Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

A family of nanoscale-sized supramolecular cage compounds with a polyhedral framework is prepared by self-assembly from tritopic building blocks and rectangular corner units via noncovalent coordination interactions. These highly symmetrical cage compounds are described as face-directed, self-assembled truncated tetrahedra with Td symmetry.

Measuring the forces involved in polyvalent adhesion of uropathogenic Escherichia coli to mannose-presenting surfaces

Mechanisms of bacterial pathogenesis have become an increasingly important subject as pathogens have become increasingly resistant to current antibiotics. The adhesion of microorganisms to the surface of host tissue is often a first step in pathogenesis and is a plausible target for new antiinfective agents. Examination of bacterial adhesion has been difficult both because it is polyvalent and because bacterial adhesins often recognize more than one type of cell-surface molecule. This paper describes an experimental procedure that measures the forces of adhesion resulting from the interaction of uropathogenic Escherichia coli to molecularly well defined models of cellular surfaces. This procedure uses self-assembled monolayers (SAMs) to model the surface of epithelial cells and optical tweezers to manipulate the bacteria. Optical tweezers orient the bacteria relative to the surface and, thus, limit the number of points of attachment (that is, the valency of attachment). Using this combination, it was possible to quantify the force required to break a single interaction between pilus and mannose groups linked to the SAM. These results demonstrate the deconvolution and characterization of complicated events in microbial adhesion in terms of specific molecular interactions. They also suggest that the combination of optical tweezers and appropriately functionalized SAMs is a uniquely synergistic system with which to study polyvalent adhesion of bacteria to biologically relevant surfaces and with which to screen for inhibitors of this adhesion.

Systemic immunization with papillomavirus L1 protein completely prevents the development of viral mucosal papillomas.

Infection of mucosal epithelium by papillomaviruses is responsible for the induction of genital and oral warts and plays a critical role in the development of human cervical and oropharyngeal cancer. We have employed a canine model to develop a systemic vaccine that completely protects against experimentally induced oral mucosal papillomas. The major capsid protein, L1, of canine oral papillomavirus (COPV) was expressed in Sf9 insect cells in native conformation. L1 protein, which self-assembled into virus-like particles, was purified on CsCl gradients and injected intradermally into the foot pad of beagles. Vaccinated animals developed circulating antibodies against COPV and became completely resistant to experimental challenge with COPV. Successful immunization was strictly dependent upon native L1 protein conformation and L1 type. Partial protection was achieved with as little as 0.125 ng of L1 protein, and adjuvants appeared useful for prolonging the host immune response. Serum immunoglobulins passively transferred from COPV L1-immunized beagles to naive beagles conferred protection from experimental infection with COPV. Our results indicate the feasibility of developing a human vaccine to prevent mucosal papillomas, which can progress to malignancy.

Lipid monolayer image dipoles.

A simple model is described for calculating the electrostatic energy of lipid domains at the air-water interface, taking account of dipole-dipole repulsions between the lipid molecules themselves, as well as interactions between the molecular dipoles and image dipoles in the subphase. The model assumes that the molecular dipoles within the monolayer arise from the terminal methyl groups of the hydrophobic hydrocarbon chains of the lipid molecules, and that on average they are oriented perpendicular to the plane of the monolayer. With this model the role of the subphase is to enhance rather than suppress the effects of dipole-dipole repulsions.

Direct measurement of hydrogen bonding in DNA nucleotide bases by atomic force microscopy.

We have used self-assembled purines and pyrimidines on planar gold surfaces and on gold-coated atomic force microscope (AFM) tips to directly probe intermolecular hydrogen bonds. Electron spectroscopy for chemical analysis (ESCA) and thermal programmed desorption (TPD) measurements of the molecular layers suggested monolayer coverage and a desorption energy of about 25 kcal/mol. Experiments were performed under water, with all four DNA bases immobilized on AFM tips and flat surfaces. Directional hydrogen-bonding interaction between the tip molecules and the surface molecules could be measured only when opposite base-pair coatings were used. The directional interactions were inhibited by excess nucleotide base in solution. Nondirectional van der Waals forces were present in all other cases. Forces as low as two interacting base pairs have been measured. With coated AFM tips, surface chemistry-sensitive recognition atomic force microscopy can be performed.

