Ultralong organic phosphorescence(UOP)materials have garnered significant interest for applications in advanced optical recording and information encryption.However,it remains a formidable challenge achieving manipula...Ultralong organic phosphorescence(UOP)materials have garnered significant interest for applications in advanced optical recording and information encryption.However,it remains a formidable challenge achieving manipulated phosphorescence due to the limited color channels and poorly populated triplet energy levels.Herein,we report a novel multiresponsive organic phosphorescence material,in which the phosphorescence color can be dynamically tuned with stimuli such as radiation duration,concentration,excitation wavelength,time,and temperature.The material is based on the confined 7H-benzo[c]carbazole(BCz)molecules in the polymermatrix,which is achieved through the size-dependent cluster-triggered emission(CTE)mechanism.The BCz molecules form isolated molecules and different-sized clusters in the matrix,resulting in multiple luminescent centers with different energy levels and phosphorescence lifetimes.Throughmatrix confinement effects,the activation states of the monomers and multiple clusters could be precisely modulated,resulting in temperature-controlled tunable orange-to-green variations.Furthermore,the multiresponsive properties of the material have been used in both civil and military applications through sophisticated mathematical modeling.This work potentially proposes a guiding strategy for the development of multiresponsive UOP materials based on CTE molecules.展开更多
Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multire...Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multiresponsive perchlorate terpyridyl Pt(Ⅱ)nano complex which could undergo fully reversible conversion between three forms stimulated by water or formaldehyde molecule due to the extent of Pt–Pt interaction.Meanwhile,a dual-visual channel,i.e.,the colorimetric channel changed from yellow to orange or red and the corresponding luminescent channel from orange to orange-red or red,has also been found.The weak and equivalent strength of ion-dipole interaction and hydrogen bond that generated between formaldehyde/water and Pt(II)salt result in the easy-control reversibility between the three forms.Furthermore,by introducing different polymer matrices,1Cl·ClO_(4)@PMMA(1Cl·ClO_(4):[Pt(tpy)Cl]·ClO4,tpy:2,2':6',2''-terpyridine),PMMA:poly(methyl methacrylate))and 1Cl·ClO4@PVA(PVA:polyvinyl alcohol)are successfully constructed,which exhibit different reversible behaviors since the PMMA and PVA matrix exert different influences on the strength of hydrogen-bond.Those smart Pt(II)salt nanostructures present great potential for high-security-level anticounterfeiting application.展开更多
A series of poly（acrylic acid） macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer （RAFT） poly- merization and characterized b...A series of poly（acrylic acid） macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer （RAFT） poly- merization and characterized by 1^H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly（potassium acrylate） macro-RAFT agents as the electrostcric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.展开更多
This paper deals with the problem of P-optimal robust designs for multiresponse approximately linear regression models. Each response is assumed to be only approximately linear in the regressors, and the bias function...This paper deals with the problem of P-optimal robust designs for multiresponse approximately linear regression models. Each response is assumed to be only approximately linear in the regressors, and the bias function varies over a given L2--neighbourhood. A kind of bivariate models with two responses is taken as an example to illustrate how to get the expression of the design measure.展开更多
