PHOTOCHROMISM AND LUMINESCENCE OF DOPANT CHROMOPHORES THROUGH TWO-PHOTON IONIZATION IN POLYMER FILMS

Two-photon ionization and recombination processes of an aromatic chromophore doped in polymer films were studied and the features of these processes were discussed in relation to photofunctional polymers. An aromatic molecule having low ionization potential, e.g., N,N,N',N'-tetramethyl-p-phenylene diamine doped in poly(methyl methacrylate)(PMMA) film was easily photoionized by intense laser light excitation, giving a colored radical cation (photochromism) and a trapped electron in PMMA matrix. As a reversed process, the radical cation recombined with the trapped electron, showing discoloration and emitting luminescence, either isothermal luminescence (ITL), or thermoluminescence (TL). In this report,ITL and TL through the charge recombination process were studied and the luminescence was suggested as a mean of the read-out of photorecording.

Characterization of Radiation Prepared Copolymer and Studies of Their Biodegradability

Blends of biodegradable copolymer based on starch, poly lactic acid (PLA), poly vinyl alcohol (PVA) and natural rubber (NR) have been prepared. Gamma radiation induced synthesis and modification of polymer hydrogel was studied. The polymer blends have been chemically surface modified by glycerol. The modified polymer blends have been investigated for swelling ratio, tensile strength and 9 scanning electron microscopy. The swelling ratio of polymer blends increased significantly after surface modification with glycerol. The swelling of polymer was decreased as a function of (NR) content in polymer blends. The gel fraction (PVA-starch-PLA) and (PVA-starch-NR) blends increased by increasing the radiation doses (kGy) to reach the maximum amount of (~99%) and (~88.2%), respectively. Addition of 2.5% (PLA) led to greater increase of the swelling ratio than 10% (NR) to blends and the maximum swelling was found at dose (5 kGy). At concentration of glycerol (5.0% w/w), tensile strength decreased and elongation at break % increased. The polymers degrading microorganisms were isolated from soil samples. The degradation ability of the microbial isolates for each polymeric material was tested on agar plates. Among these isolates, the most efficient degrader isolates for prepared blends in MSM shaking flasks were selected and the degradation was confirmed by scanning electron microscopy.

A Comparative Investigation of the Biodegradation Behaviour of Linseed Oil-Based Cross-Linked Composites Filled with Industrial Waste Materials in Two Different Soils

The biodegradation of polymeric biocomposites formed from epoxidized linseed oil and various types of fillers(pine needles,pine bark,grain mill waste,rapeseed cake)and a control sample without filler was studied during 180 days of exposure to two types of forest soil:deciduous and coniferous.The weight loss,morphological,and structural changes of polymer composites were noticed after 180 days of the soil burial test.The greatest weight loss of all tested samples was observed in coniferous forest soil(41.8%–63.2%),while in deciduous forest soil,it ranged between 37.7%and 42.3%.The most significant changes in the intensities of the signals evaluated by attenuated total reflectance infrared spectroscopy,as well as morphological changes determined by scanning electron microscopy,were assessed for polymer composite with rapeseed cake and specimen without filler in coniferous forest soil and are in a good agreement with weight loss results.Whereas significantly lower changes in weight loss,morphology,and structure of polymeric film with pine bark were noticed in both soils.It was suggested that fungi of Trichoderma,Penicillium,Talaromyces and Clonostachys genera are the possible soil microorganisms that degrade linseed oil-based cross-linked polymer composites.Moreover,the novel polymer composites have the potential to be an environmentally friendly alternative to petroleum-based mulching films.

N-heterocyclic Carbene Catalysed Polymerisation of 2,5-Diformylfuran

The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as well as the temperature and time the polymerization is running have a noticeable effect on its molar mass.The obtained material is charac­terized by nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and X-ray diffraction(XRD).An attempt at chain extension with diamine leads to precipitation of the polymer.This new biobased polymer material might be useful as a sustainable resin.

