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
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
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
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
A series of novel hybrid photoinitiators(YPhCOPhXPhI^+PhPF_6^-,Y = 4-NO_2,4-MeO or 3-Cl,X = O,OCH_2,or nothing),which contain multiple aromatic rings(PhCOPhXPh),were prepared by reaction of easily available aryl keton...A series of novel hybrid photoinitiators(YPhCOPhXPhI^+PhPF_6^-,Y = 4-NO_2,4-MeO or 3-Cl,X = O,OCH_2,or nothing),which contain multiple aromatic rings(PhCOPhXPh),were prepared by reaction of easily available aryl ketones (YPhCOPhXPh) with iodosobenzene diacetate[PhI^+OCOCH_3(CH_3CO_2)^-].The inset of an aromatic ring into p-benzoyldiphenyliodonium hexafluorophophate(PhCOPhI^+PhPF_6^-)(BDPIH,He-type photoinitiator) between diphenyliodonium and benzoyl is propitious both to the preparation and the photoinitiat...展开更多
Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [...Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [π-cyclopentadienyl）iron] hexafluorophosphate （[bis（Cp-Fe）-biphenyl] （PF6）2 was synthesized by the ligand exchange reaction between ferrocene and biphenyl. The chemical structure was characterized with FTIR and ^1HNMR. The separation of ferrocenium monocation cyclopentadien-iron-biphenyl hexafluorophosphate （[Cp-Fe-biphenyl] PF6） and dication [bis（Cp-Fe）-biphenyl] （PF6）2 was carried out by column chromatography. The photoactivity of initiating photopolyinerization of epoxide ER14221 was studied as a cationic photoinitiator. [Bis（Cp-Fe）-biphenyl] （PF6）2 can efficiently absorb radiation above 300nm and its photoactivity is higher than that of its monocation.展开更多
Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electroch...Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electrochemical study reported in this note provides further evidence for the photolysis process which is crucial for the understanding of the photoinitiation mechanism.展开更多
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
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
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
Photopolymerization process of glycerin triglycidyl ether based systems was studied by an FT-IR spectrometer.An increase in the rate of polymerization for glycerin triglycidyl ether was evident when 3,4-epoxycyclohexy...Photopolymerization process of glycerin triglycidyl ether based systems was studied by an FT-IR spectrometer.An increase in the rate of polymerization for glycerin triglycidyl ether was evident when 3,4-epoxycyclohexylmethyl-3＇,4＇-epoxycyclohexanecarboxylate was added to it.Its copolymerization mechanism was confirmed by using DSC analysis.The effect of ethoxylated trimethyol propane triacrylate on the rate of polymerization for glycerin triglycidyl ether was also studied,and the formation of interpenetrating network tightly cross-link was proposed.展开更多
Three-dimensional(3D)printing is an innovative manufacturingmethod with the potential to revolutionize topical and transdermal dosage forms.Nowadays,it is established that Vatbased photopolymerization(VP)3D printing t...Three-dimensional(3D)printing is an innovative manufacturingmethod with the potential to revolutionize topical and transdermal dosage forms.Nowadays,it is established that Vatbased photopolymerization(VP)3D printing technologies offer superior printing efficiency and versatility compared to other 3D printing technologies available on the market.However,there are some limitations that impair their full application in pharmaceutical contexts,such as the lack of a range of biocompatiblematerials for topical and transdermal applications.This reviewarticle explores all types of VP-based 3D printing and discusses the relevance of implementing this kind of technology.We start with a detailed description of the printing process,focusing on the commercial materials available and lab-made resins proposed by different authors.We also review recent studies in this field,which mainly focus on the fabrication of transdermal devices based on microneedle arrays.In the future,it is expected that the manufacturers of 3D printers invest in modifications to the printing apparatus to allow the simultaneous printing of different resins and/or compound types,which will open frontiers to the personalization of treatment approaches.展开更多
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.
