in two groups (A and B). Each group was divided in three subgroups A1, B1; A2, B2 and A3, B3. After anesthesia with pentobarbital, two open squared wounds (1cm2), 4cm distant to each other, were done in the dorsal skin of all the rats. In group A (n=30) the wounds were contaminated with multibacterial standard solution, and in group B(n=30) the wounds were maintained sterile. These wounds were named F1 (for inflammation analysis) and F2 (for collagen study). The open wounds of A1 and B1 rats were topically treated with saline solution, A2 and B2 were treated with FGFâ and subgroups A3 and B3 were treated with FGFâ and anti-FGFâ. The rats were observed until complete epitelization of F2 wounds for determination of healing time and the expression of types I and III collagen, using Picro Sirius Red staining. Inflammatory reaction in F1 wounds was studied using hematoxilineosin staining. The three variable was measured by the Image Pro-Plus Média Cybernetics software. The statistical analysis was performed by ANOVA and Tukey test, considering p<0.05 as significant. RESULTS: It was observed that infection retarded significantly (p<0.05) the time of wound scarring and the topical application of FCFb reverted the inhibition of healing caused by bacteria. The inflammatory reaction was greater in the subgroup B2 than in B1 and A3, and the difference was significant (p<0.05). It was observed greater expression of type I collagen in all the subgroups treated with FCFb, when compared with the untreated subgroups. Type III collagen was significantly decreased in wounds of B3 rats, comparing to the other subgroups. CONCLUSIONS: The FCFb accelerated the healing of open infected wounds and contributed with maturation of collagen, enhancing the type I collagen density. The anti-FCFb antibody was able to attenuate the production of both type I and III collagen

The governance of adaptation: choices, reasons, and effects. Introduction to the Special Feature

The governance of climate adaptation involves the collective efforts of multiple societal actors to address problems, or to reap the benefits, associated with impacts of climate change. Governing involves the creation of institutions, rules and organizations, and the selection of normative principles to guide problem solution and institution building. We argue that actors involved in governing climate change adaptation, as climate change governance regimes evolve, inevitably must engage in making choices, for instance on problem definitions, jurisdictional levels, on modes of governance and policy instruments, and on the timing of interventions. Yet little is known about how and why these choices are made in practice, and how such choices affect the outcomes of our efforts to govern adaptation. In this introduction we review the current state of evidence and the specific contribution of the articles published in this Special Feature, which are aimed at bringing greater clarity in these matters, and thereby informing both governance theory and practice. Collectively, the contributing papers suggest that the way issues are defined has important consequences for the support for governance interventions, and their effectiveness. The articles suggest that currently the emphasis in adaptation governance is on the local and regional levels, while underscoring the benefits of interventions and governance at higher jurisdictional levels in terms of visioning and scaling-up effective approaches. The articles suggest that there is a central role of government agencies in leading governance interventions to address spillover effects, to provide public goods, and to promote the long-term perspectives for planning. They highlight the issue of justice in the governance of adaptation showing how governance measures have wide distributional consequences, including the potential to amplify existing inequalities, access to resources, or generating new injustices through distribution of risks. For several of these findings, future research directions are suggested.

Strategic Information Disclosure through Integrated Reporting : A study on OMXS30-listed companies’ compliance with the <IR> Framework content element Strategy and Resource Allocation

Background and problem – As a result of financial crises and the realization of a broader stakeholder network, recent decades have seen an increase in stakeholder demand for non- financial information in corporate reporting. This has led to a situation of information overload where separate financial and sustainability reports have developed in length and complexity interdependent of each other. Integrated reporting has been presented as a solution to this problematic situation. The question is whether the corporate world believe this to be the solution and if the development of corporate reporting is heading in this direction. Purpose - This thesis aims to examine and assess to what extent companies listed on the OMX Stockholm 30 (OMXS30), as per 2016-02-28, comply with the Strategic content element of the <IR> Framework and how this disclosure has developed since the framework’s pilot project and official release by using a self-constructed disclosure index based on its specific items. Methodology – The purpose was fulfilled through an analysis of 104 annual reports comprising 26 companies during the period of 2011-2014. The annual reports were assessed using a self-constructed disclosure index based on the <IR> Framework content element Strategy and Resource Allocation, where one point was given for each disclosed item. Analysis and conclusions – The study found that the OMXS30-listed companies to a large extent complies with the strategic content element of the <IR> Framework and that this compliance has seen a steady growth throughout the researched time span. There is still room for improvement however with a total average framework compliance of 84% for 2014. Although many items are being reported on, there are indications that companies generally miss out on the core values of Integrated reporting. 

