As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneou...As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.展开更多
Bis (7- diethylaminocoumarin) ketone- 3(DACK) and diphenyliodonium salt (DPIO)combination as an effective photoinitiation system for radical polymerization has been investigated. The sensitized photolysis of DACK/DPIO...Bis (7- diethylaminocoumarin) ketone- 3(DACK) and diphenyliodonium salt (DPIO)combination as an effective photoinitiation system for radical polymerization has been investigated. The sensitized photolysis of DACK/DPIO leads to bleaching of DACK and decomposition of DPIO to generate initiating radical species. The electron transfer sensitization occurs mainly from the triplet state of DACK. The photobleaching obeyed a second-order kinetics and the rate constant was evaluated to be 31.3mol^(-1)·1·s^(-1) Photopolymerization of MMA initiated by DACK/DPIO was carried out in acetonitrile solution. The polymerization rate was found to be proportional to the concentration of DACK, DPIO and MMA with the exponents of 0.34, 0.40 and 1.0 respectively. The initiated efficiency is comparable to those of small molecular ketones.The sensitized photoinitiation mechanism has been discussed.展开更多
Photoinitiators(PIs), as the key substances for photopolymerized antibacterial film(PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the can...Photoinitiators(PIs), as the key substances for photopolymerized antibacterial film(PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the candidates, BDO1 has demonstrated the ability to initiate polymerization of acrylate monomers as single-component PI with the advantages of low mobility, outstanding photobleaching, excellent cytocompatibility, and suitability for light emitting diode(LED) light sources above 365 nm. Taking BDOs as examples, a novel method based on theoretical calculations aiming to assess the potential of enone molecules as single-component PIs was proposed. Finally, under the initiation of BDO1, tannic acid was photopolymerized to a colorless and transparent antibacterial film with high antibacterial ability, which indicated that BDO1 was expected to be used in environmentally friendly PAF.展开更多
Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF)...Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.展开更多
Photoinitiators(PIs),as an important component of UV inks,are widely used in the printing of paper food packaging.Nevertheless,there is limited information concerning the identification of PIs in food packaging and th...Photoinitiators(PIs),as an important component of UV inks,are widely used in the printing of paper food packaging.Nevertheless,there is limited information concerning the identification of PIs in food packaging and their potential migration rules under natural storage condition.In this study,23 target PIs detected in paper food packaging were dominated by benzophenones(BZPs),followed by amine co-initiators(ACIs),thioxanthones(TXs)and phosphine oxides(POs).The concentration of ΣPIs ranged between 48.3 and 1.11×10^(5)ng/g.Meanwhile,the concentration ofΣPIs were found to be significantly higher in Corrugated paper compared to Polyethylene(PE)coated paper,Composite paper and White card paper.Benzophenone(BP)was found as the dominant PI congener in Corrugated paper,with the concentration ranging from 923-3.66×10^(4)ng/g.The migration quantity ofΣPIs increased in a time-dependent manner in the first 13 days and then eventually reached equilibrium.Low temperatures had a certain inhibitory effect on the migration of PIs from paper packaging to food.Under high exposure scenario,the EDIs of ΣPIs for children,adolescents,and adults were 31.4 ng/(kg bw·day),17.2 ng/(kg bw·day),and 14.4 ng/(kg bw·day),respectively,all of which did not exceed the reference dose,indicating that dietary intake of PIs does not pose any health risks to the human body.展开更多
Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmos...Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmospheres(e.g.argon,nitrogen)are usually required.Moreover,the large-scale preparation of block copolymer nano-objects at room temperature is challenging.Herein,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen toleranee.The addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air conditions.Polymerization kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen tolerance.Block copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent composition.We expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.展开更多
Polyethylene terephthalate(PET)and polyethylene(PE)fibers were surface photo-grafted with acrylic acid(AA)by using UV irradiation photochemical initiationduring a continuous winding process within 1-2 min-utes.The gra...Polyethylene terephthalate(PET)and polyethylene(PE)fibers were surface photo-grafted with acrylic acid(AA)by using UV irradiation photochemical initiationduring a continuous winding process within 1-2 min-utes.The grafted fibers were characterized by measure-ments of dye uptaking,moisture regain,pull-out forcesof monofilament from cured matrix,as well as by analy-sis of ESCA and ATR-FTIR spectra.All these resultsconfirm that the surface behavior of the UV-irradiationgrafted fibers was greatly improved.It was also provedthat the original excellent mechanical properties of the fi-bers were well-retained after the surface grafting treat-ment.展开更多
