Jorgensensivertsen0024

Herein a rapid and sensitive fluorometric bioanalysis platform for mercury(ii) (Hg2+) detection was innovatively developed using ultrathin two-dimensional MXenes (Ti3C2) as fluorescence quencher and Hg2+-induced exonuclease III (Exo III)-assisted target recycling strategy for efficient signal amplification. learn more Initially, fluorophore-labeled single-stranded DNA (FAM-labeled probe) can be easily adsorbed onto the surface of ultrathin Ti3C2 nanosheets by hydrogen bonding and metal chelating interaction, and the fluorescence signal emitted by the FAM-labeled probe is quenched strongly owing to the fluorescence resonance energy transfer between the FAM and ultrathin Ti3C2 nanosheets. Upon sensing the target Hg2+, the protruding DNA fragment at the 3' end of hairpin will hybridize with primer (hairpin-Hg2+-primer), and then further digested by Exo III to produce a probe (nicker). The released target Hg2+ and primer continue to participate in the next recycling, resulting in more hairpin probes becoming nickers. The combination of a large number of nickers and FAM-probe resulted in a significant increase in the fluorescence signal of the system, which was attributed to the fact that the double helix DNA was more rigid and separated from the surface of the ultrathin Ti3C2 nanosheets. The obvious fluorescence signal change of the Ti3C2-based Exo III-assisted target recycling can be accurately monitored by fluorescence spectrometry, which is also proportional to the concentration of Hg2+. Under optimum operating conditions, the peak intensity (520 nm wavelength) of fluorescence increased with increasing Hg2+ within a wide dynamic working range from 0.05 nM to 50 nM (R2 = 0.9913) with a limit of detection down to 42.5 pM. The proposed strategy uses ultrathin MXenes as a platform for binding nucleic acids, which contributes to its potential in nucleic acid hybridization-based biosensing and/or nucleic acid signal amplification bio-applications.Lanthanide elements have well-documented similarities in their chemical behavior, which make the valuable trivalent lanthanide cations (Ln3+) particularly difficult to separate from each other in water. In this work, we apply ab initio molecular dynamics simulations to compare the free energies (ΔGads) associated with the adsorption of lanthanide cations to silica surfaces at a pH condition where SiO- groups are present. The predicted ΔGads for lutetium (Lu3+) and europium (Eu3+) are similar within statistical uncertainties; this is in qualitative agreement with our batch adsorption measurements on silica. This finding is remarkable because the two cations exhibit hydration free energies (ΔGhyd) that differ by >2 eV, different hydration numbers, and different hydrolysis behavior far from silica surfaces. We observe that the similarity in Lu3+ and Eu3+ ΔGads is the result of a delicate cancellation between the difference in Eu3+ and Lu3+ hydration (ΔGhyd), and their difference in binding energies to silica. We propose that disrupting this cancellation at the two end points, either for adsorbed or completely desorbed lanthanides (e.g., via nanoconfinment or mixed solvents), will lead to effective Ln3+ separation.In situ electrical conductivity measurements (ECMs) have been employed to gain insights into the redox and electronic behavior of ceria and surface-phosphated ceria catalysts with phosphorus contents lower than 2.2 at%. Temperature-programmed reduction under hydrogen (H2-TPR) was used to analyze the reducibility of the catalysts. Their propane oxydehydrogenation performance both in terms of activity and selectivity has been explained. It has been unambiguously shown that all the catalysts function via a heterogeneous redox mechanism involving only surface and subsurface lattice oxygen species whose availability and reactivity decrease with increasing phosphorus content with consequences on the catalytic performance.Spinal cord injury (SCI) is a neurological disorder that can lead to loss of perceptive and athletic function due to the severe nerve damage. To date, pieces of evidence detailing the precise pathological mechanisms in SCI are still unclear. Therefore, drug therapy cannot effectively alleviate the SCI symptoms and faces the limitations of systemic administration with large side effects. Thus, the development of SCI treatment strategies is urgent and valuable. Due to the application of nanotechnology in pharmaceutical research, nanopharmaceutical-based regenerative medicine will bring colossal development space for clinical medicine. These nanopharmaceuticals (i.e. nanocrystalline drugs and nanocarrier drugs) are designed using different types of materials or bioactive molecules, so as to improve the therapeutic effects, reduce side effects, and subtly deliver drugs, etc. Currently, an increasing number of nanopharmaceutical products have been approved by drug regulatory agencies, which has also prompted more researchers to focus on the potential treatment strategies of SCI. Therefore, the purpose of this review is to summarize and elaborate the research progress as well as the challenges and future of nanopharmaceuticals in the treatment of SCI, aiming to promote further research of nanopharmaceuticals in SCI.Three series of copper hydride clusters [Cu8H6L6]2+ (1), [Cu4HX2L4]+ where X- = Cl- (2a), Br- (2b), I- (2c), N3- (2d) and SCN- (2e), and [Cu4HX3L3] where X- = Br- (3b) and I- (3c) (L = 2-(diphenylphosphino)pyridine, dppy) were synthesized and characterized by single-crystal X-Ray crystallography and standard spectroscopic techniques. The metal core of 1, Cu8, can be described as a bicapped octahedron, while those of 2 and 3 series adopt tetrahedral structures. The hydride positions were deduced from