The grand challenge of food security - general lessons from a comprehensive approach to protecting stored grain from insect pests in Australia and India

We outline a philosophical approach to Grand Challenge projects, with particular reference to our experience in our food security project involving the protection of stored grain from insect attack in two countries on different continents. A key consideration throughout has been the management of resistance in these pests to the valuable fumigant phosphine. Emphasis is given to the chain of research issues that required solution and the assembly of a well-integrated team, overlapping in skills for effective communication, in each country to solve the problems identified along that chain. A crucial aspect to maintaining direction is the inclusion of key end users in all deliberations, as well as the establishment and maintenance of effective outlets for the dissemination of practical recommendations. We finish with a summary of our achievements with respect to our approach to this food security Grand Challenge.

Effects of the basic fibroblast growth factor and its anti-factor in the healing and collagen maturation of infected skin wound

PURPOSE: The infection is one of the main factors that affect the physiological evolution of the surgical wounds. The aim of this work is to evaluate the effects of fibroblast growth factor (FGFâ) and anti-FGFâ in the healing, synthesis and maturation of collagen when topically used on infected skin wounds of rats. METHODS: An experimental study was perfomed in 60 male Wistar rats. All animals were divided in two groups (A and B). Each group was divided in three subgroups A1, B1; A2, B2 and A3, B3. After anesthesia with pentobarbital, two open squared wounds (1cm2), 4cm distant to each other, were done in the dorsal skin of all the rats. In group A (n=30) the wounds were contaminated with multibacterial standard solution, and in group B(n=30) the wounds were maintained sterile. These wounds were named F1 (for inflammation analysis) and F2 (for collagen study). The open wounds of A1 and B1 rats were topically treated with saline solution, A2 and B2 were treated with FGFâ and subgroups A3 and B3 were treated with FGFâ and anti-FGFâ. The rats were observed until complete epitelization of F2 wounds for determination of healing time and the expression of types I and III collagen, using Picro Sirius Red staining. Inflammatory reaction in F1 wounds was studied using hematoxilineosin staining. The three variable was measured by the Image Pro-Plus Média Cybernetics software. The statistical analysis was performed by ANOVA and Tukey test, considering p<0.05 as significant. RESULTS: It was observed that infection retarded significantly (p<0.05) the time of wound scarring and the topical application of FCFb reverted the inhibition of healing caused by bacteria. The inflammatory reaction was greater in the subgroup B2 than in B1 and A3, and the difference was significant (p<0.05). It was observed greater expression of type I collagen in all the subgroups treated with FCFb, when compared with the untreated subgroups. Type III collagen was significantly decreased in wounds of B3 rats, comparing to the other subgroups. CONCLUSIONS: The FCFb accelerated the healing of open infected wounds and contributed with maturation of collagen, enhancing the type I collagen density. The anti-FCFb antibody was able to attenuate the production of both type I and III collagen