Owing to the special fo rmation of photopolymerized hydrogels,they can effectively control the formation of hydrogels in space and time.Moreover,the photopolymerized hydrogels have mild formation conditions and biocom...Owing to the special fo rmation of photopolymerized hydrogels,they can effectively control the formation of hydrogels in space and time.Moreover,the photopolymerized hydrogels have mild formation conditions and biocompatibility;therefore,they can be widely used in tissue engineering.With the development and application of manufacturing technology,photopolymerized hydrogels can be widely used in cell encapsulation,scaffold materials,and other tissue engineering fields through more elaborate manufacturing methods.This review covers the types of photoinitiators,manu facturing technologies for photopolymerized hydrogels as well as the materials used,and a summary of the applications of photopolymerized hydrogels in tissue engineering.展开更多
We synthesized four diphenylquinoxaline derivatives（SQs） with phenyl-thioether units, which combine photo-cleavable and hydrogen-abstracting groups in one molecule. The photochemistry and photopolymerization of SQs ...We synthesized four diphenylquinoxaline derivatives（SQs） with phenyl-thioether units, which combine photo-cleavable and hydrogen-abstracting groups in one molecule. The photochemistry and photopolymerization of SQs were investigated. SQs possess suitable UV-vis absorption in the range of 350-400 nm with high extinction coefficients. UV-vis and HPLC-MS spectra revealed that C–S bond in phenyl-thioether group of SQs can be broken by irradiation of UV-light. Photolysis and photopolymerization experiments showed that SQs can be used as photo-cleavable photointiators,their photoinitiating efficiency can be enhanced by hydrogen donor. As photo-cleavable photoinitiators,SQs could initiate hexamethylene diacrylate（HDDA） very efficiently with the double bond conversion（DBC） of 80%. In the presence of ethyl-4-（dimethylamino） benzoate（EDB） as coinitiator, photoinitiator systems initiated photopolymerization of commercial acrylate monomers with higher double bond conversion than 90%. These characteristics make SQs potential photoinitiators in photo-curing field.展开更多
Photoinitiators(PIs)are widely used in industrial polymerization processes.It has been reported that PIs are ubiquitous in indoor environments and that humans are exposed to PIs,but the occurrence of PIs in natural en...Photoinitiators(PIs)are widely used in industrial polymerization processes.It has been reported that PIs are ubiquitous in indoor environments and that humans are exposed to PIs,but the occurrence of PIs in natural environments are rarely known.In the present study,25 PIs,including 9 benzophenones(BZPs),8 amine co-initiators(ACIs),4 thioxanthones(TXs)and 4 phosphine oxides(POs),were analyzed in water and sediment samples collected from eight riverine outlets of the Pearl River Delta(PRD).Eighteen,14,and 14 of the 25 target PIs were detected in water,suspended particulatematter(SPM)and sediment samples,respectively.The total concentrations of PIs in water,SPM,and sediment were in the ranges of 2.88–96.1 ng/L,9.25–923 ng/g dry weight(dw),and 3.79–56.9 ng/g dw,with geometric mean concentration(GM)of 10.8 ng/L,48.6 ng/g dw,and 17.1 ng/g dw,respectively.A significant linear regression was observed between the log partitioning coefficients(Kd)values of PIs and their log octanol water partition coefficient(Kow)values(R^(2)=0.535,p<0.05).The annual riverine input of PIs to the coastal waters of the South China Sea via eightmain outlets of the PRD was estimated to be 4.12×10^(3)kg/year,and the∑BZPs,∑ACIs,∑TXs and∑POs contributed to 1.96×10^(3),1.24×10^(3),89.6 and 830 kg/year,respectively.This is the first report of a systematic description of the occurrence characteristics of PIs exposure in water,SPM,and sediment.The environmental fate and risks of PIs in aquatic environments need further investigations.展开更多
Dodecyl-benzophenone（DBP） and hexadecoxyl-benzophenone（HDBP） as type 11 photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTI...Dodecyl-benzophenone（DBP） and hexadecoxyl-benzophenone（HDBP） as type 11 photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%（mass fraction） tripropyleneglycol diacrylate （TPGDA）, resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry（photo-DSC）. DBP initiates the curing of acrylate more efficiently than HDBP, showing higher photopolymerization rate and unsaturation conversion, resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.展开更多
Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long...Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopendadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4. and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoinitiating activities in epoxy resins.展开更多
Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized ...Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.展开更多
The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising propert...The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.展开更多
A novel preparation of aluminum diethylphosphinate（AlPi） was carried out with free-radical addition reaction by means of UV-irradiation under atmospheric pressure.A solution of sodium hypophosphite was treated with ...A novel preparation of aluminum diethylphosphinate（AlPi） was carried out with free-radical addition reaction by means of UV-irradiation under atmospheric pressure.A solution of sodium hypophosphite was treated with ethylene and irradiated with ultraviolet light in the presence of an amount of photoinitiator effective to initiate the free-radical reaction between the hypophosphite anion and the double bond of the ethylene molecule.The ethylene was micro-bubbled into the reaction mixture with the addition of the photoinitiator,and the gas-liquid contact surface and the photoinitiator concentration in the gas-liquid interface were increased largely.The yield of the final product could be improved to about 96%.The contents of P,Al in samples were detected by ICP,and the molecular structure of the samples was confirmed by ^（31）P NMR,~1H NMR and FTIR spectroscopic analysis.Thermal stability of the final products was investigated in detail by TG-DTA.展开更多
Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator...Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator is described.展开更多
To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a serie...To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperhranched polymeric photoinitiators （hPEA-TXs, and hPEA- BPs） by introducing thioxanthone （TX） or benzophenone （BP） moieties into the periphery of the hyperbranched poly（ether amine） （hPEA） comprised of the hydrophilic poly（ethylene oxide） （PEO） short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10 wt~. The photopolymerization kinetics of water-soluble monomer acrylamide （AM） and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric （photo-DSC）. Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion （DBC） of oil-soluble monomer hexanediol diacrylate （HDDA） photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate （TMPTA） and pentaerythritol tetraacrylate （PETTA） can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.展开更多
Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long...Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopen- dadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4, and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoini- tiating activities in epoxy resins.展开更多
Dear Editor,Timely and effective hemostasis is of great significance for reducing body damage and mortality of patients [1]. Alginate is generally considered to be an excellent hemostatic polymer-based biomaterial and...Dear Editor,Timely and effective hemostasis is of great significance for reducing body damage and mortality of patients [1]. Alginate is generally considered to be an excellent hemostatic polymer-based biomaterial and has been approved by the Food and Drug Administration as Generally Recognized as Safe [2]. However, the violent crosslinking reaction and unstable structure at the wound site limit its clinical applications. Hence, we report a biocompatible and injectable composite hydrogel methacrylate alginate (Alg-AEMA)-based Eosin Y/N-phenylglycine (NPG)-initiated composite hydrogel (AEC) composed of photocrosslinkable alginate, viscosity modifiers and novel white light photoinitiator, namely Eosin Y/NPG system, for instant hemorrhage control.展开更多
Holographic parameters and photobleaching kinetics of the photopolymers with five different amine photoinitiators are studied. The maximum values of diffraction efficiency, photobleaching coefficient and quantum yield...Holographic parameters and photobleaching kinetics of the photopolymers with five different amine photoinitiators are studied. The maximum values of diffraction efficiency, photobleaching coefficient and quantum yield follow the sequence： Triethanolamine （TEA）〉 Diethanolamine （DEA）〉 Ethanolamine （EA）〉 Triethylamine （TETN）〉 Diethylamine （DETN）. The holographic capabilities of photopolymer performances are determined by the number of functional groups in the amine molecular structure. There is an optimum proportion of the photoinitiator, the photosensitizer and the monomer in the test of holographic parameters with different amine concentrations. The maximum diffraction efficiency is 59.26／%, sensitivity is 1.72／times 10^{ - 3}~cm^{2}/mJ, and the maximum refractive modulation index is 4.64／times 10^{ - 4}.展开更多
基金National Nature Science Foundation of China(Nos.52025032,52103144 and 523B2026)for their financial supportsupported by the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(No.GZC20231544)。
文摘As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.
