Synthesis and Properties of Thermosensitive Poly(N-Isopropylacrylamide)/Waterborne Polyurethane Graded Concentration Hybrid Films

Temperature-sensitive hybrid films were synthesized with a concentration gradient by casting and UV curing of N-isopropylacrylamide (NIPAAm) monomers (0%–70%) on the free surface of waterborne polyurethane (WPU) films on a Teflon substrate. The surface hardness and contact angle of the free surface with a water drop increased asymptotically with the addition of NIPAAm, whereas those on the substrate side were virtually unchanged. The diffusion coefficient (D), rates of swelling at 20°C (below the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM)) and deswelling at 50°C (above the LCST) increased with increasing NIPAM content, showing favorable thermosensitivity. In addition, the glassy state modulus and glass transition temperature (Tg) of the film increased with increasing NIPAM content, whereas the rubbery modulus decreased due to the increased molecular weight between the crosslinks. In addition, as the NIPAM content increased, the film showed a positive yield with an increased yield and fracture stress and decreased ductility. Above 50% NIPAM, the film became brittle, showing a linear stress–strain relationship.     

Visible-Light-Induced C4-Selective Functionalization of Pyridinium Salts with Cyclopropanols

The site-selective C?H functionalization of heteroarenes is of considerable importance for streamlining the rapid modification of bioactive molecules. Herein, we report a general strategy for visible-light-induced β-carbonyl alkylation at the C4 position of pyridines with high site selectivity using various cyclopropanols and N-amidopyridinium salts. In this process, hydrogen-atom transfer between the generated sulfonamidyl radicals and O?H bonds of cyclopropanols generates β-carbonyl radicals, providing efficient access to synthetically valuable β-pyridylated (aryl)ketones, aldehydes, and esters with broad functional-group tolerance. In addition, the mild method serves as an effective tool for the site-selective late-stage functionalization of complex and medicinally relevant molecules.     

The antipode of a quasitriangular quasi-Turaev group coalgebra is bijective

In order to construct a class of new Turaev-braided group category with nontrivial associativity, the concept of a quasitriangular quasi-Turaev group coalgebras was recently introduced. Inside the definition, the conditions of invertibility of the R-matrix R and bijectivity of the antipode S are required. In this article, we prove that the antipode of a quasitriangular quasi-Turaev group coalgebra without the assumptions about invertibility of the antipode and R-matrix is inner, and a fortiori, bijective. As an application, we prove that for a quasitriangular quasi-Turaev group coalgebra, two conditions mentioned above are unnecessary.     

Noncovalent Intermolecular Interaction in Cofacially Stacked 24π Antiaromatic Hexaphyrin Dimer

π–π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π–π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar β,β’-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π–π interactions between the two subunits.     

Simultaneous determination of 75 abuse drugs including amphetamines,benzodiazepines, cocaine,opioids, piperazines,zolpidem and metabolites in human hair samples using liquid chromatography–tandem mass spectrometry

A liquid chromatography–tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten‐milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q‐sep dispersive solid‐phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2–200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra‐ and inter‐assay analysis at three QC levels were 4.3–12.9% and 89.2–109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers.     

Pericyclic reactions in the synthesis of new 5-aryl-5,6-dihydroquinolino[2,1-b]quinazolin-12-ones

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MAO‐free and extremely active catalytic system for ethylene tetramerization

The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C₆F₅)₄]^?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt₂)₂]⁺[B(C₆F₅)₄]^? and one equivalent CrCl₃(THF)₃ to (acac)AlEt₂ and subsequent treatment with a PNP ligand [CH₃(CH₂)₁₆]₂C(H)N(PPh₂)₂ ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl₃(THF)]²⁺[B(C₆F₅)₄]^?₂, which exhibited high activity when combined with iBu₃Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)₃, iPrN(PPh₂)₂, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe₃, –Si(nBu)₃, or –SiMe₂(CH₂)₇CH₃ at the para‐position of phenyl groups in 1 (i.e., by using [CH₃(CH₂)₁₆]₂C(H)N[P(C₆H₄‐p‐SiR₃)₂]₂ instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE.     

Effect of irradiation for sterilization on beverage reference materials for the analysis of food additives

Accreditation and Quality Assurance - Reference materials for proficiency testing (PT) were prepared for 6&nbsp;years. The target analytes were food additives, sorbic acid, benzoic acid, and...     

A BODIPY-based highly emissive dye with thiophene-based branch harvesting the light

ABSTRACT

A novel BODIPY-based dye with highly emissive character was configured by Sonogashira coupling and routinely characterized by NMR and MS technology. The emission of dye was investigated in solution/film/solid and shows intensive emission. In solution, the emission peak appeared around 510 nm with little influence by the polar environment. The terthiophene plays an effective antenna effect, harvesting the light and transferring the energy to BODIPY. The pseudo Stoke's shift enlarged to ～170 nm in solution. In film, the emission peak shifted to 563 nm in polycarbonate matrix. And it shifted further to 585 nm in solid due to the highly twisted structure, which avoided closely regular-tight packing. The dye rendered an intense fluorescence, good optothermal stability, and high fluorescence quantum yield (0.55). The solid emission showed highly red emission with Commission Internationale de L'Eclairage (CIE) coordinates of (X = 0.69, Y = 0.31). Thus, the synthesized dye is idea candidate for emitting materials.