Designing and implementing multielectron transfer and single-molecule magnet properties in spin crossover compounds constitute a promising way to obtain a new class of multiresponsive and multifunctional materials.Thi...Designing and implementing multielectron transfer and single-molecule magnet properties in spin crossover compounds constitute a promising way to obtain a new class of multiresponsive and multifunctional materials.This contribution uses N-phenyl-substituted pyridine-2,6-diimine(PDI)ligands to explore a novel family of spin-crossover cobalt(Ⅱ)complexes,with general formula[CoL_(2)](ClO_(4))_(2)·xH_(2)O[L=4-MePhPDI(1,x=1),4-MeOPhPDI(2,x=0),4-MeSPhPDI(3,x=0),4-Me_(2)NPhPDI(4,x=0.5),and 2,4-Me_(2)PhPDI(5,x=0)].These mononuclear six-coordinate octahedral cobalt(Ⅱ)bis(chelating)complexes incorporate tridentate PDI derivatives with various electron-donating substituents at para(X_(4)=Me,OMe,SMe,and Me_(2)N)or ortho and para positions(X_(2),X_(4)=Me)of terminal phenyl rings.Our investigations reveal that these complexes exhibit both thermally-induced low-spin(LS)/high-spin(HS)transition and field-induced slow magnetic relaxation in the LS(S=1/2)and HS(S=3/2)states.Moreover,they display a dual multiredox behaviour featuring one-electron oxidation of the paramagnetic Co^(Ⅱ)ion to the diamagnetic Co^(Ⅲ)ion and stepwise two-electron reduction of each PDI ligand to the corresponding imine-type PDI·−π-radical anion and diimine-type PDI^(2−)dianion,which positions them as candidates for prototypes of spin quantum transistors and capacitors,offering potential applications in quantum information processing.展开更多
This paper considers a linear regression model involving both quantitative and qualitative factors and an m-dimensional response variable y. The main purpose of this paper is to investigate D-optimal designs when the ...This paper considers a linear regression model involving both quantitative and qualitative factors and an m-dimensional response variable y. The main purpose of this paper is to investigate D-optimal designs when the levels of the qualitative factors interact with the levels of the quantitative factors. Under a general covariance structure of the response vector y, here we establish that the determinant of the information matrix of a product design can be separated into two parts corresponding to the two marginal designs. Moreover, it is also proved that D-optimal designs do not depend on the covariance structure if we assume hierarchically ordered system of regression models.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(U2241236,1220041913,52473253)the National Key Research and Development Program of China(2022ZDZX0007)+2 种基金Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)Yunnan Major Scientific and Technological Projects(202402AB080011)the Science Fund of Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2024F15).
文摘Ultralong organic phosphorescence(UOP)materials have garnered significant interest for applications in advanced optical recording and information encryption.However,it remains a formidable challenge achieving manipulated phosphorescence due to the limited color channels and poorly populated triplet energy levels.Herein,we report a novel multiresponsive organic phosphorescence material,in which the phosphorescence color can be dynamically tuned with stimuli such as radiation duration,concentration,excitation wavelength,time,and temperature.The material is based on the confined 7H-benzo[c]carbazole(BCz)molecules in the polymermatrix,which is achieved through the size-dependent cluster-triggered emission(CTE)mechanism.The BCz molecules form isolated molecules and different-sized clusters in the matrix,resulting in multiple luminescent centers with different energy levels and phosphorescence lifetimes.Throughmatrix confinement effects,the activation states of the monomers and multiple clusters could be precisely modulated,resulting in temperature-controlled tunable orange-to-green variations.Furthermore,the multiresponsive properties of the material have been used in both civil and military applications through sophisticated mathematical modeling.This work potentially proposes a guiding strategy for the development of multiresponsive UOP materials based on CTE molecules.
基金support from the Major Science and Technology Project of Xinjiang(No.2022A01006-3)Science Foundation for Outstanding Young People of Xinjiang(No.2022D01E40)+1 种基金Youth Science Foundation of Xinjiang(No.2022D01C69)Tianchi Doctoral program(Nos.TCBS202130 and 51052300573).