Redução do Impacto Ambiental de Poluentes Orgânicos Persistentes

Nos dias de hoje a contaminação dos solos e águas subterrâneas com pesticidas através da agricultura tornou-se um problema. Problema este, considerado ainda maior nas áreas onde o abastecimento de água potável é quase totalmente à base de água subterrânea, causando deste modo risco para a saúde humana devido à exposição directa de possíveis resíduos de pesticidas na água potável. É certo que a persistência dos pesticidas no solo é importante para obter um bom controlo sob as ervas daninhas durante a sua época de crescimento, contudo o uso desses pesticidas contamina não só o solo como as águas superficiais. As questões acerca do uso de pesticidas na actualidade continuarão a persistir, uma vez que existem muitos factores e características inerentes a este processo que necessitam de ser abordadas e mais importante que isso estudadas, como por exemplo a sua degradação e toxicidade. Neste trabalho efectuou-se o encapsulamento de pesticidas em moléculas de β – ciclodextrina (β-CD). O que se pretende com este encapsulamento, é aumentar a hidrofilicidade do pesticida de forma a garantir que este persista o tempo suficiente permitindo um bom controlo das ervas daninhas, tendo sempre em conta as preocupações inerentes ao uso dos pesticidas, como por exemplo a dificuldade de biodegradação. O estudo centrou-se em torno de dois dos pesticidas mais utilizados em Portugal: MCPA e Bentazona. Estes herbicidas foram encapsulados individualmente na β-CD formando assim complexos, mais solúveis e eventualmente mais estáveis quimicamente garantindo uma redução dos efeitos dos pesticidas no meio ambiente. Este estudo foi dividido essencialmente em duas partes: a síntese e caracterização dos complexos pesticida-β-CD e posteriormente a avaliação da estabilidade química em solução aquosa e da solubilidade dos complexos formados. A utilização de diversas técnicas analíticas nomeadamente DSC, FTIR, Espectrofotometria de UV, HPLC e Electroquímica permitiram concluir que o pesticida MCPA encapsula pela acção da β-CD aquando do complexo formado em solução etanólica e numa proporção estequiométrica MCPA:β-CD de 1:2 respectivamente. Obteve-se para as várias soluções estudadas, todas elas com concentrações diferentes de β-CD, uma constante de estabilidade de 102,4. No caso da Bentazona, os resultados preliminares obtidos indiciam claramente a formação de um complexo com a β-CD para o complexo formado em solução etanólica.

Desenvolvimento de filmes nanocompósitos de isolado protéico de corvina (micropogonias furnieri) e argila organofílica

O desenvolvimento de filmes e coberturas é um processo de transformação que utiliza polímeros capazes de formar uma matriz contínua. As proteínas de pescado apresentam propriedades que são vantajosas no preparo de biofilmes, como habilidade para formar redes, plasticidade e elasticidade, apresentando boa barreira ao oxigênio, mas sua barreira ao vapor de água é baixa devido à sua natureza hidrofílica. Estas propriedades podem ser melhoradas aplicando nanotecnologia, incluindo materiais como as nanoargilas. O objetivo do presente trabalho foi desenvolver filmes nanocompósitos a partir de biopolímeros protéicos provenientes de isolados protéicos de corvina (Micropogonias furnieri) e argilas organofílicas. O isolado protéico de corvina (IPC) foi obtido utilizando processo de variação de pH para solubilizar e isolar proteína. Os filmes poliméricos foram desenvolvidos pela técnica de “casting”. Para o desenvolvimento de filmes nanocompósitos de isolado protéico de corvina (IPC) e montmorilonita foi executado um planejamento experimental de 3 níveis e 3 fatores com 3 réplicas no ponto central. Os resultados foram submetidos à metodologia de superfície de resposta (MSR) para estudar os efeitos simultâneos das variáveis independentes, concentração de IPC (IPC = 2; 3,5 e 5 g/100 g de solução filmogênica); concentração de montmorilonita (MMT = 0,3; 0,5 e 0,7 g/100 g de solução filmogênica); e plastificante glicerol (G = 25, 30 e 35 g/100 g de IPC em base seca) sobre as respostas resistência à tração (MPa), elongação (%), força na ruptura (N), permeabilidade ao vapor de água (g mm m-2 d -1 KPa-1 ) e solubilidade (%). O isolado protéico obtido de carne mecanicamente separada de corvina apresentou 97,87% de proteína (em base seca), boa capacidade de retenção de água e solubilidade. Os valores de resistência à tração variaram entre 7,2 e 10,7 MPa e os valores de elongação de 39,6 a 45,8%. Os valores encontrados para PVA no presente trabalho encontram-se entre 3,2 e 5,5 g mm m-2 d -1 KPa-1 . Os filmes nanocompósitos produzidos a partir de IPC e MMT foram promissores, do ponto de vista das propriedades mecânicas, aparência visual e fácil manuseio, bem como baixa permeabilidade ao vapor de água e a baixa solubilidade. Com relação às propriedades mecânicas, a concentração de IPC e MMT foi o principal fator que influenciou no desenvolvimento dos filmes nanocompósitos. O planejamento experimental utilizado determinou que 3,5 g de IPC; 0,5 g de MMT e 30 (g/100g de IPC) de glicerol seriam os parâmetros ideais para desenvolvimento de filmes nanocompósitos utilizando a técnica de “casting”. As coberturas de isolado protéico de corvina (IPC) e as coberturas de IPC e MMT foram aplicadas em mamão minimamente processado para avaliar sua vida- útil. O revestimento com cobertura de isolado protéico de corvina e montmorilonita aplicado em mamão minimamente processado apresentou menor perda de massa 5,26%, menor crescimento microbiano e menor diminuição de firmeza, luminosidade e pH conseqüentemente apresentou os melhores resultados na cobertura de mamão minimamente processado, quando comparados com a amostra controle sem cobertura.