NOVEL SYNTHESIS OF POLYARYLENESULFONIUM CATIONS THROUGH A MULTI-ELECTRON TRANSFER PROCESS

The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in an acidic solution under atmosphericconditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acety-lacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen ox-idative polymerization. The polymerization mechanism involves multielectron oxidation ofthe sulfides followed by successive electrophilic substitution. The resulting polyarylenesul-fonium cations are useful as a soluble precursor for the synthesis of high molecular weight(M_w】10~5) poly(thio arylne)s.

用多官能团引发剂合成超支化聚苯乙烯及其C_(60)衍生物

通过α-溴丙酰溴与 Z5(季戊四醇与 2 ,2 -二羟甲基丙酸缩聚的产物 )酯化反应制得超支化原子转移自由基聚合 ( ATRP)引发剂 Z5- B(约含 19个引发点 ) .在 10 0℃及 Cu Cl/ N,N,N ,N" ,N" -五甲基二亚乙基三胺催化下 ,用 Z5- B引发苯乙烯的 ATRP聚合 (环己酮为溶剂 ,体积分数为 50 % ) ,得到超支化的聚苯乙烯 ,将溴端基叠氮化后与 C6 0 反应 ,获得超支化聚苯乙烯 C6 0 衍生物 .该超支化 C6 0 衍生物可用于光限制材料 .

HYDRATION AND PHASE SEPARATION OF TEMPERATURE-SENSITIVE WATER-SOLUBLE POLYMERS

倒塌一( N-isopropylacrylamide )( PNIPAM ) poly 在加热之上锁住并且与很扁平的 LCST 分阶段执行水的 PNIPAM 答案的图阶段分离线理论上根据合作脱水(在一组相关顺序的界限水分子的同时的分离)被学习，并且与由光的导致温度的卷水珠转变的试验性的观察相比散布方法。转变与水和的 cooperativity 参数变得更锋利。在水和甲醇的混合溶剂的重入的 coil-globule-coil 转变也从在聚合物水和聚合物甲醇之间的竞争的氢契约的观点被学习。向下，有甲醇的鼹鼠部分的云点曲线(LCST cononsolvency ) 的移动由于比赛被计算并且与试验性的数据相比。在两链结束(telechelic PNIPAM ) 带短烷基链的修改 hydophobically 的 PNIPAM 的水的答案理论上并且试验性地被学习。这些答案的 LCST 被发现由于结束链协会(导致协会的阶段分离) 沿着大音阶的第五音胶化转变曲线向下变，并且与卷水珠转变线分开。在答案的联系结构例如花微粒， mesoglobules 和更高分数维的汇编，被 USANS 与散布功能的理论建模学习。

Human Serum Albumin Hybrid Incorporating Synthetic Hemes:A Novel O_2-Carrying Hemoprotein

Incorporation of synthetic heme(FeP) into recombinant human serum albumin(rHSA) provides an artificial hemoprotein(rHSA-FeP) which can bind and release oxygen reversibly under physiological conditions(in aqueous media, pH 7.3, 37 ℃) like hemoglobin(Hb) and myoglobin. An rHSA host absorbs maximally eight FeP molecules, and the solution properties are almost identical to those of rHSA itself. The second-order structure and surface charge distribution of rHSA were always constant independent of the binding numbers of FeP. Its O 2-binding ability satisfies the initial clinical requirements for red cell substitute. Although the NO-binding affinity is 8-fold high compared to the Hbs, administration of this fluid into rats showed negligible change in the blood pressure. Physiological responses to exchange transfusion with this rHSA-FeP into anaesthetized rats have also been evaluated.