文摘Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multiresponsive perchlorate terpyridyl Pt(Ⅱ)nano complex which could undergo fully reversible conversion between three forms stimulated by water or formaldehyde molecule due to the extent of Pt–Pt interaction.Meanwhile,a dual-visual channel,i.e.,the colorimetric channel changed from yellow to orange or red and the corresponding luminescent channel from orange to orange-red or red,has also been found.The weak and equivalent strength of ion-dipole interaction and hydrogen bond that generated between formaldehyde/water and Pt(II)salt result in the easy-control reversibility between the three forms.Furthermore,by introducing different polymer matrices,1Cl·ClO_(4)@PMMA(1Cl·ClO_(4):[Pt(tpy)Cl]·ClO4,tpy:2,2':6',2''-terpyridine),PMMA:poly(methyl methacrylate))and 1Cl·ClO4@PVA(PVA:polyvinyl alcohol)are successfully constructed,which exhibit different reversible behaviors since the PMMA and PVA matrix exert different influences on the strength of hydrogen-bond.Those smart Pt(II)salt nanostructures present great potential for high-security-level anticounterfeiting application.
文摘A series of poly（acrylic acid） macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer （RAFT） poly- merization and characterized by 1^H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly（potassium acrylate） macro-RAFT agents as the electrostcric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.
基金National Natural Science Foundation of China(10671129)the Special Funds for Doctoral Authorities of Education Ministry of China(20060270002).
文摘This paper deals with the problem of P-optimal robust designs for multiresponse approximately linear regression models. Each response is assumed to be only approximately linear in the regressors, and the bias function varies over a given L2--neighbourhood. A kind of bivariate models with two responses is taken as an example to illustrate how to get the expression of the design measure.
基金supported by the Spanish MINECO(Projects PID2019-109735GB-I00Unidad de Excelencia María de Maeztu CEX2019-000919-M)+2 种基金the Generalitat Valenciana(AICO/2020/183 and AICO/2021/295)funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no 748921-SIMOF.R.R.thanks the Generalitat Valenciana and CAPES/BRASIL for the doctoral(GRISOLIAP/2017/057)postdoctoral(88887.798611/2022-00)grants。
文摘Designing and implementing multielectron transfer and single-molecule magnet properties in spin crossover compounds constitute a promising way to obtain a new class of multiresponsive and multifunctional materials.This contribution uses N-phenyl-substituted pyridine-2,6-diimine(PDI)ligands to explore a novel family of spin-crossover cobalt(Ⅱ)complexes,with general formula[CoL_(2)](ClO_(4))_(2)·xH_(2)O[L=4-MePhPDI(1,x=1),4-MeOPhPDI(2,x=0),4-MeSPhPDI(3,x=0),4-Me_(2)NPhPDI(4,x=0.5),and 2,4-Me_(2)PhPDI(5,x=0)].These mononuclear six-coordinate octahedral cobalt(Ⅱ)bis(chelating)complexes incorporate tridentate PDI derivatives with various electron-donating substituents at para(X_(4)=Me,OMe,SMe,and Me_(2)N)or ortho and para positions(X_(2),X_(4)=Me)of terminal phenyl rings.Our investigations reveal that these complexes exhibit both thermally-induced low-spin(LS)/high-spin(HS)transition and field-induced slow magnetic relaxation in the LS(S=1/2)and HS(S=3/2)states.Moreover,they display a dual multiredox behaviour featuring one-electron oxidation of the paramagnetic Co^(Ⅱ)ion to the diamagnetic Co^(Ⅲ)ion and stepwise two-electron reduction of each PDI ligand to the corresponding imine-type PDI·−π-radical anion and diimine-type PDI^(2−)dianion,which positions them as candidates for prototypes of spin quantum transistors and capacitors,offering potential applications in quantum information processing.
基金supported by the National Natural Science Foundation of China (Nos.11971318, 11871143)the Fundamental Research Funds for the Central Universities (No.2232020D-38)。
文摘This paper considers a linear regression model involving both quantitative and qualitative factors and an m-dimensional response variable y. The main purpose of this paper is to investigate D-optimal designs when the levels of the qualitative factors interact with the levels of the quantitative factors. Under a general covariance structure of the response vector y, here we establish that the determinant of the information matrix of a product design can be separated into two parts corresponding to the two marginal designs. Moreover, it is also proved that D-optimal designs do not depend on the covariance structure if we assume hierarchically ordered system of regression models.
