One-pot diastereoselective synthesis of tetrahydroepimino-benzo[b]azocines through sequential [3+2]-cycloaddition and Staudinger-aza-Wittig reactions

The one-pot synthesis of tetrahydro-epiminobenzo[b]azocines through a sequential 1,3-dipolar cycloaddition and intramolecular Staudinger-aza-Wittig reaction sequence is reported. This methodology provides a new and efficient approach for medium-sized and bridged nitrogen heterocyclic molecules.     

Efficient glycosylation with glycosyl ortho-allylbenzoates as donors

Glycosylation reactions are significant as they provide access to model compounds that are useful for elucidating biochemical pathways. Herein, we describe the development of glycosyl ortho-alkynylbenzoates as novel, bench-top stable, and readily available glycosyl donors. Glycosylation is promoted by inexpensive trimethylsilyl triflate (TMSOTf) in combination with N-iodosuccinimide (NIS) under mild reaction conditions; hence, the novel glycosyl donors are promising reagents for the synthesis of glycosides.     

Bifunctional Phosphine Ligand Enabled Gold‐Catalyzed Alkynamide Cycloisomerization: Access to Electron‐Rich 2‐Aminofurans and Their Diels–Alder Adducts

By using biphenyl‐2‐ylphosphines functionalized with a remote tertiary amino group as a ligand, readily available acetylenic amides are directly converted into 2‐aminofurans devoid of any electron‐withdrawing and hence deactivating/stabilizing substituents. These highly electron‐rich furans have rarely been prepared, let alone applied in synthesis, because of their high reactivities and low stabilities associated with the electron‐rich nature of the furan ring. In this work, these reactive furans smoothly undergo either in situ intermolecular Diels–Alder reactions to deliver highly functionalized/substituted aniline products or intramolecular ones to furnish carbazole‐4‐carboxylates in mostly good to excellent yields. This work offers general and expedient access to this class of little studies electron‐rich furans and should lead to exciting opportunities for their applications.     

Efficient structural modification of electron-withdrawing substituents on Pt(II) complexes for red emitters: A theoretical study

In this study, the electronic structures and optical properties of a cyclometalated Pt(II) complex (M1) and a series of derivatives (M1–F, M1–CF₃, and M1–CN) with electron-withdrawing substituents (–F, –CF₃, and –CN) at the carbazole moiety were theoretically investigated by density functional theory and time-dependent density functional theory. The calculation results reveal that these Pt complexes display deep red phosphorescence emission above Λ = 640 nm. When the ³MLCT/π → π* to triplet metal-centered ³MC/d–d state decay mechanism is taken into consideration, the nonradiative decay rate constant (k_nr) decreased in the order M1 > M1–CF₃ > M1–F > M1–CN. The <T₁|H_SOC|S_m> and kr values of M1-F are similar with those of M1, however the Knr rate ofM1-F is larger than that of M1. M1–F is expected to have improved quantum yields. Moreover, through the analyses of the HOMO/LUMO level and triplet energy, it is found that the introduction of –F and –CN substituents in M1 results in efficient energy transfer from the host material 4,4′-N,N′-dicarbazole-biphenyl to these complexes. In view of the electroluminescent applications in organic light-emitting diodes, M1–F can serve as efficient deep-red guest materials with improved electron injection and transport ability.     

Hydrogen-Bond Cyclization Programming of Ultrasensitive Esters and Its Application in Gene Delivery

The ester bond as a universal linker has recently been applied in gene delivery systems owing to its efficient gene release by electrostatic repulsion after its cleavage. However, the ester bond is nonlabile and is difficult to cleave in cells. This work reports a method in which a secondary amine was introduced to the β-position of the ester bond to generate a hydrogen-bond cyclization (HBC) structure that can make the ester bond hydrolysis ultrafast. A series of molecules comprising ultrasensitive esters that can be activated by H₂O₂ were synthesized, and it was found that those able to form an HBC structure showed complete ester hydrolysis within 5 h in both water and phosphate-buffered saline solution, which was several times faster than other methods reported. Then, a series of amphiphilic poly(amidoamine) dendrimers were constructed, comprising the ultrasensitive ester groups for gene delivery; it was found that they could effectively release genes under quite a low concentration of H₂O₂ (<200 μm ) and transport them into the nucleus within 2 h in Hela cells with high safety. Their gene transfection efficiencies were higher than that of PEI_25k. The results demonstrated that the hydrogen-bond-induced ultrasensitive esters could be powerfully applied to construct gene delivery systems.     

A coupled immersed boundary‐lattice Boltzmann method with smoothed point interpolation method for fluid‐structure interaction problems

The immersed boundary‐lattice Boltzmann method has been verified to be an effective tool for fluid‐structure interaction simulation associated with thin and flexible bodies. The newly developed smoothed point interpolation method (S‐PIM) can handle the largely deformable solids owing to its softened model stiffness and insensitivity to mesh distortion. In this work, a novel coupled method has been proposed by combining the immersed boundary‐lattice Boltzmann method with the S‐PIM for fluid‐structure interaction problems with large‐displacement solids. The proposed method preserves the simplicity of the lattice Boltzmann method for fluid solvers, utilizes the S‐PIM to establish the realistic constitutive laws for nonlinear solids, and avoids mesh regeneration based on the frame of the immersed boundary method. Both two‐ and three‐dimensional numerical examples have been carried out to validate the accuracy, convergence, and stability of the proposed method in consideration of comparative results with referenced solutions.     

A Novel Method for the Improved Skin Whitening Effect Based on Nanostructured Lipid Carrier

The effect of humidity on the holographic grating diffraction efficiency and transmittance kinetics in the E204Q BR gelatin film is investigated. We found a correlation between the accumulation of the red-light absorbing O intermediate in the later part of the E204Q BR photocycle and sharpness (decay to the steady-state) of the holographic recording kinetics. As shown, at humidity exceeding 95% the ratio between the peak and steady-state of the diffraction efficiency for the weak probe beam (670 nm) can reach 8.7 in the E204Q BR film, which is sufficient for realization of an efficient novelty filter.