Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.     

Luminescent Amphiphilic Aminoglycoside Probes to Study Transfection

We report the characterization of amphiphilic aminoglycoside conjugates containing luminophores with aggregation-induced emission properties as transfection reagents. These inherently luminescent transfection vectors are capable of binding plasmid DNA through electrostatic interactions; this binding results in an emission “on” signal due to restriction of intramolecular motion of the luminophore core. The luminescent cationic amphiphiles effectively transferred plasmid DNA into mammalian cells (HeLa, HEK 293T), as proven by expression of a red fluorescent protein marker. The morphologies of the aggregates were investigated by microscopy as well as ζ-potential and dynamic light-scattering measurements. The transfection efficiencies using luminescent cationic amphiphiles were similar to that of the gold-standard transfection reagent Lipofectamine® 2000.     

CYP154C5 Regioselectivity in Steroid Hydroxylation Explored by Substrate Modifications and Protein Engineering**

CYP154C5 from Nocardia farcinica is a P450 monooxygenase able to hydroxylate a range of steroids with high regio- and stereoselectivity at the 16α-position. Using protein engineering and substrate modifications based on the crystal structure of CYP154C5, an altered regioselectivity of the enzyme in steroid hydroxylation had been achieved. Thus, conversion of progesterone by mutant CYP154C5 F92A resulted in formation of the corresponding 21-hydroxylated product 11-deoxycorticosterone in addition to 16α-hydroxylation. Using MD simulation, this altered regioselectivity appeared to result from an alternative binding mode of the steroid in the active site of mutant F92A. MD simulation further suggested that the entrance of water to the active site caused higher uncoupling in this mutant. Moreover, exclusive 15α-hydroxylation was observed for wild-type CYP154C5 in the conversion of 5α-androstan-3-one, lacking an oxy-functional group at C17. Overall, our data give valuable insight into the structure–function relationship of this cytochrome P450 monooxygenase for steroid hydroxylation.     

Estimation in Random Coefficient Autoregressive Models

Abstract. We propose the quasi‐maximum likelihood method to estimate the parameters of an RCA(1) process, i.e. a random coefficient autoregressive time series of order 1. The strong consistency and the asymptotic normality of the estimators are derived under optimal conditions.     

A novel technique for the preparation of secondary fatty amides

A technique for the synthesis of monosubstituted fatty amides at low temperature and ambient pressure was developed. This method involved the condensation of an amine with a triacylglycerol. The primary amine (ethyl,n-butyl,n-hexyl andn-octyl were tested) acted as reagent and solvent for the fatty substrates. No additional organic solvent or catalyst was added. Tallow, vegetable oils and fish oil all served well as substrates, as did pure tripalmitin. The rate of amidation was dependent upon temperature and the ratio of fat to amine. In a series of experiments conducted with tallow andn-butylamine at a fat:amine molar ratio of 1:16, amidation could be carried out at 20°C, producingn-butyltallowamide in 83% yield in 24 hr. When the fat:amine molar ratio was reduced to 1:8, and the temperature raised to 45°C, the amide yield was 87.6% in 24 hr. When the reaction was carried out at the boiling point ofn-butylamine (78°C) and at a fat:amine ratio of 1:8, the amide yield was 93.2% in 4 hr. The reaction progressed more rapidly with higher molecular weight amines. The identity and purity of the amides was assessed by thin-layer chromatography and confirmed by elemental analyses and infrared and C¹³ nuclear magnetic resonance spectroscopy.     

Preparation and characterization of surfactant‐free stimuli‐sensitive microgel dispersions

A surfactant‐free method to produce responsive polymer microgels is introduced. As an example, poly(methacrylic acid) hydrogels with varying crosslinking density have been synthesized in bulk and then chopped using a high shear mechanical cutter to form microgel particles dispersed in water. The mechanical cutting technique enables the concentration and particle size distribution of the microgel suspensions to be easily controlled, therefore making the rheology of the suspensions tuneable. The particle size distribution of the dispersions, characterized using light scattering, was dependent on the speed and duration of mechanical cutting. The particle size distribution also depended on the degree of crosslinking of the hydrogel. The higher the crosslinking density, the lower the average mean diameter of the resulting microgel particles. The lower the crosslinking density of the hydrogel, the larger the difference between the maximum and minimum particle size. The time to complete swelling of the particles upon change in pH was measured to be up to 45 s, depending on the particle size. The rheology of the resulting suspensions as a function of pH was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 104: 1912–1919, 2007     

