Feasibility experiments on time-resolved fluorosensing applied to oil slicks

The introduction of time resolved observations can provide a very penetrating tool in the practice of laser fluorosensing. The investigations have demonstrated a relevance of multispectral, time resolved analysis for oil fingerprinting. By comparative studies on a variety of crude oils and their most significant fractions, it was found that the process of time decay in a composite oil is characterized by a few steps, which are associated with specific components in the medium light range. The average decay times of these pure fractions are markedly differentiated as to absolute values and spectral spread; as a consequence, the corresponding parameters in the resultant crude are quite sensitive to the particular mixture of these components. Measurements of the time response give then a finer discrimination between oil classes, depending on the relative content of certain fractions. Experiments were pursued with an improved fluorosensor facility, in order to test the application of time resolved fluorosensing to remote samples on water

Methyl Hexadecyl Viologen Inclusion in Cucurbit[8]uril: Coexistence of Three Host-Guest Complexes with Different Stoichiometry in a Highly Hydrated Crystal

The host-guest inclusion complexes of cucurbiturils with alkyl viologen have interesting architectures, chemical properties, and potential applications in sensors and nanotechnology. A highly hydrated triclinic crystal of cucurbit[8]uril (CB[8]) complexed by methyl hexadecyl viologen (MVC16) is characterized by the unprecedented coexistence in the crystal of three host-guest complexes with 3:2, 2:2, and 1:1 stoichiometries. In all these complexes, the hook-shaped alkyl chain of the MVC16 is hosted in the CB[8] macrocycles, while the methyl viologen moieties have various environments. In the Z-shaped 3:2 complex, a central CB[8] unit hosts two viologen heads in the cavity, while the 2:2 complex is held together by \u3c0-stacking interactions between two viologen units. In the square 2D tiling crystal packing of CB[8] macrocycles, the same site which favors the dimerization observed in the 2:2 complex is also statistically occupied by a single methyl viologen moiety of the 1:1 complex. The rational interpretation of the crystal structure represented an intriguing challenge, due to the complicated statistical disorder in the alkyl chains hosted in CB[8] units and in the methyl viologen moieties of 2:2 and 1:1 complexes. In contrast with the solution behavior dominated by the 2:1 complex, the coexistence of three host-guest complexes with 3:2, 2:2, and 1:1 ratios highlights the fundamental importance of packing effects in the crystallized supramolecular complexes. Therefore, the crystallization process has permitted us to capture different host-guest systems in a single crystal, revealing a supramolecular landscape in a single photo

The Role of Chain Length in Cucurbit[8]uril Complexation of Methyl Alkyl Viologens

Viologens are among the most studied guests for cucurbit[8]uril (CB[8]) and their complexation is usually driven by bipyridyl core inclusion inside the cavity to maximize both hydrophobic and cation-dipole interactions. The presence of alkyl substituents on the guest alters this complexation mode, switching to aliphatic chain inclusion in U-folded conformation. Herein, we report a thorough study of the influence of the alkyl chain length on the binding mode of methyl alkyl viologens. The chain length of the studied guests was increased by two methylene groups starting from methyl dodecyl viologen (MVC12) to the octadecyl analogue (MVC18). Complexation in water, investigated by NMR spectroscopy and ITC, revealed a clear switch from 1 : 1 to 2 : 1 host/guest stoichiometry moving from 12 to 16 carbon atoms, as a consequence of the chain folding of the major portion of the longer alkyl chain in one CB[8] cavity and the inclusion of the full viologen unit by another host molecule. The CB[8]2.MVC18 complex crystal structure evidences the unprecedented 2 : 1 stoichiometry and quantified in 12 the number of carbon atoms necessary to fill the CB[8] cavity in U-shaped conformation

Tenebrionid secretions and a fungal benzoquinone oxidoreductase form competing components of an arms race between a host and pathogen

