Cucurbitnurils (CBn, n = 7, 8) serve as artificial receptors for steroids (21 tested), including the hormones testosterone and estradiol as well as steroidal drugs. Fluorescence displacement ...titrations and isothermal titration calorimetry (ITC) provided up to nanomolar binding affinities in aqueous solution for these hydrophobic target molecules, exceeding the values of known synthetic receptors. Remarkable binding selectivities, even for homologous steroid pairs, were investigated in detail by NMR, X-ray crystal diffraction, ITC, and quantum chemical calculations. Notably, the CBn•steroid complexes are stable in water and buffers, in artificial gastric acid, and even in blood serum. Numerous applications have been demonstrated, which range from the solubility enhancement of the steroids in the presence of the macrocycles (up to 100 times, for drug delivery) and the principal component analysis of the fluorescence responses of different CBn•reporter dye combinations (for differential sensing of steroids) to the real-time monitoring of chemical conversions of steroids as substrates (for enzyme assays).
ABSTRACT
How elliptical galaxies form is a key question in observational cosmology. While the formation of massive ellipticals is strongly linked to mergers, the low mass (M⋆/M⊙ < 109.5) regime ...remains less well explored. In particular, studying elliptical populations when they are blue, and therefore rapidly building stellar mass, offers strong constraints on their formation. Here, we study 108 blue low-mass ellipticals (which have a median stellar mass of 108.7 M⊙) at z < 0.3 in the COSMOS field. Visual inspection of extremely deep optical HSC images indicates that less than 3 per cent of these systems have visible tidal features, a factor of 2 less than the incidence of tidal features in a control sample of galaxies with the same distribution of stellar mass and redshift. This suggests that the star formation activity in these objects is not driven by mergers or interactions but by secular gas accretion. We combine accurate physical parameters from the COSMOS2020 catalogue, with measurements of local density and the locations of galaxies in the cosmic web, to show that our blue ellipticals reside in low-density environments, further away from nodes and large-scale filaments than other galaxies. At similar stellar masses and environments, blue ellipticals outnumber their normal (red) counterparts by a factor of 2. Thus, these systems are likely progenitors of not only normal ellipticals at similar stellar mass but, given their high star formation rates, also of ellipticals at higher stellar masses. Secular gas accretion therefore likely plays a significant (and possibly dominant) role in the stellar assembly of elliptical galaxies in the low-mass regime.
ABSTRACT
We use a complete, unbiased sample of 257 dwarf (10$^{8}\, {\rm M}_{\odot } \lt M_{\rm {\star }} \lt 10^{9.5}\, {\rm M}_{\odot }$) galaxies at z < 0.08, in the COSMOS field, to study the ...morphological mix of the dwarf population in low-density environments. Visual inspection of extremely deep optical images and their unsharp-masked counterparts reveals three principal dwarf morphological classes. 43 per cent and 45 per cent of dwarfs exhibit the traditional ‘early-type’ (elliptical/S0) and ‘late-type’ (spiral) morphologies, respectively. However, 10 per cent populate a ‘featureless’ class, that lacks both the central light concentration seen in early-types and any spiral structure – this class is missing in the massive-galaxy regime. 14 per cent, 27 per cent, and 19 per cent of early-type, late-type, and featureless dwarfs respectively show evidence for interactions, which drive around 20 per cent of the overall star formation activity in the dwarf population. Compared to their massive counterparts, dwarf early-types show a much lower incidence of interactions, are significantly less concentrated and share similar rest-frame colours as dwarf late-types. This suggests that the formation histories of dwarf and massive early-types are different, with dwarf early-types being shaped less by interactions and more by secular processes. The lack of large groups or clusters in COSMOS at z < 0.08, and the fact that our dwarf morphological classes show similar local density, suggests that featureless dwarfs in low-density environments are created via internal baryonic feedback, rather than by environmental processes. Finally, while interacting dwarfs can be identified using the asymmetry parameter, it is challenging to cleanly separate early and late-type dwarfs using traditional morphological parameters, such as ‘CAS’, M20, and the Gini coefficient (unlike in the massive-galaxy regime).
Transcriptionally active loci are particularly prone to breakage and mounting evidence suggests that DNA Double-Strand Breaks arising in active genes are handled by a dedicated repair pathway, ...Transcription-Coupled DSB Repair (TC-DSBR), that entails R-loop accumulation and dissolution. Here, we uncover a function for the Bloom RecQ DNA helicase (BLM) in TC-DSBR in human cells. BLM is recruited in a transcription dependent-manner at DSBs where it fosters resection, RAD51 binding and accurate Homologous Recombination repair. However, in an R-loop dissolution-deficient background, we find that BLM promotes cell death. We report that upon excessive RNA:DNA hybrid accumulation, DNA synthesis is enhanced at DSBs, in a manner that depends on BLM and POLD3. Altogether our work unveils a role for BLM at DSBs in active chromatin, and highlights the toxic potential of RNA:DNA hybrids that accumulate at transcription-associated DSBs.
We report the self-assembly of a series of highly charged supramolecular complexes in aqueous media composed of cyclobis(4,4'-(1,4-phenylene)bispyridine-p-phenylene)tetrakis(chloride) (ExBox) and ...three dicationic perylene diimides (PDIs). Efficient energy transfer (ET) is observed between the host and guests. Additionally, we show that our hexacationic complexes are capable of further complexation with neutral cucurbit7uril (CB7), producing a 3-polypseudorotaxane via the self-assembly of orthogonal recognition moieties. ExBox serves as the central ring, complexing to the PDI core, while two CB7s behave as supramolecular stoppers, binding to the two outer quaternary ammonium motifs. The formation of the 3-polypseudorotaxane results in far superior photophysical properties of the central PDI unit relative to the binary complexes at stoichiometric ratios. Lastly, we also demonstrate the ability of our binary complexes to act as a highly selective chemosensing ensemble for the neurotransmitter melatonin.