文摘Bis (7- diethylaminocoumarin) ketone- 3(DACK) and diphenyliodonium salt (DPIO)combination as an effective photoinitiation system for radical polymerization has been investigated. The sensitized photolysis of DACK/DPIO leads to bleaching of DACK and decomposition of DPIO to generate initiating radical species. The electron transfer sensitization occurs mainly from the triplet state of DACK. The photobleaching obeyed a second-order kinetics and the rate constant was evaluated to be 31.3mol^(-1)·1·s^(-1) Photopolymerization of MMA initiated by DACK/DPIO was carried out in acetonitrile solution. The polymerization rate was found to be proportional to the concentration of DACK, DPIO and MMA with the exponents of 0.34, 0.40 and 1.0 respectively. The initiated efficiency is comparable to those of small molecular ketones.The sensitized photoinitiation mechanism has been discussed.
基金financially supported by National Natural Science Foundation of China (Nos. 21925802, 22338005)Liaoning Binhai Laboratory (No. LBLB-2023–03)the Fundamental Research Funds for the Central Universities (No. DUT22LAB601)。
文摘Photoinitiators(PIs), as the key substances for photopolymerized antibacterial film(PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the candidates, BDO1 has demonstrated the ability to initiate polymerization of acrylate monomers as single-component PI with the advantages of low mobility, outstanding photobleaching, excellent cytocompatibility, and suitability for light emitting diode(LED) light sources above 365 nm. Taking BDOs as examples, a novel method based on theoretical calculations aiming to assess the potential of enone molecules as single-component PIs was proposed. Finally, under the initiation of BDO1, tannic acid was photopolymerized to a colorless and transparent antibacterial film with high antibacterial ability, which indicated that BDO1 was expected to be used in environmentally friendly PAF.
基金the financial support of the Tianjin Technical Expert Project(22YDTPJC00620)。
文摘Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.
基金supported by the National Natural Science Foundation of China(Nos.22106169,22136006,and 22021003)。
文摘Photoinitiators(PIs),as an important component of UV inks,are widely used in the printing of paper food packaging.Nevertheless,there is limited information concerning the identification of PIs in food packaging and their potential migration rules under natural storage condition.In this study,23 target PIs detected in paper food packaging were dominated by benzophenones(BZPs),followed by amine co-initiators(ACIs),thioxanthones(TXs)and phosphine oxides(POs).The concentration of ΣPIs ranged between 48.3 and 1.11×10^(5)ng/g.Meanwhile,the concentration ofΣPIs were found to be significantly higher in Corrugated paper compared to Polyethylene(PE)coated paper,Composite paper and White card paper.Benzophenone(BP)was found as the dominant PI congener in Corrugated paper,with the concentration ranging from 923-3.66×10^(4)ng/g.The migration quantity ofΣPIs increased in a time-dependent manner in the first 13 days and then eventually reached equilibrium.Low temperatures had a certain inhibitory effect on the migration of PIs from paper packaging to food.Under high exposure scenario,the EDIs of ΣPIs for children,adolescents,and adults were 31.4 ng/(kg bw·day),17.2 ng/(kg bw·day),and 14.4 ng/(kg bw·day),respectively,all of which did not exceed the reference dose,indicating that dietary intake of PIs does not pose any health risks to the human body.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21971047 and 21504017)Innovation Project of Education Department in Guangdong(No.2018KTSCX053)+1 种基金Y.C.acknowledges the support from Guangdong Special Support Program(No.2017TX04N371)J.T.acknowledges the support from Pearl River Young Scholar of Guangdong.
文摘Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmospheres(e.g.argon,nitrogen)are usually required.Moreover,the large-scale preparation of block copolymer nano-objects at room temperature is challenging.Herein,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen toleranee.The addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air conditions.Polymerization kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen tolerance.Block copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent composition.We expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.
文摘Polyethylene terephthalate(PET)and polyethylene(PE)fibers were surface photo-grafted with acrylic acid(AA)by using UV irradiation photochemical initiationduring a continuous winding process within 1-2 min-utes.The grafted fibers were characterized by measure-ments of dye uptaking,moisture regain,pull-out forcesof monofilament from cured matrix,as well as by analy-sis of ESCA and ATR-FTIR spectra.All these resultsconfirm that the surface behavior of the UV-irradiationgrafted fibers was greatly improved.It was also provedthat the original excellent mechanical properties of the fi-bers were well-retained after the surface grafting treat-ment.
