Miracle-dz/UniFAR-FTUs huggingface dataset:
Electronic Structure and Reactivity of Bioinspired Organometallic Iron Complexes Relevant to Small Molecule Activation

This PhD thesis focuses on the development and characterization of new organometallic iron complexes as models for abundant enzymatic systems. The use of a macrocyclic tetracarbene ligand system results in novel features of the organometallic iron complexes compared to literature-known nitrogen-coordinated model compounds. In particular, the strong σ-donating carbene donors induce a destabilization of the d(x²−y²) orbital and thus an increased HOMO−LUMO gap in the oxoiron(IV) complex studied in this thesis. This makes the high-valent oxoiron(IV) compound a unique system which is able to activate weak C–H bonds via the triplet pathway only. Moreover, mixed-valent and high-valent µ-nitridodiiron systems are developed and their properties are studied by a series of analytical techniques including x-ray diffraction and Mossbauer spectroscopy. Furthermore, a complete series of structurally characterized {FeNO}6–8 species is presented. Using a variety of spectroscopic and theoretical methods, the redox processes within this series are identified as largely metal centered. Finally, initial studies toward the development of new hybrid ligand systems combining N-donating and C-donating groups are described.
Optical spectroscopy study of nano- and microstructures fabricated by femtosecond laser pulses on ZnO based systems

The formation of laser induced periodic surface structures (LIPSS) upon irradiation with ultrashort laser pulses at the surface of polycrystalline ZnO based samples, and the potential use of irradiated areas as growth patterns for the production of highly ordered nanostructures have been studied. In particular, pure ZnO, ZnO:Al (5 wt% Al2O3) and ZnO:Mg (5 wt% MgO) samples have been investigated. The surface morphology of the laser fabricated structures depends on the processing parameters, such as energy, number of pulses, repetition rate and laser polarization. Three main types of periodic structures have been formed: LSF (low spatial frequency) and HSF (high spatial frequency) LIPSS and pseudo-spikes (PS). After irradiation, the samples have been used as substrates for vapor–solid growth. It has been found that the growth of micro- and nanostructures in the irradiated regions is much faster than in the non-irradiated ones. Strong differences in the final morphology of the deposited regions are appreciated, not only between irradiated and non-irradiated areas, but also between areas irradiated under different conditions. Scanning electron microscopy (SEM) and cathodoluminescence (CL) measurements at room temperature have been used to monitor the morphology and luminescence properties of the generated structures. For all processed samples, the CL analysis shows a shift of the band edge emission towards higher energies and a lower relative intensity of the defect band in the areas irradiated at higher fluence. The first effect might be attributed to the incorporation of dopants, as already observed for Al and Mg. Yet, the redistribution of defects associated with shallow levels might also be responsible for the observed shift, playing a major role in undoped samples. The decrease in the relative intensity of the defect band can be ascribed to the partial recovery of defects caused by the deposited energy (annealing effect) during the irradiation process.
Interpenetrating networks hydrogels based on hyaluronic acid for drug delivery and tissue engineering

ABSTRACT There are several techniques for preparing hydrogel biomaterials. Among these techniques, preparation of interpenetrating polymer networks hydrogel (IPNs) has been more interested during last years. IPNs are fabricated by the incorporation of monomers or polymeric chains in hydrogel network. Natural polymers such as hyaluronic acids have some advantages such as biocompatibility, biodegradability and non-toxicity. In this review, we would have a brief view to the interpenetrating polymer networks hydrogel based on hyaluronic acids and its applications as a drug delivery system and tissue engineering applications. GRAPHICAL ABSTRACT
Occurrence and control of N-nitrosodimethylamine in water engineering systems

