Hemostatic Resuscitation in youngsters
Therefore, the UCNP nanoplatform displayed potential to be a powerful tool for the control of cell differentiation and the simultaneous long-term tracking of MSCs in vivo for regenerative medicine.Liquid-liquid phase separation (LLPS) of multivalent biopolymers is a ubiquitous process in biological systems and is of importance in bio-mimetic soft matter design. The phase behavior of biomolecules, such as proteins and nucleic acids, is typically encoded by the primary chain sequence and regulated by solvent properties. One of the most important physical modulators of LLPS is temperature. Solutions of proteins and/or nucleic acids have been shown to undergo liquid-liquid phase separation either upon cooling (with an upper critical solution temperature, UCST) or upon heating (with a lower critical solution temperature, LCST). However, many theoretical frameworks suggest the possibility of more complex temperature-dependent phase behaviors, such as an hourglass or a closed-loop phase diagram with concurrent UCST and LCST transitions. Here, we report that RNA-polyamine mixtures undergo a reentrant phase separation with temperature. Specifically, at low temperatures, RNA-polyamine mixtures form a homogenous phase. Increasing the temperature leads to the formation of RNA-polyamine condensates. A further increase in temperature leads to the dissolution of condensates, rendering a reentrant homogenous phase. This dual-response phase separation of RNA is not unique to polyamines but also observed with short cationic peptides. The immiscibility gap is controlled by the charge of the polycation, salt concentration, and mixture composition. Based on the existing theories of complex coacervation, our results point to a complex interplay between desolvation entropy, ion-pairing, and electrostatic interactions in dictating the closed-loop phase behavior of RNA-polycation mixtures.Urinary tract infection (UTI) represents one of the most common nosocomial infections, which is mainly related to indwelling catheters or stents. In addition to the formation of biofilms to reduce antibiotic sensitivity, the urease-producing bacteria can also increase urine pH, causing Ca2+ and Mg2+ deposition and finally catheter obstruction. The prevention of UTIs and its complication (i.e., encrustation) thus is a great challenge in design of catheters and ureteral stents. In this work, a metal-catechol-assisted mussel chemistry (i.e., dopamine self-polymerization) was employed for surface functionalization of commercially available catheters with antimicrobial peptides (AMP), for the purpose of long-term anti-infection and encrustation prevention. To improve the stability of the polydopamine coating on polymeric stents, we used Cu2+-coordinated dopamine self-polymerization. Then, a cysteine-terminated AMP was introduced on the polydopamine coating through Michael addition. We found that the Cu2+-coordinated polydopamine coating showed improved stability and antibacterial effect. The cytotoxicity test confirmed that the bioinspired antibacterial coating showed good biocompatibility and no obvious toxicity. click here The results confirmed that the stents with AMP could in situ inhibit bacterial growth and biofilm formation, and finally reduce the deposition of struvite and hydroxyapatite crystals both in vitro and in vivo. We anticipate that this bioinspired strategy would develop a safe, stable and effective antibacterial coating on urinary tract medical devices for long-term bacterial inhibition and encrustation prevention.Sensitizer molecules affect not only the quantum yield but also the selectivity of photochemical reactions. For an appropriate design of sensitized photochemical processes, we need to elucidate the reaction mechanism in detail. Here we investigated the mechanism of photoisomerization of stilbene via the triplet state with a para-benzoquinone sensitizer using density functional theory. In general, the isomerization of stilbene via the triplet state exhibits (Z)-selectivity (cis-selectivity); however, the para-benzoquinone sensitizer changes it to (E)-selectivity (trans-selectivity). The calculations showed that stilbene and para-benzoquinone form stable exciplexes having a preoxetane structure. The E/Z isomerization occurred via this exciplex, in which para-benzoquinone acted as a photocatalyst rather than a sensitizer only providing excitation energy. The spin-density distribution of the exciplex differed from the isolated stilbene in the triplet state. Therefore, the stilbene moiety could take (E)-conformation in the exciplex. The intermolecular charge-transfer drove the exciplex formation. This specific reaction mechanism originated from the electron-accepting ability of para-benzoquinone in the triplet state.A self-powered microRNA biosensor with triple signal amplification systems was assembled through the integration of three-dimensional DNA walkers, enzymatic biofuel cells and a capacitor. The DNA walker is designed from an enzyme-free target triggered catalytic hairpin assembly of modified gold nanoparticles. When triggered by the target microRNA, the DNA walker will move along the catalytic hairpin track, resulting in a payload release of glucose oxidase. The enzymatic biofuel cell contains the glucose oxidase bioanode and a bilirubin oxidase biocathode that bring a dramatic open circuit voltage to realize the self-powered bioassays of microRNA. A capacitor is further coupled with the enzymatic biofuel cell to further amplify the electrochemical signal, and the sensitivity increases 28.82 times through optimizing the matching capacitor. Based on this design, the present biosensor shows high performance, especially for detection limit and sensitivity. Furthermore, the present biosensor was successfully applied for serum samples, directly demonstrating its good application in clinical biomedicine and disease diagnosis.The valence photoionization of light