基金financially supported by the National Natural Science Fund for Distinguished Young Scholars(No.31525009)the National Natural Science Foundation of China(Nos.31930067,31771096)+1 种基金the National Key Research and Development Program of China(No.2017YFC1103502)1·3·5 Project for Disciplines of Excellence,West China Hospital,Sichuan University(No.ZYGD18002)。
文摘Owing to the special fo rmation of photopolymerized hydrogels,they can effectively control the formation of hydrogels in space and time.Moreover,the photopolymerized hydrogels have mild formation conditions and biocompatibility;therefore,they can be widely used in tissue engineering.With the development and application of manufacturing technology,photopolymerized hydrogels can be widely used in cell encapsulation,scaffold materials,and other tissue engineering fields through more elaborate manufacturing methods.This review covers the types of photoinitiators,manu facturing technologies for photopolymerized hydrogels as well as the materials used,and a summary of the applications of photopolymerized hydrogels in tissue engineering.
基金the National Basic Research Program (No. 2013CB834506)National Nature Science Foundation of China (Nos. 51373098 and 21522403)
文摘We synthesized four diphenylquinoxaline derivatives（SQs） with phenyl-thioether units, which combine photo-cleavable and hydrogen-abstracting groups in one molecule. The photochemistry and photopolymerization of SQs were investigated. SQs possess suitable UV-vis absorption in the range of 350-400 nm with high extinction coefficients. UV-vis and HPLC-MS spectra revealed that C–S bond in phenyl-thioether group of SQs can be broken by irradiation of UV-light. Photolysis and photopolymerization experiments showed that SQs can be used as photo-cleavable photointiators,their photoinitiating efficiency can be enhanced by hydrogen donor. As photo-cleavable photoinitiators,SQs could initiate hexamethylene diacrylate（HDDA） very efficiently with the double bond conversion（DBC） of 80%. In the presence of ethyl-4-（dimethylamino） benzoate（EDB） as coinitiator, photoinitiator systems initiated photopolymerization of commercial acrylate monomers with higher double bond conversion than 90%. These characteristics make SQs potential photoinitiators in photo-curing field.
基金This work was supported by the National Natural Science Foundation of China(Nos.21876063,22076064 and 22106169)the Guangdong Special Support Program(No.2019TX05L129)+2 种基金the Science and Technology Program of Guangzhou(No.202206010191)the Guangdong(China)Innovative and Entrepreneurial Research Team Program(No.2016ZT06N258)the Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province(No.2019B121205004)。
文摘Photoinitiators(PIs)are widely used in industrial polymerization processes.It has been reported that PIs are ubiquitous in indoor environments and that humans are exposed to PIs,but the occurrence of PIs in natural environments are rarely known.In the present study,25 PIs,including 9 benzophenones(BZPs),8 amine co-initiators(ACIs),4 thioxanthones(TXs)and 4 phosphine oxides(POs),were analyzed in water and sediment samples collected from eight riverine outlets of the Pearl River Delta(PRD).Eighteen,14,and 14 of the 25 target PIs were detected in water,suspended particulatematter(SPM)and sediment samples,respectively.The total concentrations of PIs in water,SPM,and sediment were in the ranges of 2.88–96.1 ng/L,9.25–923 ng/g dry weight(dw),and 3.79–56.9 ng/g dw,with geometric mean concentration(GM)of 10.8 ng/L,48.6 ng/g dw,and 17.1 ng/g dw,respectively.A significant linear regression was observed between the log partitioning coefficients(Kd)values of PIs and their log octanol water partition coefficient(Kow)values(R^(2)=0.535,p<0.05).The annual riverine input of PIs to the coastal waters of the South China Sea via eightmain outlets of the PRD was estimated to be 4.12×10^(3)kg/year,and the∑BZPs,∑ACIs,∑TXs and∑POs contributed to 1.96×10^(3),1.24×10^(3),89.6 and 830 kg/year,respectively.This is the first report of a systematic description of the occurrence characteristics of PIs exposure in water,SPM,and sediment.The environmental fate and risks of PIs in aquatic environments need further investigations.
基金Supported by the National Natural Science Foundation of China(No50973100)
文摘Dodecyl-benzophenone（DBP） and hexadecoxyl-benzophenone（HDBP） as type 11 photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%（mass fraction） tripropyleneglycol diacrylate （TPGDA）, resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry（photo-DSC）. DBP initiates the curing of acrylate more efficiently than HDBP, showing higher photopolymerization rate and unsaturation conversion, resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.
基金Supported by the National Natural Science Foundation of China (No.20676012).
文摘Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopendadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4. and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoinitiating activities in epoxy resins.