SELECTIVE NEURITE OUTGROWTH ON SILVER NEGATIVE ION (Ag^- )-IMPLANTED POLYSTYRENE SURFACES

The negative ion implantation technique was applied to modify polymer surfaces of culture dishes for neuronal cells, PC12h. The silver negative ion (Ag-)-implantation was carried out at an ion energy of 20 keV and a dose of 3 × 1015 ions/cm2 with non-treated polystyrene (NTPS), tissue culture polystyrene (TCPS), and collagen-coated TCPS-Iwaki (CCPS). Ag--implanted surfaces of Ag/NTPS, Ag/TCPS, and Ag/CCPS were studied with respect to contact angle and/or chemical composition. The numerical values of contact angles on Ag/NTPS and Ag/TCPS were similar within experimental error, indicating the resemblance in their hydrophobicity and hydrophilicity. The PC12h cells, however, were attached only to the Ag--implanted region of NTPS, but not to the non-implanted NTPS region. Moreover, the neurite outgrowth was also observed to extend specifically along the Ag--implanted region of NTPS but not on the non-implanted NTPS region, although neurites extended towards all directions on collagen-coated TCPS as a control surface. There was no remarkable difference in neurite outgrowth among Ag--implanted regions of TCPS and CCPS. Thus Ag/NTPS region was affirmed to promote highly selective attachment, growth, and differentiation of PC12h cells, although its mechanism is still unknown.

Preparation of epoxy resin/rare earth doped aluminate nanocomposite toward photoluminescent and superhydrophobic transparent woods

A translucent wooden substrate with long-lasting phosphorescence,high photostability and durability,tough surface,ultraviolet protection,high optical transmittance,and superhydrophobicity was developed.This long-lasting phosphorescent wooden substrate is able to continue emitting light for extended time periods.Lignin-modified wood(LMW)was immobilized with a solution of epoxy resin(ER)and rare-earth doped aluminate(REDA)phosphor nanoparticles(NPs).For an improved dispersion of pigment,REDA was synthesized in a nanoscale particle size,and characterized by transmission electron microscopy(TEM)to indicate a particle size of 8-14 nm.The crystal structure of REDA nanoparticles was also proved by X-ray diffraction(XRD).For an improved production of long-persistent phosphorescent colo rless woods,REDA must be well-dispersed in MAA without aggregation.Absorption and emissio n,as well as decay and lifetime spectra were explored.The morphologies of the wooden substrates with different ratios of REDA were investigated by scanning electron microscopy(SEM),X-ray fluorescence(XRF)analysis,Fourier transform infrared spectra(FT-IR),elemental mapping,and energy-dispersion Xray(EDXA).The phosphorescent woods show changes in color from colorless to green under ultraviolet(UV)irradiation,and to yellowish-green in the dark,as proved by the colorimetric parameters of the CIE Lab system.The afterglow wood samples display an absorbance band at 365 nm and two phosphorescent bands at 431 and 520 nm.Improved UV shielding,photostability,and hydrophobicity were explored.With increasing REDA ratio,both static contact and slide angles are found to improve in the ranges of147.6°-163.6°and 9°-14°,respectively.The long-lasting photoluminescence is optimized at a REDA ratio of 8%.The present strategy shows a large-scale production approach of multiple functional woods for many potential applications,such as smart glow in the dark windows and safety signs.

Micelle-crosslinked hydrogels with stretchable,self-healing,and selectively adhesive properties:Random copolymers work as dynamic yet self-sorting domains

The design of crosslinking domains is a vital factor to create functional hydrogels with controlled physical,mechanical,and adhesive properties.This paper demonstrates versatile synthetic systems of micelle-crosslinked hydrogels with highly stretchable,self-healing,and selectively adhesive properties.For this,methacrylate-bearing random copolymer micelles are designed as physical and covalent crosslink domains via the self-assembly of amphiphilic random copolymers carrying hydrophilic poly(ethylene glycol)(PEG),hydrophobic butyl or dodecyl groups,and methacrylate-terminal PEG in water.The size,aggregation number,and pendant methacrylate number of the micelles are controlled by the composition and degree of polymerization.Hydrogels are efficiently obtained from the free radical polymerization of hydrophilic monomers such as PEG acrylate and acrylamide in the presence of the micelle crosslinkers in water.Owing to the dynamic yet selective chain exchange properties of the micelle domains,the hydrogels are highly stretchable up to over 1000%and show self-healing and selectively adhesive properties.The self-healing of hydrogels is promoted upon heating due to the fast chain exchange of the micelle domains,whereas hydrogels consisting of micelles with different alkyl groups are never adhesive because of their self-sorting properties.

