Ring-opening polymerization of macrocyclic aryl ether ketone oligomers containing the 1,2-dibenzoylbenzene moiety

Facile ring-opening polymerization of cyclic aryl ether oligomers containing the 1,2-dibenzoylbenzene moiety to form high molecular weight linear polymers in the presence of a nucleophilic initiator is described. The polymerization can be initiated in the melt in the presence of a nucleophilic initiator such as potassium carbonate, cesium fluoride, and alkali phenoxides. Various alkali phenoxides were investigated as potential nucleophilic initiators. The polymerization reaction rate in the melt increases in the order of K⁺ > Na⁺ > Cs⁺, and in the order of ⁻OPhPhO⁻ > PhO⁻ > PhOPhO⁻ > PhPhO⁻. However, the polymerization in an aprotic dipolar solvent is faster in the presence of cesium phenoxide than in the presence of potassium phenoxide. Polymerization of the cyclic oligomers in solution demonstrates that the ring-opening polymerization proceeds via a chain-growth mechanism and involves a transetherification reaction between linear and cyclic aryl ether oligomers. The ring-chain equilibrium is much more favorable towards linear polymers. Since little or no ring strain exists in the cyclic system, the transetherification reactions are indiscriminate with regards to cyclic or linear chains and the interchain equilibration is also a facile process during polymerization. This intermolecular transetherification has been demonstrated by using low molecular weight aryl ethers to control the molecular weight of the polymer formed via ring-opening polymerization. © 1996 John Wiley & Sons, Inc.     

Strategies in boosting photosensitization for biomedical applications

Science China Chemistry -     

A ray model for hard parallel noise barriers in high-rise cities

A ray model is developed and validated for prediction of the insertion loss of hard parallel noise barriers placed in an urban environment either in front of a row of tall buildings or in a street canyon. The model is based on the theory of geometrical acoustics for sound diffraction at the edge of a barrier and multiple reflections by the ground, barrier and fa?ade surfaces. It is crucial to include the diffraction and multiple reflection effects in the ray model as they play important roles in determining the overall sound pressure levels for receivers located between the fa?ade and the near-side barrier. Comparisons of the ray model with a wave-based boundary element formulation show reasonably good agreement over a broad frequency range. Results of scale model experimental studies are also presented. It is demonstrated that the ray model agrees tolerably well with the scale model experimental data.     

Reverse Thinking of the Aggregation-Induced Emission Principle: Amplifying Molecular Motions to Boost Photothermal Efficiency of Nanofibers**

Using reverse thinking of the aggregation-induced emission (AIE) principle, we demonstrate an ingenious and universal protocol for amplifying molecular motions to boost photothermal efficiency of fibers. Core–shell nanofibers having the olive oil solution of AIE-active molecules as the core surrounded by PVDF-HFP shell were constructed by coaxial electrospinning. The molecularly dissolved state of AIE-active molecules allows them to freely rotate and/or vibrate in nanofibers upon photoexcitation and thus significantly elevates the proportion of non-radiative energy dissipation, affording impressive heat-generating efficiency. Photothermal evaluation shows that the core–shell nanofibers with excellent durability can reach up to 22.36 % of photothermal conversion efficiency, which is 26-fold as the non-core–shell counterpart. Such a core–shell fiber can be used for photothermal textiles and solar steam generation induced by natural sunlight with green and carbon-zero emission.     

Key Word Index for Volume 11

Other Index

Key Word Index for Volume 11     

Functionalized Alkynylplatinum(II) Polypyridyl Complexes for Use as Sensitizers in Dye‐Sensitized Solar Cells

A series of platinum(II) alkynyl‐based sensitizers has been synthesized and found to show light‐to‐electricity conversion properties. These dyes were developed as sensitizers for the application in nanocrystalline TiO₂ dye‐sensitized solar cells (DSSCs). Their photophysical and electrochemical properties were studied. The excited‐state property was probed using nanosecond transient absorption spectroscopy, which showed the formation of a charge‐separated state that arises from the intramolecular photoinduced charge transfer from the platinum(II) alkynylbithienylbenzothiadiazole moiety (donor) to the polypyridyl ligand (acceptor). A lifetime of 3.4 μs was observed for the charge‐separated state. A dye‐sensitized solar cell based on one of the complexes showed a short‐circuit photocurrent of 7.12 mA cm^?2, an open circuit voltage of 780 mV, and a fill factor of 0.65, thus giving an overall power conversion efficiency of 3.6 %.     

A Time‐Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3′,5′‐Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction Pathway

3′,5′‐Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3′,5′‐dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs‐TA) spectroscopy and nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile (CH₃CN). To assess the electronic character and the role played by the individual sub‐chromophore, that is, the benzoyl, and the di‐meta‐methoxybenzylic moieties, for the DMBDP deprotection, comparative fs‐TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3′,5′‐dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs‐TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady‐state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub‐chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The ns‐TR³ results and their correlation with the fs‐TA spectra and dynamics provide evidence for a novel concerted deprotection–cyclization mechanism for DMBDP in CH₃CN. By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ≈1 ns. This indicates that there is little relevance for the long‐lived intermediates (>10 ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3′,5′‐dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs‐TA results on the reference compound DMBnDP in CH₃CN provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (≈2 ps) heterolytic bond cleavage after photoexcitation of meta‐methoxybenzylic compounds. This provides insight into the long‐term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds.     

Thermal and mass spectrometric fragmentation of esters of deuterated long chain carboxylic acids

A method combining thermal fragmentation and mass spectrometry for the determination of the position of double bonds in an unsaturated ester is presented. The thermal fragmentation of methyl esters of deuterated long chain carboxylic acids yields a homologous series of olefins plus a homologous series of unsaturated esters. The positions of the deuterium atoms in the original ester are revealed by the deuterium content of its fragments as determined by mass spectrometry. Therefore, the positions of double bonds of a polyunsaturated acid can be determined by pyrolysis after saturation by deuterium. The structures of the unsaturated fragments are ascertained by mass spectrometric method, and the formation of the ion [M – 32] in the mass spectrometric fragmentation of unsaturated methyl esters is studied by means of deuterium labeling.     

Applying Direct Yellow 11 to a modified Simons’ staining assay

For quantification of overall fiber accessibility of lignocellulosic substrates, Direct Yellow 11 (C.I. 40000) is a suitable alternative to the discontinued Pylam Products’ dye Direct Orange 15 (C.I. 40002/40003). In this study we present a side-by-side comparison between the two azo-stilbene dyes. We characterize individual dye fractions and provide equations to determine individual concentrations. We present a modified Simons’ staining protocol incorporating the high molecular weight fraction of Direct Yellow 11. We perform tests on lignin, cellulosic, and lignocellulosic materials. In all tests, the two dyes perform similarly and satisfy many accessibility measurement criteria. We demonstrate that the adsorption of Direct Yellow 11 onto a substrate correlates with that substrate’s propensity for enzymatic hydrolysis. We confirm this correlation on a series of organic solvent pretreatments and on a series of lignocellulosic substrates. Finally, we outline the inherent limitations of performing adsorption experiments with Direct Yellow 11 and other high molecular weight dyes.