Hybrid Capsules via Self‐Assembly of Thermoresponsive and Interfacially Active Bionanoparticle–Polymer Conjugates

New bionanoparticles have been prepared from horse spleen ferritin by grafting thermoresponsive poly(N‐isopropyl acrylamide) (PNIPAAm) and photo‐crosslinkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide (DMIAAm) from the protein surface. The 72 addressable amino groups on the exterior of HSF were modified with N‐hydroxysuccinimide‐activated 2‐bromo‐isobutyrate to form a macro‐initiator for atom transfer radical polymerization, which was performed in water/DMF solutions at low temperature. The modification of the HSF and the presence of the polymer shell were confirmed by size exclusion chromatography (SEC), sodium dodecyl sulfate‐polyacrylamide gel‐electrophoresis, transmission electron microscopy, and scanning force microscopy. The thermoresponsive behavior of the ferritin‐PNIPAAm conjugates was investigated in solution by UV–vis spectroscopy showing a phase transition in the form of a cloud point around 32 °C. Further, dynamic light scattering revealed an increasing hydrodynamic radius around this transition, indicating aggregation of the particles at elevated temperatures which was confirmed by transmission electron microscopy. Initial experiments show that the particles are highly surface active, much more than the individual components alone, which was demonstrated by pendant‐drop interfacial tension measurements. This leads to the fact that they form stable Pickering emulsions, i.e., emulsion droplets decorated with polymer‐modified bionanoparticles which can be cross‐linked successively. This allows the formation of capsules with thermoresponsiveness for controlled release purposes, e.g., in drug delivery.     

Efficient Visible-to-UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting.     

Studies on the formation of lysinomethylalanine and histidinomethylalanine in milk products

From reaction mixtures consisting ofN-acetyldehydroaminobutyric acid methyl ester andN -acetyl-l-lysine orN -acetyl-l-histidine, respectively, distinct amounts of the cross-link amino acidsN -(2-amino-2-carboxy-l-methylethyl)-l-lysine (lysinomethylalanine, LMeAL) andN -(2-amino-2-carboxy-1-methyl-ethyl)-l-histidine (histidinomethylalanine, HMeAL) were isolated via preparative ion-exchange chromatography and identified by¹H- and¹³C-nuclear magnetic resonance. In the amino acid chromatogram, both compounds eluted clearly separated from other basic amino acids. However, neither LMeAL nor HMeAL could be detected in numerous acid hydrolysates of a range of milk products. In model studies, threonine showed a significantly lower tendency for an alkali-induced -elimination reaction compared to serine. The reactivity of the resulting dehydroaminobutyric acid towards nucleophiles was more than tenfold lower as compared to dehydroalanine. Thus, the formation of LMeAL as well as of HMeAL during food processing is negligible.

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Studien zur Bildung von Lysinomethylalanin und Histidinomethylalanin in Milchprodukten

Zusammenfassung Aus Reaktionsansätzen bestehend ausN-Acetyldehydroaminobuttersäurenthylester undN -Acetyl-l-lysin beziehungsweiseN -Acetyl-l-histidin konnten die Crosslink-AminosäurenN -(2-Amino-2-carboxy-1-methyl-ethyl)-l-lysin (Lysinomethylalanin, LMeAL) undN -(2 amino-2-carboxy-2 -methyl-ethyl)-l-histidin (Histidinomethylalanin, HMeAL) durch präparative Ionenaustauschchromatographie isoliert und anschließend durch 1H-und¹³C-NMR identifiziert werden. Das Aminosäurechromatogramm zeigte eine eindeutige Trennung beider Aminosäurederivate von anderen basischen Aminosäuren. Dennoch konnten in einer großen Zahl von Säurehydrolysaten der verschiedensten Milchprodukte weder LMeAL noch HMeAL nachgewiesen werden. In Modelluntersuchungen erfolgte die -Elimination an Threonin im Vergleich zu Serin in einem deutlich geringeren Maße. Die Reaktivität der dabei entstehenden Dehydroaminobuttersäure gegenüber Nucleophilen war mehr als zehnfach geringer als die von Dehydroalanin. Damit kann die Bildung sowohl von LMeAL als auch von HMeAL bei der Verarbeitung von Nahrungsmitteln als vernachlässigbar gering eingeschätzt werden.