Effect of Functionalized Magnetite Nanoparticles and Diaminoxanthone on the Curing, Thermal Degradation Kinetic and Corrosion Property of Diglycidyl Ether of Bisphenol A-Based Epoxy Resin

To prepare a high-performance epoxy resin with excellent thermal, chemical and corrosion stability, diaminoxanthone(DAX) was used to cure diglycidylether of bisphenol-A(DGEBA)-based epoxy resin and blend of DGEBA with functionalized Fe3O4 nanoparticles. Kinetic parameters of curing and thermal degradation of epoxy resin systems were estimated by differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA), respectively. The 10% weight loss temperature has been increased from 340 °C to 366 °C and there was an increase in the char yield from 32.6% to 45.3% for the above systems. The corrosion performance of epoxy coated carbon steel was examined by potentiodynamic polarization, along with immersion test in 1.0 mol/L HCl solution. The results showed that epoxy resins cured with DAX had low tendency to corrosion. In addition, the cured epoxy resin containing 10% Fe3O4 had higher anticorrosion activity than bare DGEBA system. The results showed that functionalized Fe3O4 nanoparticles enhanced char formation and improved the thermal stability as well as anticorrosion activity of the resin.

Professor Fosong Wang on his 80th birthday:A great scientist and a great ambassador

It is a great pleasure for international colleagues in polymer science to celebrate Professor Fosong Wang on his 80th birthday. Professor Fosong Wang, a member of the Chinese Academy of Sciences, is a great polymer scientist, with over 300 publications and a few books. He is internationally recognized in his work on stereoregular polymers and electronically active polymers, particularly the development

Comparison of luminescent properties of helicene-like bibenzothiophenes with o-carborane and 5,6-dicarba-nidodecaborane

This article describes comparison of the anchoring effect on electronic properties of the helicene-like bibenzothiophene between o-carborane and 5,6-dicarba-nido-decaborane. The o-carborane and nido-decaborane-fused bibenzothiophenes were simultaneously obtained in the same reaction and successfully isolated. Initially, the X-ray single crystal analysis revealed that the helicene-like distorted structure was realized in the nido-decaborane-fused bibenzothiophene. From optical measurements in the solution state, distinct different characteristics depending on the type of anchors were observed. It was summarized that the absorption and luminescent properties originated from weak π-conjugation at the bibenzothiophene moiety in the o-carboranefused compound were obtained, whereas robust π-conjugation and significant emission from the intramolecular charge transfer state were detected from the nido-decaborane-fused compound. These data can be explained by the theoretical results that π-conjugation was restrictedly developed within the bibenzothiophene moiety in frontier orbitals of the o-carborane-fused compound. In contrast, π-conjugation can be constructed even through the distorted bibenzothiophene because of the nido-decaborane unit. Moreover, the intramolecular charge transfer state should be realized because of electronic interaction involving the nido-decaborane unit in the excited state. Furthermore, it was demonstrated that the nido-decaborane-fused compound possessed solid-state emission and mechanochromic luminescent properties. The π-conjugation on the distorted structure supported by the nido-decaborane anchor should play a significant role in suppressing aggregation-caused quenching followed by presenting solid-state emission with stimuli responsiveness.

Organic-inorganic Polymer Nano-hybrids Based on Sol-gel Reaction

1 Results Nano-ordered composite materials consisting of organic polymers and inorganic materials have been attracting attention for the purpose of the creation of high-performance or high-functional polymeric materials. Especially,the word of "polymer hybrid" claims the blends of organic and inorganic components at nano-level dispersion. By using this idea,an enhancement of mechanical strength of organic polymers with silica particles is possible.High transparency of this material is another important ...

