Hirschkeller0907

In contrast, the NPLs' LD spectrum indicates that their excitonic transitions are isotropic in the spatial space. TAK-715 This work provides a new viewpoint of the real status of anisotropic semiconductor NCs in solution.Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.The evolution of high electromagnetic absorption materials is essential in the fast growing electronic industry in overcoming electromagnetic pollution. In view of this, a series of Ni nanoparticle-decorated functionalized graphene sheets (FG/Ni) are synthesized by a solvothermal method using different ratios of FG/Ni precursors. Subsequently, FG/Ni is subjected to in situ polymerization of aniline to form FG/Ni/PANI ternary composites and characterized. The total electromagnetic interference shielding efficiency (SET) measurements on FG/Ni/PANI with an optimized FG/Ni ratio (50 mg600 mg NiCl2·6H2O) exhibit enhanced performance, i.e., ∼47-65 dB (2-3.8 GHz) and ∼65-45 dB (3.8-8 GHz), following absorption as the dominant mechanism due to the matching of dielectric loss and magnetic loss. It is anticipated that such excellent performance of robust FG/Ni/PANI ternary composites at a very low thickness (0.5 mm) has great potential in the application of microwave-absorbing materials.Members of the parvalbumin (PV) family of calcium (Ca2+) binding proteins (CBPs) share a relatively high level of sequence similarity. However, their Ca2+ affinities and selectivities against competing ions like Mg2+ can widely vary. We conducted molecular dynamics simulations of several α-parvalbumin (αPV) constructs with micromolar to nanomolar Ca2+ affinities to identify structural and dynamic features that contribute to their binding of ions. Specifically, we examined a D94S/G98E construct with a lower Ca2+ affinity (≈-18 kcal/mol) relative to the wild type (WT) (≈-22 kcal/mol) and an S55D/E59D variant with enhanced affinity (≈-24 kcal/mol). Additionally, we also examined the binding of Mg2+ to these isoforms, which is much weaker than Ca2+. We used mean spherical approximation (MSA) theory to evaluate ion binding thermodynamics within the proteins' EF-hand domains to account for the impact of ions' finite sizes and the surrounding electrolyte composition. While the MSA scores differentiated Mg2+ from Ca2V ion binding that are likely shared by members of the broad family of CBPs.Phospholipid monolayers formed at oil-water interfaces have been used to explore biological interface properties. Thus, monolayer systems need to be quantitatively understood. Previously, we investigated the formation of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) monolayers at silicone oil-water interfaces to determine the dependence of interfacial tension, γ, on the area per lipid, a, compared to that of the closely packed monolayers, acp. This study aims to develop a method to obtain the γ-a relationship from the γ-a/acp data by investigating POPC monolayers at the silicone oil-water and tricaprylin-water interfaces. Pendant drop tensiometry was used to obtain the dependence of γ on a/acp. Furthermore, by calculating the surface pressure, Π, from γ and multiplying a/acp with an estimated acp value, the dependence of Π on a was obtained. When a value approximately equal to the a of POPC bilayers was assigned to acp, the resultant Π-a profile partially or approximately completely overlapped with the Π-a isotherms obtained for the monolayers at the air-water interface using a Langmuir trough. The overlap for the silicone oil-water interface occurred at a ≤ 77 Å2, while that for the tricaprylin-water interface occurred in approximately the entire a region. The results indicate that the Π of the condensed monolayers is little affected by bulk oil. Thus, the γ-a relationship for the oil-water interface can be determined by comparing the compression isotherm with the one obtained for the air-water interface.With the microfluidics community embracing 3D resin printing as a rapid fabrication method, controlling surface chemistry has emerged as a new challenge. Fluorination of 3D-printed surfaces is highly desirable in many applications due to chemical inertness, low friction coefficients, antifouling properties, and the potential for selective hydrophobic patterning. Despite sporadic reports, silanization methods have not been optimized for covalent bonding with polymeric resins. As a case study, we tested the silanization of a commercially available (meth)acrylate-based resin (BV-007A) with a fluoroalkyl trichlorosilane. Interestingly, plasma oxidation was unnecessary for silanization of this resin and indeed was ineffective. Solvent-based deposition in a fluorinated oil (FC-40) generated significantly higher contact angles than deposition in ethanol or gas-phase deposition, yielding hydrophobic surfaces with contact angle >110° under optimized conditions. Attenuated total reflectance-Fourier transform infrared spectroscopy indicated that the increase in the contact angle correlated with consumption of a carbonyl moiety, suggesting covalent bonding of silane without plasma oxidation. Consistent with a covalent bond, silanization was resistant to mechanical damage and hydrolysis in methanol and was stable over long-term storage. When tested on a suite of photocrosslinkable resins, this silanization protocol generated highly hydrophobic surfaces (contact angle > 110°) on three resins and moderate