基金the financial support by the National Natural Science Foundation of China(Nos.22301107,52373057)the Nature Science Foundation of Jiangsu Province(No.BK20200610)+1 种基金the Fundamental Research Funds for the Central Universities(No.JUSRP122021)Jiangsu Province"Innovation and Entrepreneurship Doctor"Talent Plan(No.JSSCBS20221053)also provided support。
文摘Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.
基金financially supported by National Natural Science Foundation of China(52003231,22065037)Yunnan Fundamental Research Projects(202201AW070015)。
文摘The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.
基金support by Zhenxing Chemistry Co.,Ltd(Tianjin,China)
文摘A novel preparation of aluminum diethylphosphinate（AlPi） was carried out with free-radical addition reaction by means of UV-irradiation under atmospheric pressure.A solution of sodium hypophosphite was treated with ethylene and irradiated with ultraviolet light in the presence of an amount of photoinitiator effective to initiate the free-radical reaction between the hypophosphite anion and the double bond of the ethylene molecule.The ethylene was micro-bubbled into the reaction mixture with the addition of the photoinitiator,and the gas-liquid contact surface and the photoinitiator concentration in the gas-liquid interface were increased largely.The yield of the final product could be improved to about 96%.The contents of P,Al in samples were detected by ICP,and the molecular structure of the samples was confirmed by ^（31）P NMR,~1H NMR and FTIR spectroscopic analysis.Thermal stability of the final products was investigated in detail by TG-DTA.
文摘Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator is described.
基金the National Natural Science Foundation of China(Nos. 21522403,51373098)Education Commission of Shanghai Municipal Government(No.15SG13)IFPM2016B002 of Shanghai jiao Tong University & Affiliated Sixth People's Hospital South Campus for their financial support
文摘To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperhranched polymeric photoinitiators （hPEA-TXs, and hPEA- BPs） by introducing thioxanthone （TX） or benzophenone （BP） moieties into the periphery of the hyperbranched poly（ether amine） （hPEA） comprised of the hydrophilic poly（ethylene oxide） （PEO） short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10 wt~. The photopolymerization kinetics of water-soluble monomer acrylamide （AM） and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric （photo-DSC）. Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion （DBC） of oil-soluble monomer hexanediol diacrylate （HDDA） photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate （TMPTA） and pentaerythritol tetraacrylate （PETTA） can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.
基金the National Natural Science Foundation of China (No.20676012).
文摘Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopen- dadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4, and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoini- tiating activities in epoxy resins.
基金National Key Research and Development Program(2022YFA1104604,2017YFC1103303)Science Fund for National Defense Distinguished Young Scholars(2022-JCJQ-ZQ-016)+2 种基金National Nature Science Foundation of China(32000969,82002056,92268206)Military Medical Research Projects(145AKJ260015000X,2022-JCJQ-ZD-096-00)Key Support Program for Growth Factor Research(SZYZ-TR-03).
文摘Dear Editor,Timely and effective hemostasis is of great significance for reducing body damage and mortality of patients [1]. Alginate is generally considered to be an excellent hemostatic polymer-based biomaterial and has been approved by the Food and Drug Administration as Generally Recognized as Safe [2]. However, the violent crosslinking reaction and unstable structure at the wound site limit its clinical applications. Hence, we report a biocompatible and injectable composite hydrogel methacrylate alginate (Alg-AEMA)-based Eosin Y/N-phenylglycine (NPG)-initiated composite hydrogel (AEC) composed of photocrosslinkable alginate, viscosity modifiers and novel white light photoinitiator, namely Eosin Y/NPG system, for instant hemorrhage control.
基金supported by the Natural Science Foundation of Henan University, China (Grant No. 06ZDZR002)
文摘Holographic parameters and photobleaching kinetics of the photopolymers with five different amine photoinitiators are studied. The maximum values of diffraction efficiency, photobleaching coefficient and quantum yield follow the sequence： Triethanolamine （TEA）〉 Diethanolamine （DEA）〉 Ethanolamine （EA）〉 Triethylamine （TETN）〉 Diethylamine （DETN）. The holographic capabilities of photopolymer performances are determined by the number of functional groups in the amine molecular structure. There is an optimum proportion of the photoinitiator, the photosensitizer and the monomer in the test of holographic parameters with different amine concentrations. The maximum diffraction efficiency is 59.26／%, sensitivity is 1.72／times 10^{ - 3}~cm^{2}/mJ, and the maximum refractive modulation index is 4.64／times 10^{ - 4}.
