Mcnamarabraun2739

Proline based receptors (1-14) attached with phenylboronic acid and benzaldehyde binding groups at the N-/C- or C-/N-termini of the proline residue were created for chiral recognition of l-/d-DOPA, in an attempt to examine if balancing the two binding events would influence the recognition. By changing the positions of boronic acid and aldehyde groups substituted on the phenyl rings (1-4, 5-8) and the site at which phenylboronic acid and benzaldehyde moieties attached respectively to the N- and C-termini or C- and N-termini of the proline residue (1-4vs.5-8), and by introducing an electron-withdrawing fluorine atom in the phenyl ring of the weaker binder the benzaldehyde moiety (11vs.1, 14vs.5), we were able to show that a better balance of the two binding events does improve the chiral recognition. This finding can only be made with the current version of receptors that were equipped with two different binding groups. Together with the finding that the chiral recognition performance in mixed organic-aqueous solutions is tunable by varying the solvent composition, we have now arrived at a protocol for designing proline based receptors for extended applications in chiral recognition.Three positional isomers of thiophosphoranyl anthracene were synthesized and their photophysical properties were investigated. By varying the position of the substituents, blue, green and yellow solid-state fluorescence with differences in the emission wavelength of over 100 nm, assigned to the intra- and intermolecular effects, could be established.ArNMeCH(SiMe3)2 has been developed as a useful precursor of a formal α-aminoalkyl diradical in Ru(bpy)3Cl2-catalzyed addition with alkenes under visible-light-mediated photoredox conditions. This approach leads to homo-diaddition with two identical alkenes in one-pot, or hetero-diaddition with two different alkenes via a sequential operation.Ferroelectric (FE) materials, especially ABO3 FE perovskite oxides, have been extensively studied for their important applications in memory devices, electronics and sensors. However, the integration of FE perovskite oxides into miniaturized memory and electronic devices has been impeded by the critical thickness limitation, as out-of-plane ferroelectricity in most FE perovskite oxides will disappear when the oxide thin film thickness is below a critical value. On the other side, CuInP2S6 (CIPS) nano-flake, a prototypical two-dimensional (2D) FE material, has recently been demonstrated to display stable out-of-plane ferroelectricity at the atomic layer thickness by experiment, which offers a new candidate for developing FE devices in the 2D nanoscale regime. Herein, after investigation of the structural and ferroelectric properties of 2D CIPS layers, especially the interactions between out-of-plane polarization and the corresponding depolarization field using first-principles calculations, we reveal that out-of-plane ferroelectricity can even persist in the CIPS monolayer, which is only 3.4 Å in thickness. Moreover, in order to explore the potential application of 2D FE CIPS layers as minimized FE devices, we design an ultrathin ferroelectric tunneling junction (FTJ) composed of a graphene/CIPS monolayer/graphene vertical van der Waals (vdW) heterostructure. Our transport simulations based on the non-equilibrium Green's function formalism predict that such an ultrathin FTJ device can still exhibit the typical tunneling electroresistance (TER) effect, where tunneling current strongly depends on the direction of FE polarization. Our work not only elucidates the origin of stable out-of-plane ferroelectricity appearing in 2D CIPS layers, but also demonstrates the practical application of a CIPS based 2D FTJ as a miniaturized, multi-functional and low-power consumption memory device for modern electronics.A copper-catalyzed borylative amidation of vinyl arenes with isocyanates and bis(pinacolato)diboron has been developed. This new protocol, which can be performed on a gram-scale, utilizes isocyanates as simple precursors to provide access to a range of boryl alkyl amides. The products contain valuable amide and boronate, which are amenable for further elaboration, and have versatile synthetic utilities.We evaluate experimentally the force exerted by flexible metal-organic frameworks through expansion for a representative model system, namely MIL-53(Al). The results obtained are compared with data collected from intrusion experiments while molecular simulations are performed to shed light on the re-opening of the guest-loaded structure. The critical impact of the transition stimulating medium on the magnitude of the expansion force is demonstrated.The photocatalytic generation of an NADH synthetic analogue, i.e. 1-benzyl-1,4-dihydronicotinamide (1,4-BNAH), has been studied using the cobalt diimino-dioxime complexes and the BF2-bridged derivative as catalysts. 1,4-BNAH was produced in both aqueous and organic media at unprecedented turnover numbers with metal and organic photosensitizers, respectively.Hollow mesoporous copper sulfide nanoparticles (HMCuS NPs) are advantageous for loading small-molecule therapeutic drugs coupled with photothermal ablation for synergistic tumor therapy. NCT-503 However, treatment efficacy mediated by HMCuS NPs is not always satisfactory owing to their insensitivity toward the tumor microenvironment (TME), and unpredictable drug leakage may also result in deleterious systemic toxicity. Here, a novel HMCuS@MnO2-based core-shell nanoplatform was developed as a highly efficient TME modulator, which could alleviate tumor hypoxia, deplete the level of intracellular glutathione (GSH) and trigger the dissolution of Mn2+. Moreover, MnO2, in situ grown on the surface of HMCuS, may act as a gatekeeper by forming a stimulus-responsive plug within the mesoporous structure, which effectively prevented the premature release of encapsulated photosensitizer chlorin e6 (Ce6) and was responsive to the acidic TME for demand-based drug release. Under the condition of 660/808 nm dual-wavelength laser irradiation, hyperthermia-mediated photothermal therapy (PTT) and reactive oxygen species (ROS)-mediated photodynamic therapy (PDT) can be triggered for tumor eradication, which were further enhanced upon the modification of the TME. In the meantime, splendid photoacoustic (PA)/fluorescence (FL)/magnetic resonance (MR) imaging properties of HMCuS@MnO2/Ce6 (CMC) NPs could enable the realization of more precise, reliable and on-demand combination therapy. In a word, this study illustrated a promising approach to strengthen the efficacy of HMCuS-based nanotherapeutics, which would definitely promote the further exploitation of smarter nanoplatforms for synergistic disease management.