Espécies polinucleares de cobre e ferro com catalisadores de oxidação e modelos de sítios ativos

Diferentes complexos de cobre(II), contendo ligantes do tipo base de Schiff e um grupamento imidazólico, com interesse bioinorgânico, catalítico e como novos materiais, foram preparados na forma de sais perclorato, nitrato ou cloreto e caracterizados através de diferentes técnicas espectroscópicas (UV/Vis, IR, EPR, Raman) e espectrometria de massa Tandem (ESI-MS/MS), além de análise elementar, condutividade molar e medidas de propriedades magnéticas. Alguns destes compostos, obtidos como cristais adequados, tiveram suas estruturas determinadas por cristalografia de raios-X. As espécies di- e polinucleares contendo pontes cloreto, mostraram desdobramentos das hiperfinas nos espectros de EPR, relacionados à presença do equilíbrio com a respectiva espécie mononuclear, devido à labilidade dos íons cloretos, dependendo do contra-íon e do tipo de solvente utilizado. Adicionalmente, em solução alcalina, estes compostos estão em equilíbrio com as correspondentes espécies polinucleares, onde os centros de cobre estão ligados através de um ligante imidazolato. Em meio alcalino, estes compostos polinucleares contendo ponte imidazolato foram também isolados e caracterizados por diferentes técnicas espectroscópicas e magnéticas. Através da variação estrutural e também do ligante-ponte foi possível modular o fenômeno da interação magnética entre os íons de cobre em estruturas correlatas di- e polinucleares. Os respectivos parâmetros magnéticos foram obtidos com ajuste das curvas experimentais de XM vs T, correlacionando-se muito bem com a geometria, ângulos e distâncias de ligação entre os íons, quando comparado com outros complexos similares descritos na literatura. Posteriormente, estudaram-se os fatores relacionados com a reatividade de todas essas espécies como catalisadores na oxidação de substratos de interesse (fenóis e aminas), através da variação do tamanho da cavidade nas estruturas cíclicas ou de variações no ligante coordenado ao redor do íon metálico. Vários deles se mostraram bons miméticos de tirosinases e catecol oxidases. Um novo complexo-modelo da citocromo c oxidase (CcO), utilizando a protoporfirina IX condensada ao quelato N,N,-bis[2-(1,2-metilbenzimidazolil)etil]amino e ao resíduo de glicil-L-histidina, foi sintetizado e caracterizado através de diferentes técnicas espectroscópicas, especialmente EPR. A adição de H2O2 ao sistema completamente oxidado, FeIII/CuII, a -55°C, ou o borbulhamento de oxigênio molecular a uma solução do complexo na sua forma reduzida, FeII/CuI, saturada de CO, resultou na formação de adutos com O2, de baixo spin, estáveis a baixas temperaturas.

Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.

Reducing and recycling mercury switch thermostats and vehicle components : a report to Governor Blagojevich and the Illinois General Assembly.

Over the last two years, Governor Blagojevich and the Illinois General Assembly have enacted a number of laws to reduce the health risks associated with the use and disposal of consumer, household and commercial products that contain mercury. These products include thermometers, switches, electrical relays and scientific instruments used in schools. The purpose of these laws is to reduce mercury releases into the environment. Mercury is a strong neurotoxin that can be harmful to the health of humans and wildlife. Mercury exposure poses a particular risk to young children and pregnant women because mercury may inhibit the development of the brain and nervous system. This report presents recommendations for improving efforts to reduce and recycle mercury components that are found in thermostats and motor vehicles. Illinois EPA prepared the report in response to Public Act 93-0964. In drafting the report, Illinois EPA conducted research on mercury reduction and recycling programs in other states, reviewed technical studies and consulted with officials in the private and public sectors.

Stress associated with the transition from high school to university: The effect of social support and self-efficacy

The present study aimed to evaluate the role of social support and self-efficacy on the level of stress associated with the transition from high school to university. One hundred and eight-five university students who had completed high school in the previous year completed a three-part questionnaire designed to gather information on their levels of self-efficacy, social support, and stress associated with their transition. The results showed that self-efficacy was a significant predictor of stress associated with the transition to university in that higher levels of self-efficacy were associated with lower levels of stress while social support was a non-significant predictor of stress. [Author abstract]

Loyalty without Conformity: Tailoring Self-perception as a Means of Balancing Belonging and Differentiation

We argue that members of individualist cultures balance their desire to belong with their desire to be different by maintaining a self-image as being loyal but relatively immune to group influence. Consistent with this, in Study 1 there was a strong tendency for people to rate themselves as being more independent (i.e., less conformist) than other people in their college. College students also rated themselves as being highly loyal to the group, however no self - other discrepancies were found on this dimension. This is despite the fact that traits of loyalty were rated more positively than were traits of independence. Study 2 provided evidence that culture influences the pattern of self - other discrepancies. Whereas people from individualist countries self-enhance on independence dimensions, people from collectivist countries self-enhance on loyalty dimensions. Again, these effects could not be explained as being a function of how positive these traits were seen to be, suggesting a cultural explanation rather than a straight forward superiority bias explanation for the observed discrepancies in self - other ratings. Results are discussed in relation to the SCENT model.

