Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics.

Photocurrent generation in organic photovoltaics (OPVs) relies on the dissociation of excitons into free electrons and holes at donor/acceptor heterointerfaces. The low dielectric constant of organic semiconductors leads to strong Coulomb interactions between electron-hole pairs that should in principle oppose the generation of free charges. The exact mechanism by which electrons and holes overcome this Coulomb trapping is still unsolved, but increasing evidence points to the critical role of hot charge-transfer (CT) excitons in assisting this process. Here we provide a real-time view of hot CT exciton formation and relaxation using femtosecond nonlinear optical spectroscopies and non-adiabatic mixed quantum mechanics/molecular mechanics simulations in the phthalocyanine-fullerene model OPV system. For initial excitation on phthalocyanine, hot CT excitons are formed in 10(-13) s, followed by relaxation to lower energies and shorter electron-hole distances on a 10(-12) s timescale. This hot CT exciton cooling process and collapse of charge separation sets the fundamental time limit for competitive charge separation channels that lead to efficient photocurrent generation.

A novel tool for quantitative measurement of distortion in keratoconus.

BACKGROUND: Keratoconus is associated with thinning and anterior protrusion of the cornea resulting in the symptoms of blurry and distorted vision. The commonly used clinical vision tests such as visual acuity and contrast sensitivity may not reflect the symptoms experienced in keratoconus and there are no quantitative tools to measure visual distortion. In this study, we used a quantitative test based on vernier alignment and field matching techniques to quantify visual distortion in keratoconus and assess its relation to corneal structural changes. METHODS: A total of 50 participants (25 keratoconus and 25 visually normal) completed the experiment where they aligned supra-threshold white target circles in opposite field in reference to guidelines and circles to complete a square structure monocularly. The task was repeated five times and the global distortion index (GDI) and global uncertainty index (GUI) were calculated as the mean and standard deviation respectively of local perceived misalignment of target circles over five trials. RESULTS: Both GDI and GUI were higher in participants with keratoconus compared to controls (p < 0.01). Both parameters correlated with the best corrected visual acuity, maximum corneal curvature (Kmax), topographical keratoconus classification (TKC) and central corneal thickness (CCT). CONCLUSION: Our findings show that the quantitative measure of distortion could be a useful tool for behavioural assessment of progressive keratoconus.

Monolayer properties of chloroplast lipids.

The properties of seven monogalactosyldiacylglycerols and six digalactosyldiacylglycerols, isolated from photosynthetic membranes and possessing different levels of fatty acid unsaturation, have been studied by the monolayer technique and compared with those of the fully saturated compounds. In addition, the monolayer properties of sulphoquinovosyldiacylglycerols and phosphatidylglycerols from higher plant chloroplasts, and several hexadecenoic acids have been measured. Monogalactosyldiacylglycerols containing saturated fatty acids form a condensed monolayer similar to that of saturated phosphatidylcholines. The naturally occurring monogalactosyldiacylglycerols, of which the double bond index ranged from 0.6 to 3.9, possessed comparable force-area curves suggesting that headgroup interactions play a more important role in packing behaviour than in phosphatidylcholines. Although digalactosyldiacylglycerols containing fully saturated fatty acids form a more expanded monolayer than the corresponding monogalactosyldiacylglycerols, the degree of expansion of the monolayer due to the presence of unsaturated fatty acids in the naturally occurring digalactosyldiacylglycerols is much less than in monogalactosyldiacylglycerols. Monogalactosyldiacylglycerols and digalactosyldiacylglycerols from a single species have very similar monolayer properties, and the presence of sulphoquinovosyldiacylglycerols and phosphatidylglycerols in the proportions in which they occur in higher plant chloroplasts does not have any condensing effect on a monolayer of galactolipids.

Molecular basis of IgE-recognition of Lol p 5, a major allergen of rye-grass pollen.

