Strong overtones and combination bands in ultraviolet resonance Raman spectroscopy

Ultraviolet resonance Raman spectroscopy is carried out using a continuous wave frequency-doubled argon ion laser operated at 229, 244, and 257 nm in order to characterize the overtones and combination bands for several classes of organic compounds in liquid solutions. Contrary to what is generally anticipated, for molecules such as pyrene and anthracene, strong overtones and combination bands can show up; it is demonstrated that their intensity depends critically on the applied laser wavelength. If the excitation wavelength corresponds with a purely electronic transition--this applies to a good approximation for 244-nm excitation in the case of pyrene and for 257-nm excitation in the case of anthracene--mostly fundamental vibrations (up to 1700 cm(-1)) are observed. Overtones and combination bands are detected but are rather weak. However, if the laser overlaps with the vibronic region--as holds for 229- and 257-nm excitation for pyrene and 244-nm excitation for anthracene--very strong bands are found in the region 1700-3400 cm(-1). As illustrated for pyrene at 257 nm, all these bands can be assigned to first overtones or binary combinations of fundamental vibrations. Their intensity distribution can roughly be simulated by multiplying the relative intensities of the fundamental bands. Significant bands can also be found in the region 3400-5000 cm(-1), corresponding with second overtones and ternary combinations. It is shown that these findings are not restricted to planar and rigid molecules with high symmetry. Substituted pyrenes exhibit similar effects, and relatively strong overtones are also observed for adenosine monophosphate and for abietic acid. The reasons for these observations are discussed, as well as the potential applicability for analytical purposes.     

Quantum dots with a paramagnetic coating as a bimodal molecular imaging probe

MRI detectable and targeted quantum dots were developed. To that aim, quantum dots were coated with paramagnetic and pegylated lipids, which resulted in a relaxivity, r(1), of nearly 2000 mM(-1)s(-1) per quantum dot. The quantum dots were functionalized by covalently linking alphavbeta3-specific RGD peptides, and the specificity was assessed and confirmed on cultured endothelial cells. The bimodal character, the high relaxivity, and the specificity of this nanoparticulate probe make it an excellent contrast agent for molecular imaging purposes.     

Kinetic and stoichiometric characterisation of streptavidin-binding aptamers

Aptamers are oligonucleotide ligands that are selected for high-affinity binding to molecular targets. Only limited knowledge relating to relations between structural and kinetic properties that define aptamer-target interactions is available. To this end, streptavidin-binding aptamers were isolated and characterised by distinct analytical techniques. Binding kinetics of five broadly similar aptamers were determined by surface plasmon resonance (SPR); affinities ranged from 35-375 nM with large differences in association and dissociation rates. Native mass spectrometry showed that streptavidin can accommodate up to two aptamer units. In a 3D model of one aptamer, conserved regions are exposed, strongly suggesting that they directly interact with the biotin-binding pockets of streptavidin. Mutational studies confirmed both conserved regions to be crucial for binding. An important result is the observation that the most abundant aptamer in our selections is not the tightest binder, emphasising the importance of having insight into the kinetics of complex formation. To find the tightest binder it might be better to perform fewer selection rounds and to focus on post-selection characterisation, through the use of complementary approaches as described in this study.     

Fermentation, degradation and microbial nitrogen partitioning for three forage colour phenotypes within anthocyanidin-accumulating Lc-alfalfa progeny

BACKGROUND: Alfalfa has the disadvantage of having a rapid initial rate of protein degradation, which results in pasture bloat, low efficiency of protein utilisation and excessive nitrogen (N) pollution into the environment for cattle. Introducing a gene that stimulates the accumulation of monomeric/polymeric anthocyanidins might reduce the ruminal protein degradation rate (by fixing protein and/or direct interaction with microbes) and additionally reduce methane emission. The objectives of this study were to evaluate in vitro fermentation, degradation and microbial N partitioning of three forage colour phenotypes (green, light purple‐green (LPG) and purple‐green (PG)) within newly developed Lc‐progeny and to compare them with those of parental green non‐transgenic (NT) alfalfa. RESULTS: PG‐Lc accumulated more anthocyanidin compared with Green‐Lc (P < 0.05), with LPG‐Lc intermediate. Volatile fatty acids and potentially degradable dry matter (DM) and N were similar among the four phenotypes. Gas, methane and ammonia accumulation rates were slower for the two purple‐Lc phenotypes compared with NT‐alfalfa (P < 0.05), while Green‐Lc was intermediate. Effective degradable DM and N were lower in the three Lc‐phenotypes (P < 0.05) compared with NT‐alfalfa. Anthocyanidin concentration was negatively correlated (P < 0.05) with gas and methane production rates and effective degradability of DM and N. CONCLUSION: The Lc‐alfalfa phenotypes accumulated anthocyanidin. Fermentation and degradation parameters indicated a reduced rate of fermentation and effective degradability for both purple anthocyanidin‐accumulating Lc‐alfalfa phenotypes compared with NT‐alfalfa. Copyright © 2012 Society of Chemical Industry     