N-nitrosodimethylamine (NDMA) is a typical nitrogen disinfection by-product, which has posed a potential threat to human health during drinking water disinfection. Because of the well-known effects of mutagenesis, carcinogenesis and teratogenesis, the high detection rate in water engineering systems (such as coagulation, membrane filtration and biological systems), and difficulty to remove, it has received wide concern in the field of water engineering systems. The NDMA is a low molecular weight hydrophilic organic substance, which is difficult to remove. Also, the mechanism for NDMA formation is also recognized to be complex, and many steps still needed to be further evaluated. Therefore, the mechanistic knowledge on NDMA formation potential and their removal processes is of particularly interest. Few papers summarize the occurrence and control of NDMA in water engineering systems. It is for this reason that the content of this paper is particularly important for us to understand and control the amount of NDMA thus reducing the threat of disinfection by-products to drinking water. Four parts including the mechanisms for the NDMA formation potential, the factors affecting the NDMA formation potential, the technologies for removal of NDMA are summarized. Finally, some definite suggestions are given.
Effects of vacuum rapid thermal annealing on the electrical characteristics of amorphous indium gallium zinc oxide thin films

We investigated the effects of vacuum rapid thermal annealing (RTA) on the electrical characteristics of amorphous indium gallium zinc oxide (a-IGZO) thin films. The a-IGZO films deposited by radiofrequency sputtering were subjected to vacuum annealing under various temperature and pressure conditions with the RTA system. The carrier concentration was evaluated by Hall measurement; the electron concentration of the a-IGZO film increased and the resistivity decreased as the RTA temperature increased under vacuum conditions. In a-IGZO thin-film transistors (TFTs) with a bottom-gate top-contact structure, the threshold voltage decreased and the leakage current increased as the vacuum RTA temperature increased. As the annealing pressure decreased, the threshold voltage decreased, and the leakage current increased. X-ray photoelectron spectroscopy indicated changes in the lattice oxygen and oxygen vacancies of the a-IGZO films after vacuum RTA. At higher annealing temperatures, the lattice oxygen decreased and.
Temporal and spatial variability in concentrations of phosphorus species under thermal pollution conditions of a dam reservoir – the Rybnik Reservoir case study

Abstract The research objective was to study temporal and spatial relations between specific phosphorus species as well as to examine total phosphorus content in the bottom sediments of an anthropogenic, hypertrophic limnic ecosystem Rybnik Reservoir, functioning under thermal pollution conditions. The chemical extraction procedure for the speciation of bioavailable phosphorus forms was used. It was found that available algae phosphorus was the most dominant phosphorus species in both sediment layers (83%), while the lower share was readily desorbed phosphorus form (0.1%). The phosphorus species concentrations depended on the organic matter concentration. The differences between phosphorus species contents in the upper (5 cm) and lower (15–20 cm) sediment core layers were low. The biologically active sediment layer extended from the sediment surface to at least 20 cm depth of the sediment core. Distributions of the concentrations within the year and at specific sampling points resulted from the variability observed for particular points and transformation intensity. Furthermore in the following study, the reaction rate constant for the increase and decrease in the concentrations of the phosphorus species in sediments was given. It was indicated that the speed of the phosphorus species transformations was affected by the environment temperature. In the heated water discharge zone (water temp. 17–35°C) the concentrations of selected speciation phosphorus forms increased more than in the dam zone (5–25°C). It was also found that the abundance of the bottom sediments with phosphorus species was related to the oblong and transverse asymmetry of reservoir depth.
Herstellung von L-tert-Leucin mit immobilisierten Zellen und verkapselten Enzymen mit Cofaktorregenerierung