Grass pollen, especially of rye-grass (Lolium perenne). represents an important cause of type I allergy. Identification of IgE-binding (allergenic) epitopes of major grass pollen allergens is essential for understanding the molecular basis of interaction between allergens and human IgE antibodies and therefore facilitates the devising of safer and more effective diagnostic and immunotherapy reagents. The aim of this study was to identify the allergenic epitopes of Lol p 5, a major allergen of rye-grass pollen, immunodissect these epitopes further so that the amino acid residues critical for antibody binding can be determined and investigate the conservation and nature of these epitopes within the context of the natural grass pollen allergens. Peptides, 12-13 amino acid residues long and overlapping each other by 4 amino acid residues, based on the entire deduced amino acid sequence of the coding region of Lol p 5, were synthesised and assayed for IgE-binding. Two strong IgE-binding epitopes (Lol p 5 (49-60) and (265-276), referred to as peptides 7 and 34, respectively) were identified. These epitopes were further resolved by truncated peptides and amino acid replacement studies and the amino acid residues critical for IgE-binding determined (Lol p 5 (49-60) residue Lys57 and (265-276) residue Lys275). Sequences of these epitopes were conserved in related allergens and may form the conserved allergenic domains responsible for the cross-reactivity observed between pollen allergens of taxonomically related grasses. Furthermore, due to its strong IgE-reactivity, synthetic peptide Lol p 5 (265-276) was used to affinity-purify specific IgE antibodies which recognised proteins of other clinically important grass pollens. further indicating presence of allergenic cross-reactivity at the level of allergenic epitope. Moreover, Lol p 5 (265 276) demonstrated a strong capacity to inhibit IgE-binding to natural rye-grass pollen proteins highlighting the antibody accessibility to these sequences within the context of the natural allergens. Strong IgE-binding epitopes of Lol p 5 have been identified down to single critical amino acid residues and are shown to occur as linear or continuous domains in the natural conformation of natural Lol p 5 and other group 5 grass pollen allergens. The fact that such an allergenic synthetic epitope has the capacity to strongly inhibit IgE-binding to natural allergens highlight its potential for use as a candidate in future therapeutics to treat pollen-associated allergies.

A novel grass pollen allergen mimotope identified by phage display peptide library inhibits allergen-human IgE antibody interaction.

The aim of this study was to investigate the molecular basis of human IgE-allergen interaction by screening a phage-displayed peptide library with an allergen-specific human IgE-mimicking monoclonal antibody (mAb). A mAb that reacted with major grass pollen allergens was successfully identified and shown to inhibit human IgE-allergen interaction. Biopanning of a phage-displayed random peptide library with this mAb yielded a 12 amino acid long mimotope. A synthetic peptide based on this 12-mer mimotope inhibited mAb and human IgE binding to grass pollen extracts. Our results indicate that such synthetic peptide mimotopes of allergens have potential as novel therapeutic agents.

Preparation and comparison of model bilayer systems from chloroplasts thylakoid membrane lipids for 13C-NMR studies.

Model bilayer systems from individual purified chloroplast thylakoid membrane lipids, from reconstituted mixtures of these purified lipids, and from leaf total polar lipid extracts have been prepared in water, and the longitudinal relaxation times (T1's) of the individual carbon atoms of the fatty acyl chains measured by 13C-NMR spectroscopy. The T1's increase with increasing distance of the carbon atoms from the polar headgroups in all cases, and as the results from each of the preparations are similar, all can be used as models of chloroplast membrane bilayers. Relaxation time measurements on intact chloroplast thylakoid membranes indicate the presence of chlorophyll resonances in the 13C-NMR spectrum of the membrane.

Fatty acid composition of symbiotic zooxanthellae in relation to their hosts.

Gymnodinoid dinoflagellate symbionts, commonly referred to as zooxanthellae, are widely distributed among marine invertebrates. It has been assumed that they represent only one species,Gymnodinium microadriaticum. The fatty acid composition of total lipids and galactolipids of zooxanthellae isolated from 8 species of corals, 3 species of clams and a foraminiferan have been analyzed and found to vary according to the host. For example, the content of eicosapentaenoic acid in clam zooxanthellae monogalactosyldiacylglycerol was less than 2%, whereas in the same lipid from coral zooxanthellae, the content ranged from 9 to 22%. Corresponding values for the acid in digalactosyl-diacylglycerol were 1-8% from clam zooxanthellae and 23-40% from coral zooxanthellae. Coral zooxanthellae monogalactosyldiacylglycerol contain higher levels of octadecatetraenoic acid than are found in digalactosyldiacylglycerol, whereas the reverse is true in clam zooxanthellae. The fatty acid composition of the lipids of an axenic culture of zooxanthellae isolated from the clamTridacna maxima are similar to those of cells freshly isolated from the host. The results suggest either that the host is capable of affecting the fatty acid metabolism of the symbiont or that different strains of zooxanthellae occur in corals and clams.