and deuterated methanol dimers was studied by imaging photoelectron photoion coincidence spectroscopy in the 10.00-10.35 eV photon energy range. Methanol clusters were generated in a rich methanol beam in nitrogen after expansion into vacuum. They generally photoionize dissociatively to protonated methanol cluster cations, (CH3OH)nH+. However, the stable dimer parent ion (CH3OH)2+ is readily detected below the dissociation threshold to yield the dominant CH3OH2+ fragment ion. In addition to protonated methanol, we could also detect the water- and methyl-loss fragment ions of the methanol dimer cation for the first time. These newly revealed fragmentation channels are slow and cannot compete with protonated methanol cation formation at higher internal energies. In fact, the water- and methyl-loss fragment ions appear together and disappear at a ca. 150 meV higher energy in the breakdown diagram. Experiments with selectively deuterated methanol samples showed H scrambling inter CH3 loss. The roaming pathways are quickly outcompeted by hydrogen bond breaking to yield CH3OH2+, which explains the dominance of the protonated methanol fragment ion in the mass spectrum.The design of materials with enhanced luminescence properties is a fast-developing field due to the potential applicability of these materials as light-emitting diodes or for bioimaging. A transparent way to enhance the emission properties of interesting molecular candidates is blocking competing and unproductive non-radiative relaxation pathways by the restriction of intramolecular motions. Rationalized functionalization is an important possibility to achieve such restrictions. Using time-dependent density functional theory (TD-DFT) based on the ωB97XD functional and the semiempirical tight-binding method including long-range corrections (TD-LC-DFTB), this work investigates the effect of functionalization of the paradigmatic tetraphenylethylene (TPE) on achieving restricted access to conical intersections (RACI). Photodynamical surface hopping simulations have been performed on a larger set of compounds including TPE and ten functionalized TPE compounds. Functionalization has been achieved by means of electron-withdrawing groups, bulky groups which block the relaxation channels via steric hindrance and groups capable of forming strong hydrogen bonds, which restrict the motion via the formation of hydrogen bond channels. Most of the investigated functionalized TPE candidates show ultrafast deactivation to the ground state due to their still existing structural flexibility, but two examples, one containing -CN and -CF3 groups and a second characterized by a network of hydrogen bonds, have been identified as interesting candidates for creating efficient luminescence properties in solution.Photoactive proteins typically rely on structural changes in a small chromophore to initiate a biological response. While these changes often involve isomerization as the "primary step", preceding this is an ultrafast relaxation of the molecular framework caused by the sudden change in electronic structure upon photoexcitation. Here, we capture this motion for an isolated model chromophore of the photoactive yellow protein using time-resolved photoelectron imaging. It occurs in less then 150 fs and is apparent from a spectral shift of ∼70 meV and a change in photoelectron anisotropy. Electronic structure calculations enable the quantitative assignment of the geometric and electronic structure changes to a planar intermediate from which the primary step can then proceed.Osteoarthritis is a significant driver of disability in the elderly with increasing prevalence, and inflammation plays a vital role on its etiology. Licorice is commonly used as a traditional Chinese medicine or food additive, and its prenylated phenolic compounds were recently reported to be able to inhibit osteoarthritis with anti-inflammatory activity. In order to explore more anti-osteoarthritic prenylated phenolic compounds from licorice, we isolated ten compounds (1-10), with three new ones (1-3), from the ethyl acetate extract of Glycyrrhiza uralensis. Compound 2 (glycyuralin R) was a racemic 3-phenoxy-chromanone, and we achieved its chiral separation for the first time. Compounds 1, 2, 7 and 8 showed significant NO inhibitory ability in IL-1β-stimulated mouse primary chondrocytes, and we further confirmed the anti-inflammatory activity of 1 (glycyuralin Q) by evaluating its effect on osteoarthritis-related iNOS, COX-2, TNF-α, IL-6, MMP3, MMP13 and NF-κB based on various experimental methods. These results clarified the potential of several prenylated phenolic compounds, especially 1 in licorice, as the lead compounds for osteoarthritis.Precise determination of structural organization of semi-conducting polymers is of paramount importance for the further development of these materials in organic electronic technologies. Yet, prior characterization of some of the best-performing materials for transistor and photovoltaic applications, which are based on polymers with rigid backbones, often resulted in conundrums in which X-ray scattering and microscopy yielded seemingly contradicting results. Here we solve the paradox by introducing a new structural model, i.e., semi-paracrystalline organization. The model establishes that the microstructure of these materials relies on a dense array of small paracrystalline domains embedded in a more disordered matrix. Thus, the overall structural order relies on two parameters the novel concept of degree of paracrystallinity (i.e., paracrystalline volume/mass fraction, introduced here for the first time) and the lattice distortion parameter of paracrystalline domains (g-parameter from X-ray scattering). Structural parameters of the model are correlated with long-range charge carrier transport, revealing that charge transport in semi-paracrystalline materials is particularly sensitive to the interconnection of paracrystalline domains.