L-tert-Leucin ist eine nicht-proteinogene Aminosaure, die in der Medizin als wichtiger Bestandteil zahlreicher potenzieller pharmakologischer Peptid-Wirkstoffe und Arzneimittel (Antitumorreagenzien, antivirale Medikamente, Wirkstoffe gegen Arthritis) sowie in der asymmetrischen Synthese als chirales Auxiliar und chiraler Ligand in enantioselektiven Katalysatoren verwendet wird. L-tert-Leucin kann enzymatisch mit Hilfe der Leucindehydrogenase (LeuDH) aus Trimethylpyruvat hergestellt werden. Zur Regenerierung des Cofaktors NADH wird dabei eine Formiatdehydrogenase genutzt. Um die Produktivitat zu steigern und die Prozesskosten zu senken, ist es sinnvoll, die Enzyme durch Immobilisierung zu stabilisieren und mehrfach wieder einsetzen zu konnen. In dieser Arbeit wurde die Immobilisierung der FDH (Candida boidinii) und LeuDH (Bacillus cereus) in zwei unterschiedlichen Formen - als isolierte Enzyme und in Ganzzellkatalysatoren, die diese Enzyme direkt exprimieren konnen- untersucht. Die isolierten Enzyme konnten erfolgreich in Polyelektrolytkugeln aus Cellulosesulfat und Polydiallyldimethylammioniumchlorid eingeschlossen werden. Durch verschiedene Optimierungsschritte konnten stabile Hohlkugeln hergestellt werden, die eine hohe Restaktivitat (80 %) besasen und im Mehrfacheinsatz keinen Enzymverlust aufwiesen. Als beste Immobilisierungsmethode fur die Ganzzellkatalysatoren erwies der Einschluss in (K+/NH4+)-Carrageenankugeln. Die Restaktivitat lag bei 75 %, die sich auch nach einem 17-tagigen Einsatzes des Immobilisates nicht verringerte. Fur beide Formen - fur den Ganzzellkatalysator und fur die isolierten Enzyme- wurden daher sehr gute Immobilisierungssysteme gefunden werden, welche einerseits kostengunstig und einfach herzustellen und leicht zu handhaben sind und auserdem eine hohe Restaktivitat und eine gute Langzeitaktivitat besitzen.
The functional and molecular consequences of oxidation in the skeletal muscle myofilament.

It is becoming increasingly evident that redox state leading to post-translational modifications of structural proteins, enzymes and ion channels can cause activation or inhibition of cellular function (Andrade et al., 1998a, Jackson, 2008, Kelly et al., 1996). While low levels of nitric oxide (NO) synthesised by endothelial and neuronal nitric oxide synthase have been shown to provide a beneficial effect to tissues, the elevated release of NO accompanying inflammation has a detrimental effect, resulting in dysfunction (Khanna et al., 2005). We investigated the functional consequence and molecular substrate of NO and another potentially harmful reactive oxygen species, H ₂O ₂, on the skeletal muscle myofilament. In a rat model we used functional myography of demembranated single fast- and slow-twitch skeletal muscle fibers to examined the consequence of the addition of the free radical NO and reactive oxygen species H₂O₂ on the Ca²⁺ sensitivity of the myofilament. The reversibility of oxidative modifications following NO or H ₂O ₂ treatment was examined using the general anti-oxidant dithiothreitol. Isoelectric focusing combined with SDS-PAGE separation of proteins investigated the post-translational modification of free-radical exposed myofilament proteins. Molecular substitution of endogenous troponin C (TnC) with WT cardiac/slow TnC or C84S TnC, incapable of being oxidized at Cys84, investigated the molecular and functional consequence of oxidation of TnC at Cys84. Exposure of fast-twitch muscle fibers to NO resulted in a decrease in Ca²⁺ sensitivity, while H ₂O ₂ had the opposite effect, increasing Ca²⁺ sensitivity. In contrast, slow-twitch fibers were insensitive to both NO and H ₂O ₂. Following myofilament exposure to NO (~2 uM) proteomic analysis revealed that many proteins underwent post-translational modification, including myosin light chain (LC ₂₀) and TnC. Molecular substitution of endogenous fast-twitch TnC with WT-cardiac/slow TnC demonstrated a similar sensitivity to NO as WT skeletal muscle. In contrast TnC, non-oxidizable at Cys84, rendered fast-twitch skeletal muscle insensitive to NO. Many myofilament proteins, including myosin light chains were identified as being post-translationally modified by NO exposure, however, molecular substitution experiments clearly identify TnC, specifically residue Cys84 as the functional substrate responsible for fast-twitch skeletal muscle sensitivity to NO. Although slow-twitch muscle contains the same isoform of TnC, it was insensitive to NO. This suggests that slow-twitch muscle may have a greater capacity for anti-oxidant defense than fast-twitch muscle. The contrasting increase in Ca²⁺ sensitivity following H ₂O ₂ to the decline caused by NO demonstrates that not all oxidative molecules act alike, possibly targeting differing substrates and causing differing post-translational modifications.
Tunable luminescence from two dimensional BCNO nanophosphor for high-contrast cellular imaging