Publication productivity in academic family medicine departments.

BACKGROUND AND OBJECTIVES: The purpose of this study was to quantify research publication productivity of family medicine departments in selected family medicine and interdisciplinary journals. METHODS: A 5-year journal search was conducted to identify original research articles published by family medicine department faculty. Publication productivity of all departments was ranked, and regression analysis was used to identify predictors of publication productivity. RESULTS: The departments leading in publication productivity published more than 25 articles over the 5-year period. The number of faculty and mean dollar value of family medicine department establishment grants were the strongest predictors of publication productivity. When adjusted for departmental size, some departments were found to have high publication productivity per faculty member, even though total numbers of departmental publications were low in comparison to other departments. CONCLUSIONS: This study identified one way of comparing departments in terms of publication productivity. Large departments, and those with more developmental grant support, have the highest publication productivity.

Psychological considerations in colonoscopy.

In summary, psychological issues around the colonoscopy procedure have not yet been fully studied or even formulated. The framework taken here is to consider psychological preconditions to disease, psychological barriers to screening, and ways to maximize the psychological strength of patients when presenting serious diagnoses. Two common themes are present in this review. First, the idea of hopelessness and loss of personal control is present throughout the research in terms of personality predispositions, decisions to seek care, and outcome of disease when present. Physicians need to address the question, what can I do to maximize the hopefulness of this person before, during, and after screening? Are we encouraging an optimistic perspective in the lives of others? The second theme is closely related and that is the critical nature of the patient/physician relationship in all stages of health/illness behavior. It is often the positive, empathic strength of this relationship that affects patient behavior and ultimately the patient's medical outcome. Future research as well as physician self-examination and increased knowledge in this area are truly important. It is in this way that the procedure of colonoscopy truly becomes part of the total patient care.

Hot electron injection from graphene quantum dots to TiO2.

The Shockley-Queisser limit is the maximum power conversion efficiency of a conventional solar cell based on a single semiconductor junction. One approach to exceed this limit is to harvest hot electrons/holes that have achieved quasi-equilibrium in the light absorbing material with electronic temperatures higher than the phonon temperature. We argue that graphene based materials are viable candidates for hot carrier chromophores. Here we probe hot electron injection and charge recombination dynamics for graphene quantum dots (QDs, each containing 48 fused benzene rings) anchored to the TiO2(110) surface via carboxyl linkers. We find ultrafast electron injection from photoexcited graphene QDs to the TiO2 conduction band with time constant τ(i) < 15 fs and charge recombination dynamics characterized by a fast channel (τ(r1) = 80-130 fs) and a slow one (τ(r2) = 0.5-2 ps). The fast decay channel is attributed to the prompt recombination of the bound electron-hole pair across the interface. The slow channel depends strongly on excitation photon energy or sample temperature and can be explained by a "boomerang" mechanism, in which hot electrons are injected into bulk TiO2, cooled down due to electron-phonon scattering, drifted back to the interface under the transient electric field, and recombine with the hole on graphene QDs. We discuss feasibilities of implementing the hot carrier solar cell using graphene nanomaterials.

Hot-electron transfer from semiconductor nanocrystals.

In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO2) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub-50-femtosecond charge separation across the PbSe-TiO2 interface excited coherent vibrations of the TiO2 surface atoms, whose motions could be followed in real time.

Strong electronic coupling in two-dimensional assemblies of colloidal PbSe quantum dots.

