UV Photoelectron Spectroscopy and Outer Valence Electronic Structure of Dihalobenzenes

The electronic structures of nine dihalobenzenes (C6H4FX; X = Cl, Br, I) have been studied by UV photoelectron spectroscopy (UPS) and assigned by comparison with the reported spectra of monoha-lobenzenes (C6H5X; X = Cl, Br, I). and quantum chemical calculations. Our results show that the fluorine substituent modifies energies of π- and halogen lone pair orbitals to a significant degree depending on its location (topology). We also demonstrate that the inductive effect of fluorine atom on the benzene ring can be readily observed and interpreted

Stimuli-responsive thiol-epoxy networks with photo-switchable bulk and surface properties

In the present work, the versatile nature of o-nitrobenzyl chemistry is used to alter bulk and surface properties of thiol-epoxy networks. By introducing an irreversibly photocleavable chromophore into the click network, material properties such as wettability, solubility and crosslink density are switched locally by light of a defined wavelength. The synthesis of photo-responsive thiol-epoxy networks follows a photobase-catalyzed nucleophilic ring opening of epoxy monomers with photolabile o-nitrobenzyl ester (o-NBE) groups across multi-functional thiols. To ensure temporal control of the curing reaction, a photolatent base is employed releasing a strong amidine-type base upon light exposure, which acts as an efficient catalyst for the thiol epoxy addition reaction. The spectral sensitivity of the photolatent base is extended to the visible light region by adding a selected photosensitizer to the resin formulation. Thus, in the case of photoactivation of the crosslinking reaction the photorelease of the base does not interfere with the absorbance of the o-NBE groups. Once the network has been formed, the susceptibility of the o-NBE groups towards photocleavage reactions is used for a well-defined network degradation upon UV exposure. Sol–gel analysis evidences the formation of soluble species, which is exploited to inscribe positive tone micropatterns by photolithography. Along with the localized tuning of network structure, the irreversible photoreaction is exploited to change the surface wettability of thiol-epoxy networks. The contact angle of water significantly decreases upon UV exposure due to the photo-induced formation of hydrophilic cleavage products enabling the inscription of domains with different surface wettability by photolithography

Seismogenic depth and seismic coupling estimation in the transition zone between Alps, Dinarides and Pannonian Basin for the new Slovenian seismic hazard model

Seismogenic depth and seismic coupling are important inputs into seismic hazard estimates. Although the importance of seismic coupling is often overlooked, it significantly impacts seismic hazard results. We present an estimation of upper and lower seismogenic depth and expected hypocentral depth and seismic coupling in the transition zone between the Alps, Dinarides and Pannonian Basin, characterized by a complex deformation pattern, highly variable crustal thickness, and moderate seismic hazard, supporting the development of the 2021 seismic hazard model of Slovenia. The hazard model was based on three seismic source models: area source model, fault source model and smoothed seismicity (point) source model. We estimated the lower seismogenic depth using seismological and geological data and compared them. The seismological estimate was based on two regional earthquake catalogues prepared for this study. In the area source model, estimates of lower seismogenic depth from seismological data are deeper or equal to the ones derived from geological data, except in one case. In the fault source model, we analysed each fault individually and chose seismological lower depth estimates in 12 among 89 faults as more representative. The seismogenic thickness for each individual fault source was determined for seismic coupling determination. The seismic coupling was assessed by two approaches, i.e. we chose the most trusted value from the literature, and the value determined for each fault individually by using the approach based on the updated regional fault and earthquake data sets. The final estimate of seismic coupling ranges from 0.77 to 0.38. We compared the tectonic moment rate based on long-term slip rate using different values of seismic coupling with the seismic moment rate obtained from the earthquake catalogue. The analysis is done for the whole area, as well as for the individual area zones. The analysis of N–S components of estimated slip for the largest faults in the area of west Slovenia shows that the regional geological and geodetic shortening rates are comparable. The total activity rate of three global seismic source models is compared, which gives up to a 10 % difference. Our results contribute to a better understanding of the seismic activity in the region. The presented approach for seismic coupling estimation can be applied in cases where the total slip rate is given instead of its seismic part and can be used at regional or national level. The approach is also suitable for the cross-border harmonization of the European seismic hazard modelling data.</p

Urine and Fecal 1^1H-NMR metabolomes differ significantly between pre-term and full-term born physically fit healthy adult males

Preterm birth (before 37 weeks gestation) accounts for ~10% of births worldwide and remains one of the leading causes of death in children under 5 years of age. Preterm born adults have been consistently shown to be at an increased risk for chronic disorders including cardiovascular, endocrine/metabolic, respiratory, renal, neurologic, and psychiatric disorders that result in increased death risk. Oxidative stress was shown to be an important risk factor for hypertension, metabolic syndrome and lung disease (reduced pulmonary function, long-term obstructive pulmonary disease, respiratory infections, and sleep disturbances). The aim of this study was to explore the differences between preterm and full-term male participants’ levels of urine and fecal proton nuclear magnetic resonance ($^1$H-NMR) metabolomes, during rest and exercise in normoxia and hypoxia and to assess general differences in human gut-microbiomes through metagenomics at the level of taxonomy, diversity, functional genes, enzymatic reactions, metabolic pathways and predicted gut metabolites. Significant differences existed between the two groups based on the analysis of $^1$H-NMR urine and fecal metabolomes and their respective metabolic pathways, enabling the elucidation of a complex set of microbiome related metabolic biomarkers, supporting the idea of distinct host-microbiome interactions between the two groups and enabling the efficient classification of sampleshowever, this could not be directed to specific taxonomic characteristics

Guided Assembly of Tetramolecular G-Quadruplexes

Nucleic acids are finding applications in nanotechnology as nanomaterials, mechanical devices, templates, and biosensors. G-quadruplex DNA, formed by pi-pi stacking of guanine (G) quartets, is an attractive alternative to regular B-DNA because of the kinetic and thermodynamic stability of quadruplexes. However, they suffer from a fatal flaw: the rules of recognition, i.e., the formation of a G-quartet in which four identical bases are paired, prevent the controlled assembly between different strands, leading to complex mixtures. In this report, we present the solution to this recognition problem. The proposed design combines two DNA elements: parallel-stranded duplexes and a quadruplex core. Parallel-stranded duplexes direct controlled assembly of the quadruplex core, and their strands present convenient points of attachments for potential modifiers. The exceptional stability of the quadruplex core provides integrity to the entire structure, which could be used as a building block for nucleic acid-based nanomaterials. As a proof of principle for the design\u27s versatility, we assembled quadruplex-based 10 structures and visualized them using atomic force and transmission electron microscopy. Our findings pave the way to broader utilization of G-quadruplex DNA in structural DNA nanomaterials