Rare-earth free and biocompatible two dimensional carbon based boron oxynitride (2D BCNO) nanophosphors were synthesized using facile auto-combustion of inexpensive compounds such as urea, boric acid and polyethylene glycol at ambient atmosphere and relatively low temperatures. The surface morphology and microstructure images indicate that the nanophosphor has 2D layered structures and analogous mixed hexagonal lattices of boron nitride (BN) and graphene (C). The nanophosphor exhibits a single, distinct and broad photoluminescence emission and this emission colour can be easily tuned from violet to deep red by varying the amount of boron/carbon content. The time-resolved and photoluminescence spectroscopic results indicate that B–O act as luminescence centers, which are responsible for the tunable luminescent properties while carbon impurities induce energy levels in the band gap of 2D BCNO nanophosphors. These tunable and biocompatible luminescent nanophosphors are used for in vitro high-contrast cellular imaging of HeLa cells derived from human cervical cancer cells as well as in vivo imaging in C57BL/6J mice. Hence, these novel multi-colour emitting nanophosphors provide a paradigm shift in rare-earth free biocompatible nanoprobes for next generation high-contrast in vitro and in vivo imaging applications.
Anodic dissolution growth of metal–organic framework HKUST-1 monitored via in situ electrochemical atomic force microscopy

In situ electrochemical atomic force microscopy (ec-AFM) is utilised for the first time to probe the initial stages of metal–organic framework (MOF) coating growth via anodic dissolution. Using the example of the Cu MOF HKUST-1, real time surface analysis is obtained that supports and verifies many of the reaction steps in a previously proposed mechanism for this type of coating growth. No evidence is observed however for the presence or formation of Cu2O, which has previously been suggested to be both key for the formation of the coating and a potential explanation for the anomalously high adhesion strength of coatings obtained via this methodology. Supporting in situ electrochemical Raman spectroscopy also fails to detect the presence of any significant amount of Cu2O before or during the coating's growth process.
Resistance of industrial nickel-containing methanation catalysts to the poisoning by organic carbon dioxide absorbents

We report the results of studies on the influences of the organic carbon dioxide absorbent – aqueous solution of activated methyldiethanolamine (MDEA) – on the physico-chemical and mechanical characteristics of nickel-alumina catalyst NIAP-07-01 (NKM-1) and cement-containing catalysts NIAP-07-07 (NKM-7), Meth-134 and Meth-135 for the hydrogenation of carbon oxide (methanation). It is established that for the nickel-alumina and nickel-cement-containing catalysts subjected to activated methyldiethanolamine (MDEA) it’s possible to restore their strength and catalytic properties. In order to increase the time of operation of the methanator it is recommended to apply a new Nickel cement-containing catalyst NIAP-07-07 (NKM-7), which can be produced as tablets, rings or extrudates.
Keeping community groups and activities going - Sustainable Community Interventions for people affected by Dementia: Recommendations for practice from the SCI-Dem Project

Running a community-based group or activity for people affected by dementia can be challenging. Keeping a group or activity going long-term can be even more so – especially in a climate where community awareness and resources can vary dramatically from place to place; where funding is hard to come by and often short term; and where there is no standard model of formal support for such groups, applied consistently, across the country. The SCI-Dem review has gathered together information from various sources about the common problems that face regularly-meeting groups and activities for people living with dementia (or people supporting someone who is). By doing so, we can share possible tips, strategies and good practices from this review that might help a community group or activity to keep going long-term, after getting established. This booklet outlines recommendations, built upon the information we have found. This booklet aims to help those in practice (whether that’s planning for a group or activity, managing one, running one day-to-day or supporting one through volunteering). There is a separate booklet of recommendations aimed at funders/commissioners and policy makers. The information these recommendations are based upon was gathered and put together from dozens of sources of all types: research studies and papers, evaluation reports, magazine articles, info guides and how-to booklets, conference talks, even videos and artistic output from some groups. All examples given are fictional, but based upon what we found. We hope that what we have found resonates with your group or activity and that you find something useful and informative in these pages, so that the important and much-needed work of such groups can be better helped to sustain long term.
IDENTIFICATION OF POTENTIAL SALMONELLA TYPHI BETA-LACTAMASE TEM 1 INHIBITORS USING PEPTIDOMIMETICS, VIRTUAL SCREENING, AND MOLECULAR DYNAMICS SIMULATIONS