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}.
基金supported by the National Natural Science Foundation of China(No.20772102)Doctor Student Research Foundation of Chinese Education Ministry(No.20060530002)
文摘A series of novel hybrid photoinitiators(YPhCOPhXPhI^+PhPF_6^-,Y = 4-NO_2,4-MeO or 3-Cl,X = O,OCH_2,or nothing),which contain multiple aromatic rings(PhCOPhXPh),were prepared by reaction of easily available aryl ketones (YPhCOPhXPh) with iodosobenzene diacetate[PhI^+OCOCH_3(CH_3CO_2)^-].The inset of an aromatic ring into p-benzoyldiphenyliodonium hexafluorophophate(PhCOPhI^+PhPF_6^-)(BDPIH,He-type photoinitiator) between diphenyliodonium and benzoyl is propitious both to the preparation and the photoinitiat...
基金Supported by the National Natural Science Foundation of China （20676012）.
文摘Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [π-cyclopentadienyl）iron] hexafluorophosphate （[bis（Cp-Fe）-biphenyl] （PF6）2 was synthesized by the ligand exchange reaction between ferrocene and biphenyl. The chemical structure was characterized with FTIR and ^1HNMR. The separation of ferrocenium monocation cyclopentadien-iron-biphenyl hexafluorophosphate （[Cp-Fe-biphenyl] PF6） and dication [bis（Cp-Fe）-biphenyl] （PF6）2 was carried out by column chromatography. The photoactivity of initiating photopolyinerization of epoxide ER14221 was studied as a cationic photoinitiator. [Bis（Cp-Fe）-biphenyl] （PF6）2 can efficiently absorb radiation above 300nm and its photoactivity is higher than that of its monocation.
基金Supported by the National Natural Science Foundation of China
文摘Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electrochemical study reported in this note provides further evidence for the photolysis process which is crucial for the understanding of the photoinitiation mechanism.
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.
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.
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Funded by the Innovatory Group Program of the Natural Science Foundation of Hubei Province (2004ABC001)the National "863" Hi-tech Foundation of China (2002AA6Z3083)
文摘Photopolymerization process of glycerin triglycidyl ether based systems was studied by an FT-IR spectrometer.An increase in the rate of polymerization for glycerin triglycidyl ether was evident when 3,4-epoxycyclohexylmethyl-3＇,4＇-epoxycyclohexanecarboxylate was added to it.Its copolymerization mechanism was confirmed by using DSC analysis.The effect of ethoxylated trimethyol propane triacrylate on the rate of polymerization for glycerin triglycidyl ether was also studied,and the formation of interpenetrating network tightly cross-link was proposed.
基金funded by the Fundacao para a Ciencia e Tecnologia,Portugal[UIDB/04138/2020 and UIDP/04138/2020 to iMed.ULisboa,CEECINST/00145/2018 to J Marto,fellowship 2020.10138BD to A.Graca and UI/BD/153624/2022 to S.Bom].
文摘Three-dimensional(3D)printing is an innovative manufacturingmethod with the potential to revolutionize topical and transdermal dosage forms.Nowadays,it is established that Vatbased photopolymerization(VP)3D printing technologies offer superior printing efficiency and versatility compared to other 3D printing technologies available on the market.However,there are some limitations that impair their full application in pharmaceutical contexts,such as the lack of a range of biocompatiblematerials for topical and transdermal applications.This reviewarticle explores all types of VP-based 3D printing and discusses the relevance of implementing this kind of technology.We start with a detailed description of the printing process,focusing on the commercial materials available and lab-made resins proposed by different authors.We also review recent studies in this field,which mainly focus on the fabrication of transdermal devices based on microneedle arrays.In the future,it is expected that the manufacturers of 3D printers invest in modifications to the printing apparatus to allow the simultaneous printing of different resins and/or compound types,which will open frontiers to the personalization of treatment approaches.