Xylem plugging and postharvest longevity of cut Acacia holosericea

An inherently short vase life is a problematic characteristic of cut flowers and foliage for otherwise attractive native Australian Acacia spp. Reasons underlying the poor postharvest water uptake of cut acacia stems have been elusive. A. holosericea was used to investigate possible bacteria-induced and wound-induced xylem occlusion. The effects of bacterial-and wound-induced xylem blockage on water uptake were investigated by light and scanning and transmission electron microscopy. Observations were made on cut stems that stood into either deionised water (DIW; control) or 0.5 mM Cu2+ solution and on stems pulsed with 2.2 mM Cu2+ solution and then stood into DIW. The stem-end region of cut A. holosericea that stood into DIW or Cu2+ solution became covered with bacterial growth after 3 days. Regardless of the bacterial biofilm, the Cu2+ treated stems had improved water relations and vase life. Therefore, the biofilm had little or no effect on cut A. holosericea longevity. Further observations revealed presence of a vessel-occluding substance (gel) originating from axial parenchyma cells in direct physical contact with xylem vessels. The gel exuded into vessel lumens through pit membranes, evidently as a wound-response. Xylem occlusion by gels in A. holosericea may be especially problematic due to an abundance of secretory contact cells relative to xylem elements. Nonetheless, active wound response processes may be the key determinant of short postharvest longevity for this and possibly other cut Acacia spp. Cu2+ treatments, however, disrupted the secretory function of axial parenchyma cells thereby preventing vessel occlusion by the gels.

Postharvest handling practices and irradiation increase lenticel discolouration in ‘B74’ mango fruit

ABSTRACT 'B74' mango is a recently commercialised cultivar in Australia, with an appealing skin colour and firm fibreless flesh. However, fruit can develop lenticel discolouration (LD) after harvest, with loss of commercial value, especially after γ-irradiation as a disinfestation treatment. We hypothesised that postharvest practices could increase fruit sensitivity to LD and tested that by sequentially sampling fruit between the orchard and the end of the packing line over two seasons, followed by ripening without and with irradiation treatment. Exposure of 441-610 Gy γ-irradiation significantly increased the severity of LD by 6.8-fold in commercially picked and packed ripe fruit, reducing the proportion of marketable fruit from 98% to 2%, compared to irradiated fruit harvested directly from the trees and not exposed to de-sapping solution and packing operations. Also, LD increased progressively as the fruit passed through the harvesting and packing processes, and exposure to only bore water increased LD severity compared with no water contact. Results suggest that the typical de-sapping process used during harvesting is a major contributor to skin sensitivity to LD in 'B74' mango fruit, and that other packing operations involving wetting of the fruit have an additive effect on it. These effects are exacerbated if fruit is irradiated.