Living ring-opening metathesis polymerization of norbornenes bay-functionalized perylene diimides

Ring-opening metathesis polymerization (ROMP)-derived poly(oxanorbornene imide)s bearing bay-linked mono - alkoxy -M1 and 1,7-di-alkoxy M2 functionalized perylene diimides (PDIs) were synthesized using Grubb's third ( G3 ) and Hoveyda-Grubbs second generation ( HG2 ) ruthenium-alkylidene metathesis initiators. The mono-alkoxy-derived PDI-based non-ladderphane polymer poly M1 displayed 67% to 77% of the trans olefin content in the polymer chain depending on the initiator used for the polymerization. When using the symmetrical 1,7-di-alkoxy-derived PDI-based polymer poly M2 having the ladderphane type-structure, this displayed a significant amount of cis and trans olefin contents in the polymer chains, irrespective of the type of initiators used for the polymerization. ROMP of both monomers M1 and M2 proceeded in a well-controlled manner with a linear dependence of molecular weight on the monomer/initiator ratio using G3 as initiator. Optical properties of the ladderphane-based poly M2 and non-ladderphane-based poly M1 were characterized in both solution and the film state. X-ray diffraction (XRD) analysis for all the polymers showed significant π-stacking in the thin film state with ordered molecular packing and closer values of d-spacing for both poly M1 and poly M2 . Film morphology examined by AFM elucidated homogenous smooth polymer surface for both polymers in general, but with some irregularities observed for poly M1 . In addition, CV analysis revealed both polymers could be good candidates as electron-accepting materials, with excellent film-forming ability, and thermal stability.     

Two New Nitrogenous Compounds from the Seeds of Brassica napus

Chemistry of Natural Compounds - Two new nitrogenous compounds identified as (2S)-2-sinapoyl-4-pentenenitrile (1) and brassicalkaloid A (2) have been isolated from the seed of Brassica napus L....     

Two algorithms for the exchange lemma

Numerical Algorithms - In this note, we present two new algorithms for the Steinitz Exchange Lemma. They are grounded on a single application of a procedure (finding either a row echelon form or a...     

Catalytic Kinetic Resolution of Biaryl Compounds

Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds.     

Bioprinting of Collagen: Considerations,Potentials, and Applications

Collagen is the most abundant extracellular matrix protein that is widely used in tissue engineering (TE). There is little research done on printing pure collagen. To understand the bottlenecks in printing pure collagen, it is imperative to understand collagen from a bottom‐up approach. Here it is aimed to provide a comprehensive overview of collagen printing, where collagen assembly in vivo and the various sources of collagen available for TE application are first understood. Next, the current printing technologies and strategy for printing collagen‐based materials are highlighted. Considerations and key challenges faced in collagen printing are identified. Finally, the key research areas that would enhance the functionality of printed collagen are presented.     

A Tri-state Fluorescent Switch with “Gated” Solid-state Photochromism Induced by an External Force

Mr. Chen Qian, Dr. Zhimin Ma, Mr. Jianwei Liu, Mrs. Xue Zhang, Prof. Shitao Wang and Prof. Zhiyong Ma. In this article, we report a newly designed molecule composed of a dihydroazulene (DHA) group and a phenothiazine (PTZ) moiety, which achieves aggregation-induced emission enhancement (AIEE), mechanochromism and “gated” solid-state photochromism upon stimulation by an external force. Grinding loosens intermolecular interactions in the crystal and causes a red-shift of fluorescence from 570 nm to 600 nm. Meanwhile, the ring-opening reaction of DHA unit is activated by grinding and a remarkable photochromism could be observed from the grinded powder. The reddish emission of the grinded powder peaked at 600 nm weakened gradually and finally became dark, and a new absorption band at 470 nm emerged in the absorption spectra. Time-dependent density functional theory (TD-DFT) calculation results reveal that the intramolecular intramolecular charge-transfer (ICT) process is replaced by a locally excited (LE) emission on the DHA group, which leads to the quenching of fluorescence. Its impressive photochromic property inspired us to a simple but effective way to develop an encryption system which can let the correct information be displayed upon external stimulation.     

Remote Fluorination and Fluoroalkyl(thiol)ation Reactions

Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides.     

Solubilization of Hexyl Aminolevulinate by Surfactants for Tumor Fluorescence Detection

Hexyl aminolevulinate (HAL) is a lipophilic derivative of 5-aminolevulinic acid (5-ALA) and can induce more protoporphyrin IX (PpIX) formation and stronger fluorescence intensity (FI) than 5-ALA, which will greatly facilitate photodynamic diagnosis and therapy. The main drawback of HAL is its low solubility in neutral aqueous media. In this study, surfactants were used to increase HAL solubility in the cell culture medium and serum, followed by in vitro fluorescence formation measurement in human pancreatic cancer cells (SW1990) and in vivo fluorescence detection in tumor-bearing mice. The results showed that Tween 80 (TW80) and Kolliphor® HS 15 (HS15) increased the solubility of HAL in the selected media. Although TW80 and HS15 exhibited in vitro cytotoxicity at high concentrations (5 mg mL⁻¹), they facilitated fluorescent signal formation at the early stage of cell incubation. When surfactants were used, the FI should be determined without the routine washing process because surfactant-containing culture medium caused the loss of synthesized PpIX during the washing process. When HAL dissolved in TW80 solution was injected intraperitoneally into pancreatic cancer-bearing mice at a dose of 50 mg kg⁻¹, the tumors exhibited red fluorescence, which indicated that systemic administration of surfactant-solubilized HAL might be applicable for tumor fluorescence detection in vivo.     

Subtle Alignment of Organic Semiconductors at the Donor/Acceptor Heterojunction Facilitates the Photoelectric Conversion Process

Chinese Journal of Polymer Science - The aligned molecular packing structure is vital to the anisotropic charge transport in conjugated polymer and small molecule thin films. However, how this...