hydrophobicity (90-100°) on the remainder. Selective patterning of hydrophobic regions in an open 3D-printed microchannel was possible in combination with simple masking techniques. Thus, this facile fluorination strategy is expected to be applicable for resin-printed materials in a variety of contexts including micropatterning and multiphase microfluidics.The structures and binding topologies of two binary van der Waals complexes 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)···Ne and ···Ar were investigated. The rotational spectra of these two complexes including several isotopic species containing 20Ne, 22Ne, 40Ar, 13C, and hydroxyl D were measured using a chirped pulse Fourier transform microwave spectrometer and a cavity-based Fourier transform microwave spectrometer. While HFIP was shown to exist in both the gauche and trans configurations based on previous reports, the rare gas atom is predicted to attach to HFIP in several different binding topologies, leading to a total of nine possible structural isomers for each complex. Only one isomer was detected for each species, and it corresponds to the most stable one predicted, based on the comparison of the experimental rotational constants and electric dipole moment components with the theoretical predictions and on the isotopic data. We applied quantum theory of atoms in molecules (QTAIM) and electrostatic potential calculations to examine the different rare gas binding sites and to explore the nature of the interactions in these two complexes and several previously reported alcohol···Ar complexes. The effects of fluorination are also discussed by comparison with the binary complexes of isopropanol···Ne and ···Ar.Cationic nanoparticles are known to interact with biological membranes and often cause serious membrane damage. Therefore, it is important to understand the molecular mechanism for such interactions and the factors that impact the degree of membrane damage. Previously, we have demonstrated that spatial distribution of molecular charge at cationic nanoparticle surfaces plays an important role in determining the cellular uptake and membrane damage of these nanoparticles. In this work, using diamond nanoparticles (DNPs) functionalized with five different amine-based surface ligands and small phospholipid unilamellar vesicles (SUVs), we further investigate how chemical features and conformational flexibility of surface ligands impact nanoparticle/membrane interactions. 31P-NMR T2 relaxation measurements quantify the mobility changes in lipid dynamics upon exposing the SUVs to functional DNPs, and coarse-grained molecular dynamics simulations further elucidate molecular details for the different modes of DNP-SUV interactions depending on the surface ligands. Collectively, our results show that the length of the hydrophobic segment and conformational flexibility of surface ligands are two key factors that dictate the degree of membrane damage by the DNP, while the amount of surface charge alone is not predictive of the strength of interaction.A series of Al-doped BiVO4 composites have been synthesized via the hydrothermal method for methylene blue (MB) degradation application. The reasons for the improvement of photocatalytic performance was explained from the perspective of optics. Transient photovoltage (TPV) measurements suggested that the surface states have the priority to capture photogenerated carriers, and the Al2O3 surface passivation layer can prolong the lifetime of charge carrier. The results of surface photovoltage (SPV), transient photovoltage (TPV), and surface photocurrent (SPC) measurements suggested that the coexistence of Al3+ and Al2O3 caused by the appropriate doping would improve the transfer property and prolong the lifetime of photogenerated carriers. Finally, the possible photocatalytic mechanism is expounded to illustrate the photogenerated charge behavior under visible light irradiation. This work provides a better understanding of the synergistic effect of Al-doping and Al2O3 passivation layer on enhancing the photocatalytic performance.A protocol in the preparation of functionalized N-allyl-N-aryl sulfonamides via palladium-catalyzed intramolecular decarboxylative N-allylation reaction is presented. The alkylated 2,5-cyclohexadienyl ketoesters reacted with arylsulfonamides in the presence of titanium tetrachloride and pyridine, which allows the formation of alkylated 2,5-cyclohexadienyl sulfonyl iminoesters which then undergo a palladium-catalyzed intramolecular allylic amidation through decarboxylative aromatization to provide functionalized N-allyl-N-aryl sulfonamides. This allylation protocol proceeds with good regioselectivity. Moreover, we have also shown that N-allyl-N-aryl sulfonamide can be transformed into 4-aryl-1,2,3,4-tetrahydroquinoline and nitrogen-containing β-hydroxysulfide bioactives.An intramolecular carbometallation of a triple bond promoted by electrochemistry and mediated by nickel catalysis is described. This domino process transforms various aryl halides bearing a propargyl chain into substituted heterocycles in one single operation, with high stereoselectivities and in good to high yields. This reaction, characterized by a cyclic voltammetry set of experiments, proceeds following a syn-exo-dig cyclization process. When run at 80 °C, vinylbenzofuranes that are suitable substrates for cycloaddition reactions are obtained.