In the huge field of polymer structure and dynamics, including intrinsically disordered peptides, protein folding, and enzyme activity, many questions remain that cannot be answered by methodology ...based on artificial intelligence, X-ray, or NMR spectroscopy but maybe by fluorescence spectroscopy. The theory of Förster resonance energy transfer (FRET) describes how an optically excited fluorophore transfers its excitation energy through space to an acceptor moiety-with a rate that depends on the distance between donor and acceptor. When the donor and acceptor moiety are conjugated to different sites of a flexible peptide chain or any other linear polymer, the pair could in principle report on chain structure and dynamics, on the site-to-site distance distribution, and on the diffusion coefficient of mutual site-to-site motion of the peptide chain. However, the dependence of FRET on distance distribution and diffusion is not defined by a closed analytical expression but by a partial differential equation (PDE), by the Haas-Steinberg equation (HSE), which can only be solved by time-consuming numerical methods. As a second complication, time-resolved FRET measurements have thus far been deemed necessary. As a third complication, the evaluation requires a computationally demanding but indispensable global analysis of an extended experimental data set. These requirements have made the method accessible to only a few experts. Here, we show how the Haas-Steinberg equation leads to a closed analytical expression (CAE), the Haas-Steinberg-Jacob equation (HSJE), which relates a diffusion-diagnosing parameter, the effective donor-acceptor distance, to the augmented diffusion coefficient,
, composed of the diffusion coefficient,
, and the photophysical parameters that characterize the used FRET method. The effective donor-acceptor distance is easily retrieved either through time-resolved or steady-state fluorescence measurements. Any global fit can now be performed in seconds and minimizes the sum-of-square difference between the experimental values of the effective distance and the values obtained from the HSJE. In summary, the HSJE can give a decisive advantage in applying the speed and sensitivity of FRET spectroscopy to standing questions of polymer structure and dynamics.
Functional electrical stimulation therapy (FEST) is a state-of-the-art treatment for retraining motor function after neurological injuries. Recent literature suggests that FEST can be further ...improved with brain-computer interface (BCI) technology. In this case study, we assessed the feasibility of using BCI-triggered FEST (BCI-FEST) to restore upper limb function in a 57-yr-old man with severe left hemiplegia resulting from a stroke 6 yrs before enrollment in the study. The intervention consisted of two blocks of forty 1-hr BCI-FEST sessions, with three sessions delivered weekly. During therapy, a single-channel BCI was used to trigger the stimulation programmed to facilitate functional movements. The measure of the feasibility of the BCI-FEST included assessing the implementation and safety of the intervention. Clinical improvements were assessed using (a) Functional Independence Measure, (b) Action Research Arm Test, (c) Toronto Rehabilitation Institute - Hand Function Test, and (d) Fugl-Meyer Assessment Upper Extremity test. Upon completion of 80 therapy sessions, 14-, 17-, and 18-point changes were recorded on Action Research Arm Test, Fugl-Meyer Assessment Upper Extremity test, and Toronto Rehabilitation Institute - Hand Function Test, respectively. The participant also indicated improvement as demonstrated by his ability to perform various day-to-day tasks. The results suggest that BCI-FEST is safe and viable.
Integrating brain-computer interface (BCI) technology with functional electrical stimulation therapy (FEST) is an emerging strategy for upper limb motor rehabilitation after spinal cord injury (SCI). ...Despite promising results, the combined use of these technologies (BCI-FEST) in clinical practice is minimal. To address this issue, we developed KITE-BCI, a BCI system specifically designed for clinical application and integration with dynamic FEST. In this paper, we report its technical features and performance. In addition, we discuss the differences in distributions of the BCI- and therapist-triggered stimulation latencies.
Two single-arm 40-session interventional studies to test the feasibility of BCI-controlled FEST for upper limb motor rehabilitation in individuals with cervical SCI.
Rehabilitation programs within the University and Lyndhurst Centres of the Toronto Rehabilitation Institute - University Health Network, Toronto, Canada.
Five individuals with sub-acute (< 6 months post-injury) SCI at the C4-C5 level, AIS B-D, and three individuals with chronic (> 24 months post-injury) SCI at C4 level, AIS B-C.
We measured BCI setup duration, and to characterize the performance of KITE-BCI, we recorded BCI sensitivity, defined as the percentage of successful BCI activations out of the total number of cued movements.
The overall BCI sensitivities were 74.46% and 79.08% for the sub-acute and chronic groups, respectively. The average KITE-BCI setup duration across the two studies was 11 min and 13 s.
KITE-BCI demonstrates a clinically viable single-channel BCI system for integration with FEST resulting in a versatile technology-enhanced upper limb motor rehabilitation strategy after SCI.
A detailed investigation of the chloride induced corrosion damage was performed on a 40 years old reinforced concrete beam exposed in marine environment. Visual observations, electrochemical ...measurements, carbonation depth, total chloride content were carried out. Half-cell potential measurements were used to locate corrosion areas. It appeared that the interpretation based on gradient of the potential was in good concordance with real state of damage. Complementary destructive methods are applied to observe the real corrosion state of steel rebars and characterize the corrosion products and the steel/concrete interface (optical and electronical microscopy tools (XRD, SEM, EDS and μ-Raman).
All these data indicate that on the beam, one may distinguish two types of areas: “high-corrosion zones” and “low-corrosion zones.” Given the fact that the “high corrosion zones” were found to be close to corrosion induced cracks and that they have a different morphology, this contribution concludes that the position of these areas did not shift in time.
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