Benchmarking Fluvial Dynamics for Process‐Based River Restoration: the Upper Rhine River (1816–2014)

Multi‐temporal analysis of river‐floodplain processes is a key tool for the identification of reference conditions or benchmarks and for the evaluation of deviations or deficits as a basis for process‐based river restoration in large modified rivers. This study developed a methodology for benchmarking fluvial processes at river segment level, focusing on those interrelations between morphodynamics (aggradation, erosion, channel shift) and vegetation succession (initial, colonization, transition) that condition habitat structure. Habitat maps of the free‐flowing Upper Rhine River downstream from Iffezheim dam (France–Germany border) were intersected with a geographic information system‐based approach. Patches showing trajectories of anthropization, changeless, progression and regression allowed for the identification of natural and human‐induced processes over almost 200 years. Before channelization, the riverine system was characterized by a shifting habitat mosaic with natural heterogeneity, high degree of surface water connectivity and equilibrium between progression and regression processes. On the other hand, the following 175 years of human interventions led to severe biogeomorphologic deficits evidenced by loss of natural processes and habitat heterogeneity, hydrological disconnection between the river and its floodplain and imbalance of progression versus regression dynamics. The main driving forces of change are found in hydromorphological impacts (channelization, regulation and hydropower plant construction). Regression processes are now almost absent and have to be the objective of process‐based river restoration measures for the studied river‐floodplain system. A sustainable view on water management and river restoration should aim at a more resilient riverine system by balancing the recovery of natural processes with societal needs. Copyright © 2016 John Wiley & Sons, Ltd.     

Scalable,low complexity,and fast greedy scheduling heuristics for highly heterogeneous distributed computing systems

For heterogeneous distributed computing systems, important design issues are scalability and system optimization. Given such systems, it is crucial to develop low computational complexity algorithms to schedule tasks in a manner that exploits the heterogeneity of the resources and applications. In this paper, we report and evaluate three scalable, and fast scheduling heuristics for highly heterogeneous distributed computing systems. We conduct a comprehensive performance evaluation study using simulation. The benchmarking outlines the performance of the schedulers, representing scalability, makespan, flowtime, computational complexity, and memory utilization. The set of experimental results shows that our heuristics perform as good as the traditional approaches, for makespan and flowtime, while featuring lower complexity, lower running time, and lower used memory. The experimental results also detail the various scenarios under which certain algorithms excel and fail.     

Geschäftsmodelle

The business model concept, although a relatively new topic for research, has garnered growing attention over the past decade. Whilst it has been robustly defined, the concept has so far attracted very little substantive research. In the context of the wide-spread digitization of businesses and society at large, the logic inherent in a business model has become critical for business success and, hence, a focus for academic inquiry. The business model concept is identified as the missing link between business strategy, processes, and Information Technology (IT). The authors argue that the BISE community offers distinct and unique competencies (e.g., translating business strategies into IT systems, managing business and IT processes, etc.) that can be harnessed for significant research contributions to this field. Within this research gap three distinct streams are delineated, namely, business models in IT industries, IT enabled or digital business models, and IT support for developing and managing business models. For these streams, the current state of the art, suggest critical research questions, and suitable research methodologies are outlined.     

Hydrolytic degradation of ionically cross-linked polyphosphazene microspheres

The hydrolytic degradation of gel microspheres based on calcium cross-linked phosphazene polyelectrolytes, poly[di(carboxylatophenoxy)phosphazene] (PCPP) and poly[(carboxylatophenoxy) (glycinato)phosphazene] (PCGPP), was investigated. These microspheres are of importance as carriers in protein and cell encapsulation. Both PCPP and PCGPP ionotropic polyphosphazene hydrogels are degradable in an aqueous environment (pH 7.4, 37°C). The degradation rates can be increased by incorporation of hydrolysis sensitive glycinato groups as the pendant structures in the polymer (PCGPP). Hydrolysis of these polymer hydrogels led to low molecular weight (<1,000 Da) products. The erosion and molecular weight profiles varied also according to the molecular weight of the polyphosphazene constituting the gel beads. Another approach to affect the degradation rates consists of coating microspheres with poly-L -lysine. Ionotropic polyphosphazene hydrogels have potential as biodegradable devices for controlled drug delivery systems. © 1994 John Wiley & Sons, Inc.