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Dedicated to Prof. Dr. W. Baltes on the occasion of his 65th birthday     

CDM potential of solar water heating systems in India

The Clean Development Mechanism (CDM) provides industrialized countries with an incentive to invest in emission reduction projects in developing countries to achieve a reduction in CO₂ emissions at lowest cost that also promotes sustainable development in the host country. Solar water heating systems (SWHs) could be of interest under the CDM because they directly displace greenhouse gas emissions while contributing to sustainable development by reducing local pollutants. However, there are only three solar water heating projects under the CDM so far. An attempt has been made to estimate the CDM potential of SWHs in India in this study. Our estimates indicate that there is a vast theoretical potential of CO₂ mitigation by the use of SWHs in India. The annual CER potential of SWHs in India could theoretically reach 27 million tonnes. Under more realistic assumptions about diffusion of SWHs based on past experiences with the government-run programmes, annual CER volumes by 2012 could reach 4–9 million and 15–22 million by 2020. This would require that the government sets the subsidy level for SWHs at a level that allows them to become viable with the CER revenue. From a macro-economic point of view this makes sense if the sustainability benefits are deemed sufficiently high to warrant promotion of this project type.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Plasmon‐Induced Sub‐Bandgap Photodetection with Organic Schottky Diodes

Organic materials for near‐infrared (NIR) photodetection are in the focus for developing organic optical‐sensing devices. The choice of materials for bulk‐type organic photodetectors is limited due to effects like high nonradiative recombination rates for low‐gap materials. Here, an organic Schottky barrier photodetector with an integrated plasmonic nanohole electrode is proposed, enabling structure‐dependent, sub‐bandgap photodetection in the NIR. Photons are detected via internal photoemission (IPE) process over a metal/organic semiconductor Schottky barrier. The efficiency of IPE is improved by exciting localized surface plasmon resonances, which are further enhanced by coupling to an out‐of‐plane Fabry–Pérot cavity within the metal/organic/metal device configuration. The device allows large on/off ratio (>1000) and the selective control of individual pixels by modulating the Schottky barrier height. The concept opens up new design and application possibilities for organic NIR photodetectors.     

Effect of Drought and Methyl Jasmonate Treatment on Primary and Secondary Isoprenoid Metabolites Derived from the MEP Pathway in the White Spruce Picea glauca

White spruce (Picea glauca) emits monoterpenes that function as defensive signals and weapons after herbivore attack. We assessed the effects of drought and methyl jasmonate (MeJA) treatment, used as a proxy for herbivory, on monoterpenes and other isoprenoids in P. glauca. The emission of monoterpenes was significantly increased after MeJA treatment compared to the control, but drought suppressed the MeJA-induced increase. The composition of the emitted blend was altered strongly by stress, with drought increasing the proportion of oxygenated compounds and MeJA increasing the proportion of induced compounds such as linalool and (E)-β-ocimene. In contrast, no treatment had any significant effect on the levels of stored monoterpenes and diterpenes. Among other MEP pathway-derived isoprenoids, MeJA treatment decreased chlorophyll levels by 40%, but had no effect on carotenoids, while drought stress had no impact on either of these pigment classes. Of the three described spruce genes encoding 1-deoxy-D-xylulose-5-phosphate synthase (DXS) catalyzing the first step of the MEP pathway, the expression of only one, DXS2B, was affected by our treatments, being increased by MeJA and decreased by drought. These findings show the sensitivity of monoterpene emission to biotic and abiotic stress regimes, and the mediation of the response by DXS genes.