Entomopathogenic fungi and their insect hosts represent a model system for examining invertebrate-pathogen coevolutionary selection processes. Here we report the characterization of competing components of an arms race consisting of insect protective antimicrobial compounds and evolving fungal mechanisms of detoxification. The insect pathogenic fungus Beauveria bassiana has a remarkably wide host range; however, some insects are resistant to fungal infection. Among resistant insects is the tenebrionid beetle Tribolium castaneum that produces benzoquinone-containing defensive secretions. Reduced fungal germination and growth was seen in media containing T. castaneum dichloromethane extracts or synthetic benzoquinone. In response to benzoquinone exposure, the fungus expresses a 1,4-benzoquinone oxidoreductase, BbbqrA, induced >40-fold. Gene knockout mutants (ΔBbbqrA) showed increased growth inhibition, whereas B. bassiana overexpressing BbbqrA (Bb::BbbqrAO) displayed increased resistance to benzoquinone compared with wild type. Increased benzoquinone reductase activity was detected in wild-type cells exposed to benzoquinone and in the overexpression strain. Heterologous expression and purification of BbBqrA in Escherichia coli confirmed NAD(P)H-dependent benzoquinone reductase activity. The ΔBbbqrA strain showed decreased virulence toward T. castaneum, whereas overexpression of BbbqrA increased mortality versus T. castaneum. No change in virulence was seen for the ΔBbbqrA or Bb::BbbqrAO strains when tested against the greater wax moth Galleria mellonella or the beetle Sitophilus oryzae, neither of which produce significant amounts of cuticular quinones. The observation that artificial overexpression of BbbqrA results in increased virulence only toward quinone-secreting insects implies the lack of strong selection or current failure of B. bassiana to counteradapt to this particular host defense throughout evolution.Instituto de Investigaciones Bioquímicas de La Plat

Association of plasma neurofilament light chain with glycaemic control and insulin resistance in middle-aged adults

Aims: This study aimed to determine the association of plasma neurofilament light (NfL), a marker of neurodegeneration, with diabetes status and glycaemic parameters in people with normal glycaemia (NG), pre-diabetes (PD) and type 2 diabetes (T2D). Methods: Clinical and descriptive data for the diagnostic groups, NG (n=30), PD (n=48) and T2D (n=29), aged between 40 and 75 years were included in this cross-sectional analysis. Plasma NfL levels were analyzed using the ultra-sensitive single-molecule array (Simoa) platform. Results: A positive correlation was evident between plasma NfL and fasting glucose (r = 0.2824; p = 0.0032). Plasma NfL levels were not correlated with fasting insulin and insulin resistance. Plasma Nfl levels were significantly different across the diabetes groups (T2D \u3e PD \u3e NG, p = 0.0046). Post-hoc analysis indicated significantly higher plasma NfL levels in the T2D [12.4 (5.21) pg/mL] group than in the PD [10.2 (4.13) pg/mL] and NG [8.37 (5.65) pg/mL] groups. The relationship between diabetes status and NfL remained significant after adjusting for age, sex, BMI, HOMA-IR and physical activity (adjusted r2 = 0.271, p = 0.035). Conclusions: These results show biomarker evidence of neurodegeneration in adults at risk or with T2D. Larger sample size and longitudinal analysis are required to better understand the application of NfL in people with risk and overt T2D

A genus at risk: Predicted current and future distribution of all three Lagopus species reveal sensitivity to climate change and efficacy of protected areas