difference electron density maps and corroborated by NMR and DFT calculations. For 1, there are two μ4-H-, one each in the two tetrahedral cavities of the two capping atoms and four μ3-H- on the six triangular faces around the waist of the octahedron. For [Cu4HX2L4]+ and [Cu4HX3L3] series, the single μ4-H- resides in the center of the Cu4 tetrahedron. It was found that these three series of copper clusters are intimately connected and can convert from one to another under specific reaction conditions. Their transformation pathways were investigated in detail. Spontaneous resolution to form optically pure enantiomeric single crystals was observed for [Cu4H(SCN)2L4]+ (2e) and [Cu4HBr3L3] (3b). Photoluminescence was observed for [Cu4HX2L4]+, as well as [Cu4HX3L3] with strong emissions from green to yellow regions.We have designed a new chiral receptor based on two salen zinc(ii) complex units connected with a spirobifluorene framework. The chiral receptor is proven to enantioselectively bind chiral carboxylate guests and the differences between the binding constants of enantiomeric guests were up to more than one order of magnitude.Thermodynamic properties and structure of binary mixtures of patchy and spherical colloids are studied using a recently developed theory [Y. V. Kalyuzhnyi, et al., Soft Matter, 2020, 16, 3456]. The theory is based on a solution of the multidensity Ornstein-Zernike equation and provides completely analytical expressions for the structure factors of these systems and for all their major thermodynamical quantities. The considered mixtures are made up of particles of different size and with a different number of patches. A set of molecular simulation data has been generated to enable a systematic comparison and to access thus accuracy of the theoretical predictions. In general, the predictions of the theory appear to be in good agreement with computer simulation data. For the models with a lower number of patches (np = 1, 2) the theoretical results show very good accuracy. Less accurate are the predictions for the four-patch versions of the model. While theoretical results for the radial distribution functions are, generally, relatively accurate for all the models, results for thermodynamics deteriorate with increasing concentration of the spherical colloids. Possible ways to improve the theory are briefly outlined.The relationship between structure and dynamical behavior (super-Arrhenius temperature dependence of relaxation time accompanied by heterogeneous dynamics) in glassy materials remains an open issue in the physics of condensed matter. The question of whether this dynamic phenomena have a thermodynamic origin or not still remains unanswered. In this work we analyze several dynamic and structural parameters in a polymer glass-former by means of molecular dynamics simulations. The results obtained in this work indicate that the structure does affect dynamic behavior, whereas structural conditioning becomes noticeable below the temperature at which the non-Arrhenius behavior manifests and increases as the system approaches the glass transition temperature. Moreover, we observed that the short-range order parameters are related to local dynamics at the single-particle level. These results reinforce the idea of a connection between the structure and dynamics and that could indicate the thermodynamic nature of glass transition.Thermolysis of [(Cp*Nb)2(B2H6)2], 1b (Cp* = η5-C5Me5), with 2-mercaptobenzothiazole, C6H4NSCSH (MBT), and 2-mercaptobenzoxazole, C6H4NOCSH (MBO), yielded hydrogen substituted compounds 2 and 3 with a general formula [(Cp*Nb)2(B2H6)(B2H5L)] (2 L = C6H4NSCS and 3 L = C6H4NOCS). A similar reaction of 1b with Ph2Se2 yielded the monosubstituted derivative [(Cp*Nb)2(B2H6)B2H5(PhSe)], 4. All further efforts towards persubstitution of 1b under various drastic conditions were unfruitful. In parallel, in an effort to find a better synthetic route to the known Ta-aziridine complex [Cp*TaBH(C7H4NS2)CH2S2NC6H4], Cp*TaCl4 was treated with a 2-mercaptobenzothiazolyl-based borate ligand Na[H2B(C6H4NSCS)2]. Surprisingly, the reaction led to the formation of the half-sandwich trichloroaryltantalum(v) complex [Cp*TaCl3κ2-N,S-C6H4NSCS], 5, containing a heterocyclic thiol ligand. Using an alternative method complex 5 was isolated in good yield when Cp*TaCl4 was treated with the potassium salt of 2-mercaptobenzothiazole K[C6H4NSCS]. All the compounds were characterized by 1H, 11B1H, and 13C1H NMR spectroscopy, and their structures were unequivocally established by crystallographic analysis.Second-order rate constants of the reduction of histidine radicals by tryptophan were obtained for all combinations of the two amino acids and their N-acetyl derivatives. For the dipeptide N-acetyl histidine-tryptophan, contributions from inter- and intramolecular reduction were revealed. The pH dependences of the rate constants were found to be determined by the protonation state of the amino group of tryptophan. Proton coupled electron transfer is proposed as a reaction mechanism.We present a microfluidic platform that allows in operando nuclear magnetic resonance (NMR) observation of serial mixing experiments. Gradually adding one reagent to another is a fundamental experimental modality, widely used to quantify equilibrium constants, for titrations, and in chemical kinetics studies. NMR provides a non-invasive means to quantify concentrations and to follow structural changes at the molecular level as a function of exchanged volume. Using active pneumatic valving on the microfluidic device directly inside an NMR spectrometer equipped with a transmission-line NMR microprobe, the system allows injection of aliquots and in situ mixing in a sample volume of less than 10 μL.