Enhanced energy status of corals on coastal, high-turbidity reefs

Sedimentation and high turbidity have long been considered a major threat to corals, causing world-wide concern for the health of coral reefs in coastal environments. While studies have demonstrated that sediment conditions characteristic of inshore reefs cause stress in corals, the consequences of such conditions for the physiological status of corals require testing in field situations. Here, I compare the size of energy stores (as lipid content), a proxy for physiological condition, of 2 coral species (Turbinaria mesenterina and Acropora valida) between coastal and offshore environments. Corals on coastal reefs contained 4-fold (T mesenterina) and 2-fold (A. valida) more lipid than conspecifics offshore, despite 1 order of magnitude higher turbidity levels inshore. Results were consistent across 4 sites in each environment. Reproductive investment in A. valida (a seasonal mass spawner) did not vary between environments, suggesting that the larger lipid stores in corals on coastal reefs are mainly somatic energy reserves. These results demonstrate that the environmental conditions on inshore, high-turbidity reefs do not always impact negatively on the physiology of corals. The contrasting lipid levels of T. mesenterina between environments may explain its greater success on coastal reefs.

Reversible active switching of the mechanical properties of a peptide film at a fluid-fluid interface

Designer peptides have recently been developed as building blocks for novel self-assembled materials with stimuli-responsive properties. To date, such materials have been based on self-assembly in bulk aqueous solution or at solid-fluid interfaces. We have designed a 21-residue peptide, AM1, as a stimuli-responsive surfactant that switches molecular architectures at a fluid-fluid interface in response to changes in bulk aqueous solution composition. In the presence of divalent zinc at neutral pH, the peptide forms a mechanically strong 'film state'. In the absence of metal ions or at acid pH, the peptide adsorbs to form a mobile 'detergent state'. The two interfacial states can be actively and reversibly switched. Switching between the two states by a change in pH or the addition of a chelating agent leads to rapid emulsion coalescence or foam collapse. This work introduces a new class of surfactants that offer an environmentally friendly approach to control the stability of interfaces in foams, emulsions and fluid-fluid interfaces more generally.

Perspectives on quality of life by people with aphasia and their family: Suggestions for successful living

Understanding the client's perspective is essential for good practitioner care in rehabilitation after stroke, and nothing is more relevant than enquiring directly about our clients' quality of life to inform our management. Relatively little is known about how older people with aphasia consider the quality of their current lives, and this article seeks to explore this issue. Four women's accounts of their life quality are presented, as well as their husbands' or daughter's accounts of their lives. Their stories share some common elements. Who you love or share your life with; where you live; feeling independent and/or in control; and engaging in satisfying activities mattered to these women's life quality. The impact of aphasia varies across the cases, and the need to accept change for successful living is illustrated in all accounts.

Self-efficacy and task performance: An investigation from two levels of analysis and specificity

This research adopts a resource allocation theoretical framework to generate predictions regarding the relationship between self-efficacy and task performance from two levels of analysis and specificity. Participants were given multiple trials of practice on an air traffic control task. Measures of task-specific self-efficacy and performance were taken at repeated intervals. The authors used multilevel analysis to demonstrate dynamic main effects, dynamic mediation and dynamic moderation. As predicted, the positive effects of overall task specific self-efficacy and general self-efficacy on task performance strengthened throughout practice. In line with these dynamic main effects, the effect of general self-efficacy was mediated by overall task specific self-efficacy; however this pattern emerged over time. Finally, changes in task specific self-efficacy were negatively associated with changes in performance at the within-person level; however this effect only emerged towards the end of practice for individuals with high levels of overall task specific self-efficacy. These novel findings emphasise the importance of conceptualising self-efficacy within a multi-level and multi-specificity framework and make a significant contribution to understanding the way this construct relates to task performance.

Gold nanoparticles decorated with oligo(ethylene glycol) thiols:enhanced Hofmeister effects in colloid−protein mixtures

Oligo(ethylene glycol) (OEG) thiol self-assembled monolayer (SAM) decorated gold nanoparticles (AuNPs) have potential applications in bionanotechnology due to their unique property of preventing the nonspecific absorption of protein on the colloidal surface. For colloid-protein mixtures, a previous study (Zhang et al. J. Phys. Chem. A 2007, 111, 12229) has shown that the OEG SAM-coated AuNPs become unstable upon addition of proteins (BSA) above a critical concentration, c*. This has been explained as a depletion effect in the two-component system. Adding salt (NaCl) can reduce the value of c*; that is, reduce the stability of the mixture. In the present work, we study the influence of the nature of the added salt on the stability of this two-component colloid-protein system. It is shown that the addition of various salts does not change the stability of either protein or colloid in solution in the experimental conditions of this work, except that sodium sulfate can destabilize the colloidal solutions. In the binary mixtures, however, the stability of colloid-protein mixtures shows significant dependence on the nature of the salt: chaotropic salts (NaSCN, NaClO4, NaNO3, MgCl2) stabilize the system with increasing salt concentration, while kosmotropic salts (NaCl, Na2SO4, NH4Cl) lead to the aggregation of colloids with increasing salt concentration. These observations indicate that the Hofmeister effect can be enhanced in two-component systems; that is, the modification of the colloidal interface by ions changes significantly the effective depletive interaction via proteins. Real time SAXS measurements confirm in all cases that the aggregates are in an amorphous state.