Aim: Cold-adapted species are considered vulnerable to climate change. However, our understanding of how climate-induced changes in habitat and weather patterns will influence habitat suitability remains poorly understood, particularly for species at high latitudes or elevations. Here, we assessed potential future distributions for a climate-sensitive genus, Lagopus, and the effectiveness of protected areas in tracking shifting distributions. Location: British Columbia, Canada. Methods: Using community science observations from 1970 to 2020, we built species distribution models for white-tailed (L. leucura), rock (L. muta) and willow ptarmigan (L. lagopus) across British Columbia, a globally unique region harbouring all three ptarmigan species. We assessed the impact of climate (direct) and climate-induced habitat change (indirect) on potential future distributions of ptarmigan. Results: White-tailed and rock ptarmigan were associated with colder temperatures and tundra-like open habitats and willow ptarmigan with open, shrub habitats. Future projections based on climate and vegetation scenarios indicated marked losses in suitable habitat by the 2080s (RCP +8.5 W/m2), with range declines of 85.6% and 79.5% for white-tailed and rock ptarmigan, respectively, and a lower 61.3% for willow ptarmigan. Predicted current and future suitable habitat occurred primarily outside of current protected areas (67%–82%), yet range size declined at a less pronounced rate within protected areas suggesting a capacity to buffer habitat loss. Main conclusions: Ptarmigan are predicted to persist at higher elevations and latitudes than currently occupied, with the magnitude of elevation shifts consistent with trends observed elsewhere in the Holarctic. Our spatially explicit assessment of potential current and future distributions of ptarmigan species provides the first comprehensive evaluation of climate change effects on the distribution of three congeneric, cold-adapted species with different habitat preferences and life-history traits. We also highlight the potential role of protected areas in preserving suitable future sites for ptarmigan and other climate-sensitive or high-elevation species

Identification of a miRNAs signature associated with exposure to stress early in life and enhanced vulnerability for schizophrenia: New insights for the key role of miR-125b-1-3p in neurodevelopmental processes

Epidemiological and clinical studies have provided evidence for a role of both genetic and environmental factors, such as stressful experiences early in life, in the pathogenesis of Schizophrenia (SZ) and microRNAs (miRNAs) have been suggested to play a key role in the interplay between the environment and our genome. In this study, we conducted a miRNOme analysis in different samples (blood of adult subjects exposed to childhood trauma, brain (hippocampus) of rats exposed to prenatal stress and human hippocampal progenitor cells treated with cortisol) and we identified miR-125b-1-3p as a down-regulated miRNA in all the three datasets. Interestingly, a significant down-regulation was observed also in SZ patients exposed to childhood trauma. To investigate the biological systems targeted by miR-125b-1-3p and also involved in the effects of stress, we combined the list of biological pathways modulated by predicted and validated target genes of miR-125b-1-3p, with the biological systems significantly regulated by cortisol in the in vitro model. We found, as common pathways, the CXCR4 signaling, the G-alpha signaling, and the P2Y Purigenic Receptor Signaling Pathway, which are all involved in neurodevelopmental processes. Our data, obtained from the combining of miRNAs datasets across different tissues and species, identified miR-125b-1-3p as a key marker associated with the long-term effects of stress early in life and also with the enhanced vulnerability of developing SZ. The identification of such a miRNA biomarker could allow the early detection of vulnerable subjects for SZ and could provide the basis for the development of preventive therapeutic strategies

NMR and dc-susceptibility studies of NaVGe2O6

We report the results of measurements of the dc magnetic susceptibility chi(T) and of the 23Na nuclear magnetic resonance (NMR) response of NaVGe2O6, a material in which the V ions form a network of interacting one-dimensional spin S=1 chains. The experiments were made at temperatures between 2.5 and 300 K. The chi(T) data suggest that the formation of the expected low-temperature Haldane phase is intercepted by an antiferromagnetic phase transition at 18 K. The transition is also reflected in the 23Na NMR spectra and the corresponding spin-lattice relaxation rate 1/T1(T). In the ordered phase, 1/T1(T) decreases by orders of magnitude with decreasing temperature, indicating the formation of a gap of the order of 12 K in the magnetic excitation spectrum.Comment: 10 pages, 15 figures; v2 with minor revisions of the tex

A real-world study on unmet medical needs in triptan-treated migraine: Prevalence, preventive therapies and triptan use modification from a large Italian population along two years

Although migraine is a disabling neurological condition that causes important disability, it remains an area of underdiagnosis and undertreatment worldwide. The aim of this study was to depict the burden of the unmet medical needs in migraine treated with triptans in a large Italian population