Thin films of colloidal PbSe quantum dots can exhibit very high carrier mobilities when the surface ligands are removed or replaced by small molecules, such as hydrazine. Charge transport in such films is governed by the electronic exchange coupling energy (beta) between quantum dots. Here we show that two-dimensional quantum dot arrays assembled on a surface provide a powerful system for studying this electronic coupling. We combine optical spectroscopy with atomic force microscopy to examine the chemical, structural, and electronic changes that occur when a submonolayer of PbSe QDs is exposed to hydrazine. We find that this treatment leads to strong and tunable electronic coupling, with the beta value as large as 13 meV, which is 1 order of magnitude greater than that previously achieved in 3D QD solids with the same chemical treatment. We attribute this much enhanced electronic coupling to reduced geometric frustration in 2D films. The strongly coupled quantum dot assemblies serve as both charge and energy sinks. The existence of such coupling has serious implications for electronic devices, such as photovoltaic cells, that utilize quantum dots.

The Fatty Acid composition of phosphatidylglycerol and sulfoquinovosyldiacylglycerol of higher plants in relation to chilling sensitivity.

The fatty acid composition of phosphatidylglycerol and sulfoquinovosyldiacylglycerol has been measured in the leaves of 27 species of higher plants from six families whose members differed in their degrees of chilling sensitivity. The content of high melting point fatty acids (represented by the sum of hexadecanoic, trans-3-hexadecenoic and octadecanoic acids) in phosphatidylglycerols varied little between members of the same plant family and was not obviously related to the relative chilling sensitivity of members of that family. The saturated fatty acid content (hexadecanoic + octadecanoic acids) of sulfoquinovosyldiacylglycerols also appeared to be characteristic of a plant family, although some exceptions were found. In one case, (Carica papaya) the content of saturated fatty acids in sulfoquinovosyldiacylglycerol was sufficiently high to suggest that this lipid could undergo phase separations above 0 degrees C. It is concluded that the content of high melting point fatty acids in leaf phosphatidylglycerol is not a direct indication of the chilling sensitivity of a plant, but rather may be a reflection of the genetic origin of that plant.

Self-incompatibility in the nitrogen-fixing tree, Acacia retinodes: quantitative cytology of pollen tube growth.

A 10×10 diallel of crosses involving trees in two natural populations of A. retinodes (Leguminosae: Mimosoideae) showed a high level of self-incompatibility, with ISI (Index of Self-Incompatibility) of 0.08. In both self- and cross pollinations, pollen tubes grew through the style to the ovules within 11 h. Tube growth rate is approximately similar in both types of mating: 3.3 to 4.5 µm/min for the first 6 h, and 1.2 to 2.0 µm/min for the succeeding 5 h. Three potential explanations for self incompatibility are proposed: (1) an S-gene controlled system in which pollen tubes are arrested in the nucellus of the ovule; (2) sperm: egg interactions at fertilization and (3) action of post-zygotic lethal genes.

Self-incompatibility in Acacia retinodes: Site of pollen-tube arrest is the nucellus.

In self-incompatible Acacia retinodes Schldl. var. uncifolia J.M. Black there is no inhibition of self pollen tubes before entry into the ovule, but the frequency of fertilized embryo sacs observed after self pollination is only 0.09-0.24 of that observed after outcrossing. Fluorescence- and light-microscope studies of sectioned, squashed or cleared whole ovules indicate that most self pollen tubes are arrested within the first or second layer of cells of the nucellus. The probability that nucellar arrest represents a primitive feature of self-incompatibility is discussed.

Eating attitudes and disorder in young women: a general practice based survey.

A postal survey with selected follow-up interviews was conducted on a complete population of females aged 18-22 registered with two group general practices in Leicestershire. The mailing included the Eating Attitudes Test (EAT) and the Crown-Crisp Experiential Index (CCEI). There was a 70% response rate and 411 usable questionnaires were returned. Twenty-eight respondents (6.8%) produced EAT scores of 30 or more. One case of anorexia nervosa and one of bulimia were identified. Interviews of high EAT scoring subjects revealed several subjects with partial syndromes which failed to fulfil diagnostic criteria for either clinical eating disorder.