The first example of phantom ring‐closing condensation polymerization for the synthesis of oligoguanidines is presented. A new oligoguanidine with a ring structure was achieved in one step by the condensation reaction of a triamine, like diethylenetriamine, with guanidine hydrochloride. The condensation reaction proceeded by selective ring‐closure towards the formation of five‐membered rings in the oligomer backbone. The resulting polymer repeat unit structure was different from the starting monomers (phantom polymer) and was formed by elimination of three molecules of ammonia per repeat unit. The inter‐, intra‐, and inter‐molecular reaction sequences led to the new structure as proved by different spectroscopic techniques (atmospheric pressure chemical‐ionization mass spectrometry, and one‐dimensional and two‐dimensional homo‐ and heteronuclear correlation NMR experiments) as well as supported by quantum chemical investigations. Preliminary results regarding antibacterial use of the resulting oligoguanidine were also promising and showed its effect within 15–30 min as an antibacterial material.
Herein, we report synthesis and self‐association properties of amphiphilic double‐comb polymers with polyglycidol backbones. First, a bifunctional polyglycidol precursor is synthesized via monomer activated anionic polymerization. Next, two efficient and orthogonal polymer analogous reactions are carried out for grafting hydrophilic oligoethylene glycol side chains and hydrophobic linear aliphatic side‐chains. The polymers are analyzed by means of NMR, GPC, and DSC. From the DSC analysis of the bulk samples it is evident that aliphatic side chains segregate from the polar backbone and thus crystallize. Furthermore, in aqueous media the double‐comb polymers spontaneously self‐assemble to form a multilayer structure. The present results pave a way to tailor and design amphiphilic polymers based on glycidols. Major advantages are spontaneous self‐assembly in water and the possibility to form onion polymersomes relevant to encapsulation.
The use of decatungstate in combination with silanes to generate silyl radicals under green fluorescence bulb irradiation as well as sunlight exposure is described. The mechanisms are investigated by ESR and laser flash photolysis experiments. The high potential of this reaction is evidenced here when using a decatungstate/silane/diphenyl iodonium salt combination as an initiating system for the ring opening photopolymerization of epoxides.
The eight‐shaped poly(ethylene oxide) (PEO) is synthesized by a combination of Glaser coupling with ring‐opening polymerization (ROP). Firstly, the star‐shaped (PEO‐OH) 4 is synthesized by ROP of ethylene oxide (EO) using pentaerythritol as an initiator and diphenylmethyl potassium (DPMK) as a deprotonated agent, and then the alkyne group is introduced onto the PEO arm‐end to give (PEO‐Alkyne) 4 in a NaH/tetrahydrofuran (THF) system. The intramolecular cyclization is carried out by a Glaser coupling reaction in a pyridine/CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) system at room temperature in an air atmosphere, and eight‐shaped PEO was formed with high efficiency (almost 100%). The target polymers and intermediates were well characterized by SEC, MALDI‐TOF MS, 1H NMR and FT‐IR in detail.
This paper summarizes the properties of strongly correlating liquids, i.e., liquids for which the virial/potential energy correlation coefficient is above 0.9 for equilibrium fluctuations in the NVT ensemble. The definition and properties of strongly correlating liquids' isomorphs are given, and various isomorph invariants are discussed. The cause of strong virial/potential energy correlations is also discussed, and it is argued that strongly correlating liquids are not merely to be thought of as approximate inverse power-law liquids. The experimental predictions for strongly correlating glass-forming liquids include: i) density scaling; ii) isochronal superposition; iii) that there is a single function of frequency from which all frequency-dependent viscoelastic response functions may be calculated; iv) that strongly correlating liquids are approximately single-parameter liquids with close to unity Prigogine-Defay ratio; v) that the fictive temperature initially decreases for an isobaric temperature up jump. The paper also briefly discusses the “isomorph filter”, which provides a necessary condition for universality of theories for the non-Arrhenius temperature dependence of the relaxation time. 相似文献
A design strategy is discussed in this paper,and it provides much convenience for effectively exploring achievable linear optics and globally investigating the flexibility of a complex lattice with superperiodicity.A matching method of fractional steps,which means separately finding the standard cell setting and the matching cell setting,is adopted to simplify the complexity of the linear beam optics design in the complex lattice.The multi-objective genetic algorithm is used to find most of all the stable linear optics,and reach a target solution after multi-generational propagation,both in the standard cell and the matching cell.A fitting algorithm with gradient information is used to restore the periodicity and symmetry of the lattice,and finely adjust the linear optics for further optimization.This design strategy is applied in the Shanghai Synchrotron Radiation Facility(SSRF)storage ring,and the results are presented. 相似文献