Enhanced hot-carrier cooling and ultrafast spectral diffusion in strongly coupled PbSe quantum-dot solids

PbSe quantum-dot solids are of great interest for low cost and efficient photodetectors and solar cells. We have prepared PbSe quantum-dot solids with high charge carrier mobilities using layer-by-layer dip-coating with 1,2-ethanediamine as substitute capping ligands. Here we present a time and energy resolved transient absorption spectroscopy study on the kinetics of photogenerated charge carriers, focusing on 0-5 ps after photoexcitation. We compare the observed carrier kinetics to those for quantum dots in dispersion and show that the intraband carrier cooling is significantly faster in quantum-dot solids. In addition we find that carriers diffuse from higher to lower energy sites in the quantum-dot solid within several picoseconds.     

Anomalous independence of multiple exciton generation on different group IV-VI quantum dot architectures

Multiple exciton generation (MEG) in PbSe quantum dots (QDs), PbSe(x)S(1-x) alloy QDs, PbSe/PbS core/shell QDs, and PbSe/PbSe(y)S(1-y) core/alloy-shell QDs was studied with time-resolved optical pump and probe spectroscopy. The optical absorption exhibits a red-shift upon the introduction of a shell around a PbSe core, which increases with the thickness of the shell. According to electronic structure calculations this can be attributed to charge delocalization into the shell. Remarkably, the measured quantum yield of MEG, the hot exciton cooling rate, and the Auger recombination rate of biexcitons are similar for pure PbSe QDs and core/shell QDs with the same core size and varying shell thickness. The higher density of states in the alloy and core/shell QDs provide a faster exciton cooling channel that likely competes with the fast MEG process due to a higher biexciton density of states. Calculations reveal only a minor asymmetric delocalization of holes and electrons over the entire core/shell volume, which may partially explain why the Auger recombination rate does not depend on the presence of a shell.     

Analysis of the inhibition of food spoilage yeasts by vanillin

The antimicrobial potential of vanillin, the major component of vanilla flavour, was examined against the growth of three yeasts associated with food spoilage, Saccharomyces cerevisiae, Zygosaccharomyces bailii and Zygosaccharomyces rouxii. Minimum inhibitory concentration (MIC) values of 21, 20 and 13 mM vanillin were determined for the three yeast strains, respectively. The observed inhibition was found to be biostatic. During fermentation, the bioconversion of sub-MIC levels of vanillin in the culture medium was demonstrated. The major bioconversion product was identified as vanillyl alcohol, however low levels of vanillic acid were also detected. Neither the vanillyl alcohol nor the vanillic acid was found to be antagonistic to yeast cell growth. The results indicate the importance of the aldehyde moiety in the vanillin structure regarding its antimicrobial activity and that the bioconversion of vanillin could be advantageous for the yeasts, but only at levels below MIC. These bioconversion activities, presumably catalysed by non-specific dehydrogenases, were shown to be expressed constitutively. It was observed that increased vanillin concentrations inhibited its own bioconversion suggesting that the activity required intact cells with metabolic capacity.     

Dairy herd management practices that impact nitrogen utilization efficiency

Improving the efficiency of feed N utilization by dairy cattle is the most effective means to reduce nutrient losses from dairy farms. The objectives of this study were to quantify the impact of different management strategies on the efficiency of feed N utilization for dairy farms in the Chesapeake Bay Drainage Basin. A confidential mail survey was completed in December 1998 by 454 dairy farmers in PA, MD, VA, WV, and DE. Nitrogen intake, urinary and fecal N, and efficiency of feed N utilization was estimated from survey data and milk analysis for each herd. Average efficiency of feed N utilization for milk production by lactating dairy cows (N in milk/N in feed x 100) was 28.4% (SD = 3.9). On average, farmers fed 6.6% more N than recommended by the National Research Council, resulting in a 16% increase in urinary N and a 2.7% increase in fecal N. Use of monthly milk yield and component testing, administration of bovine somatotropin (bST), and extending photoperiod with artificial light each increased efficiency of feed N utilization by 4.2 to 6.9%, while use of a complete feed decreased efficiency by 5.6%. Increased frequency of ration balancing and more frequent forage nutrient testing were associated with higher milk production, but not increased N utilization efficiency. Feeding protein closer to recommendations and increasing production per cow both contributed to improving efficiency of feed N utilization.