New insights into the effects of molecular weight and end group on the temperature-induced phase transition of poly(N-isopropylacrylamide) in water

In an attempt to clarify issues related to the molecular weight dependence of the phase transition of poly(N-isopropylacrylamide) (PNIPAM) in water,we prepared a library of PNIPAM samples of well-controlled molecular weight (7000 to 45000 g/mol) bearing identical groups on each chain end.The polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) with a bifunctional chain tranfer agent and further end group modification.The effects of the end group chemical structure,hydroxyethyl (HE),propargyl (Pr),chloroethyl (CE),n-butyl (nBu),n-hexyl (nHe),and isobutylsulfanylthiosulfanyl (IBS) on the phase transition temperature of aqueous PNIPAM solutions were investigated by high-sensitivity differential scanning calorimetry (HS-DSC),yielding the enthalpy ΔH and the endotherm maximum temperature (T M),and turbidimetry,providing the cloud point (T CP) of each solution.The T CP and T M of the PNIPAM sample of lowest molar mass (M n 7,000 g/mol,0.5 g/L) ranged,respectively,from 38.8 to 22.5 °C and 42.2 to 26.0 °C,depending on the structure of the end-group,whereas H showed no strong end-group dependence.The phase transition of all polymers,except,-di(n-butyl-PNIPAM),exhibited a marked dependence on the polymer molar mass.

Charge generation in organic solar cells: Journey toward 20% power conversion efficiency

The power conversion efficiencies of organic solar cells(OSCs)have routinely lagged far behind those of their inorganic counterparts.However,owing to the enor-mous contributions of many researchers,the power conversion efficiencies of OSCs have rapidly improved and now exceed 19%.The charge generation mechanisms in OSCs have been heavily debated during this period while acquiring valuable knowl-edge.This review highlights fundamental and cutting-edge research that rationalizes why OSCs can generate photocurrent so efficiently.In particular,a photophysi-cist’s views on exciton diffusion to donor:acceptor interfaces,charge transfer at the donor:acceptor interface,and long-range spatial dissociation of charge transfer states are discussed.Although a general consensus in this area has not been reached yet,recent time-resolved spectroscopic measurements provide important photophys-ical insights that can help achieving a better understanding of the charge generation mechanism in OSCs.Based on these observations,future research directions for realizing further improvements in OSC performance are discussed.

Positive Luminescent Sensor for Aerobic Conditions Based on Polyhedral Oligomeric Silsesquioxane Networks

There are numerous numbers of hypoxia-selective luminescent probes based on oxygen quenching of phosphorescence.We show a unique design for luminescent probes to detect hyperoxia utilizing hybrid networks consisting of aggregation-induced emission(AIE)-active dyes and disulfide linkers.At the initial state,emission from the AIE-active dyes is inducible by suppressing energy-consumable intramolecular motions in the hybrid matrices,while the decrease in intensity was detected by releasing molecular motions corresponded to bond scission at the disulfide linkers.Particularly,it was shown that this process selectively proceeds in hypoxia.As a result,positive luminescent signals were obtained in hyperoxia.

Rational design for thermochromic luminescence in amorphous polystyrene films with bis-o-carborane-substituted enhanced conjugated molecule having aggregation-induced luminochromism

We designed the triad molecule,bis-o-carborane-substituted bis(thienylethynyl)benzene,as a filler for realizing thermochromic luminescent behaviors based on conventional polymer films,such as polystyrene.From the optical measurements,it was found that the triad can show solid-state emission and dual-luminescent properties with variable intensity ratios depending on media.From the mechanistic studies including the experiments with the methyl-substituted model compound,it was revealed that dual emission should be originated from the locally excited and twisted intramolecular charge transfer states,and the latter emission band is significantly enhanced in the solid states.We prepared amorphous films containing variable concentrations of the triad with the spin-coating method and investigated optical properties.It was found that intensity ratios were drastically changed by altering the concentration of the triad.By increasing the proportion of the triad,aggregation occurred,and emission color was apparently varied through the changes in intensity ratios of the dual emission property.Based on the aggregationinduced luminochromic property of the triad,thermochromic luminescence was finally realized by heating the amorphous films.The rational design for obtaining thermochromic luminescent amorphous films is illustrated in this paper.