Objective: The purpose of this study was to identify a potential peptidomimetic S. typhi Beta-lactamase TEM 1 inhibitor to tackle the antibiotic resistance among S. typhi . Methods: The potential peptidomimetic inhibitor was identified by in silico docking of the small peptide WFRKQLKW with S. typhi Beta-lactamase TEM 1. The 3D coordinate geometry of the residues of small peptide interacting with the active site of the receptor was generated and mimics were identified using PEP: MMs: MIMIC server. All the identified mimics were docked at the active site of the receptor using Autodock 4.2 and the best-docked complex was selected on the basis of binding energy and number of H-bonds. The complex was then subjected to molecular dynamics simulations of 30 ns using AMBER 12 software package. The stereochemical stability of the Beta-lactamase TEM 1-WFRKQLKW complex was estimated with the help of Ramachandran plot using PROCHECK tool. Results: In the present study, a new potential peptidomimetic inhibitor (ZINC05839264) of Beta-lactamase TEM 1 has been identified based on antimicrobial peptide WFRKQLKW by virtual screening of the MMsINC database. The docking and molecular simulation studies revealed that the mimic binds more tightly to the active site of the receptor than the peptide. The Ramachandran plot also shows that the Beta-lactamase TEM 1-mimic complex is stereo chemically more stable than Beta-lactamase TEM 1-WFRKQLKW complex as more number of residues (93.6%) are falling under the core region of the plot in case of the former. Conclusion: The study shows that the peptidomimetic compound can act as a potential inhibitor of S. typhi Beta-lactamase TEM 1 and further it can be developed into more effective therapeutic to tackle the problem of antibiotic resistance.
A review of the status of e-government implementation in Kenya

Rationale of Study – Successful implementation of today’s government operations requires effective policy making and system monitoring through relevant data and information. E-government offers an increased portfolio of public services in a cost-effective and efficient manner hence enabling governments to reinvent the ways through which they interact with citizens, private sector, employees and other stakeholders. Consequently, many countries have invested significant resources into collecting, processing, integrating, analysing and reporting data through information and communication technologies (ICTs). The aim of this paper is to review the status of e-government implementation in Kenya. Methodology – In order to measure the status of e-government, two indexes were used: 1) E-government Development Index (EGDI); and 2) Network Readiness Index (NRI). The study adopted a theoretical approach by conducting a review of literature on e-government in Kenya. Fit-Viability theory was used to assess the capacity of the Government of Kenya to roll out viable e-services to its citizens. Findings – The findings indicate that Kenya has made significant progress in e-government implementation. The benefits of e-government implementation in Kenya currently include enhanced e-participation, accountability, planning, monitoring and information sharing. However, challenges such as inadequate infrastructure, policy and human capital development hamper the effectiveness of e-government projects in Kenya. These challenges may be surmounted through increased digital inclusivity, enhanced broadband connectivity, strengthened staff ICT skills and openness to new technologies. Implications – The findings of this study may be used by the Government of Kenya to plan, roll out and monitor e-government projects with a view to enhancing their success and impact. Originality – A number of studies on e-government in Kenya exist. Their focus has been on the factors affecting the effective implementation of e-government in Kenya. Periodical assessment of the status of the projects is lacking. This study seeks to fill this gap.
Process for the purification and/or isolation of biologically active granulocyte colony stimulating factor

The method of the present invention relates to granulocyte colony stimulating activity for biological separation factor (G-CSF) of which can be fixed by using such metal affinity monomeric G-CSF molecule chromatography properly folded biologically active and improperly folded biologically active monomeric form of oligo - or multimeric G-CSF may also be separated and separating the aggregated form with G-CSF molecule; if desired, then the entire process, the method of the present invention It can be advantageously carried out under natural conditions. Higher purity can be obtained G-CSF 95% of the biological activity. Then, preferably with only two additional chromatographic steps - cation exchange chromatography and gel filtration chromatography to remove traces of impurities. Overall process may be prepared G-CSF purity of more than 99% higher yield. The method is particularly suitable for the industrial production of G-CSF.