A methodology to select suppliers to increase sustainability within supply chains

Central European Journal of Operations Research - Sustainability practice within supply chains remains in an early development phase. Enterprises still need tools that support the integration of...     

Record-high near-band-edge optical nonlinearities and two-level model correction of poled polymers by spectroscopic electromodulation and ellipsometry

The determination of nonlinearities near the band edge of organic and polymeric electro-optic(EO)materials is important from the viewpoint of molecular nonlinear optics(NLO)and photonic device applications.Based on transmission-mode Stark effect electromodulation(EM)spectroscopy,we study the electric-field-induced changes in optical absorption and refraction of newly developed EO polymers from the visible to near-infrared(NIR)wavelengths and report record-high near-band-edge complex EO effects from poled thin films.Values ofΔn andΔk up to 10^-3 and 10^-2 are found at an applied electric field of 2.0×10⁵-3.0×10⁵V/cm.The study of linear optical properties of poled films by spectroscopic ellipsometry shows large polinginduced birefringence and a nearly two-fold increase in the extinction coefficients at the extraordinary polarization.Through the Kramers-Kronig analysis,we obtained the real and imaginary second-order nonlinear coefficients up to~3,500 and~5,600 pm/V,respectively,which are believed to be the highest NLO coefficients of poled polymers through the resonance enhancement.Our approach goes beyond the previous works,applicable only to several discrete wavelengths,to a full-spectral analysis with independent verification of slab waveguide measurements.By considering both the electroabsorption and electrorefraction effects,our study overcomes the limitation of the classic qualitative two-level model and provides a quantitative understanding of near-resonance optical nonlinearities of organic EO materials.It can inspire the exploration of high-speed,absorptive,or phase-shifting light-modulators using EO polymers for on-chip applications.     

利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

化学工业生产中，用氢气为还原剂，通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物，而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径，但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb₂O₅(PVP: 聚乙烯吡咯烷酮)催化剂，该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应，系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能，在最优条件下，5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。     

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.     

Transition‐Metal‐Free Cross‐Coupling of Benzothiophenes and Styrenes in a Stereoselective Synthesis of Substituted (E,Z)‐1,3‐Dienes

A transition metal‐free one‐pot stereoselective approach to substituted (E,Z)‐1,3‐dienes was developed by using an interrupted Pummerer reaction/ligand‐coupling strategy. Readily available benzothiophene S‐oxides, which can be conveniently prepared by oxidation of the parent benzothiophenes, undergo Pummerer coupling with styrenes. Reaction of the resultant sulfonium salts with alkyllithium/magnesium reagents generates underexploited hypervalent sulfurane intermediates that undergo selective ligand coupling, resulting in dismantling of the benzothiophene motif and the formation of decorated (E,Z)‐1,3‐dienes.     

Validation of quartz crystal rheometry in the megahertz frequency regime

The utility of the quartz crystal microbalance (QCM) as a high‐frequency rheometer operating at 15 MHz was demonstrated. High‐frequency data obtained from a series of rubbery materials were compared with results obtained from traditional dynamic mechanical analysis (DMA) at much lower frequencies. The high‐frequency data enable meaningful shift factors to be obtained at temperatures much further above glass‐transition temperature (T _g) than would otherwise be possible, giving a more complete picture of the temperature dependence of the viscoelastic properties. The QCM can also be used to quantify mass uptake and changes in viscoelastic properties during sample oxidation. The viscoelastic response spanning the full range of behaviors from the rubber to glassy regimes was found to fit well with a six‐element model consisting of three power‐law springpot elements. One of these elements is particularly sensitive to the behavior in the transition regime where the phase angle is maximized. The value of this quantity is obtained from the maximum phase angle, which can be obtained from a temperature sweep at fixed frequency, proving a means for more detailed frequency‐dependent rheometric information to be obtained from a fixed‐frequency measurement at a range of temperatures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1246–1254     

Aggregation‐Induced Electrochemiluminescence of Carboranyl Carbazoles in Aqueous Media

The aggregation‐induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane‐free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds show a reductive–oxidative mechanism in contrast to other organic materials that show oxidative–reductive mechanisms. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications.     

Mycopyranone: A 8,8ˈ-binaphthopyranone with potent anti-MRSA activity from the fungus Phialemoniopsis sp.

A new 8,8?-binaphthopyranone (mycopyranone, 1) was isolated from a solid fermentation of Phialemoniopsis sp. (fungal strain MSX61662), and the structure was elucidated via analysis of the NMR and HRESIMS data. The axial chirality of 1 was determined to be M by ECD. The central chirality at C-4/C-4? was assigned through a modified Mosher’s method, while the absolute configuration at C-3/C-3? was deduced based on analysis of the ³J_H-3-H-4 values and NOESY correlations. Compound 1 was evaluated for its antimicrobial properties against Staphylococcus aureus SA1199 and a clinically relevant methicillin-resistant S. aureus strain (MRSA USA300 LAC strain AH1263). Compound 1 inhibited the growth of both strains in a concentration dependent manner with IC₅₀ values in the low μM range. Molecular docking indicated that compound 1 binds to the FtsZ (tubulin-like) protein in the same pocket as viriditoxin (2), suggesting that 1 targets bacterial cell division.