Organic-inorganic hybrid perovskites(OIHPs)offer precise control over material properties through the substitution of organic cations and halogens.In this study,two OIHPs,[(C_(6)H_(10)P)(n-BA)]Sb_(2)X_(9)([C_(6)H_(10)...Organic-inorganic hybrid perovskites(OIHPs)offer precise control over material properties through the substitution of organic cations and halogens.In this study,two OIHPs,[(C_(6)H_(10)P)(n-BA)]Sb_(2)X_(9)([C_(6)H_(10)P]^(+)=[Me_(3)PCH_(2)CH_(2)CH_(3)]+,[n-BA]+=n-butylamine cation,X=I(1),Br(2)),were synthesized by varying halogens within a mixed-cation system.The halogen substitution induced a shift from compound 1,which remains stable without phase transitions,to compound 2,which undergoes a ferroelastic phase transition(mmmF2/m).Compound 1 crystallizes in the non-centrosymmetric Pca2_(1) space group and demonstrates a second harmonic generation(SHG)response,while compound 2 displays elasticity in nanoindentation tests.Halogen substitution alters Sb—X bond lengths,inducing structural distortions in the inorganic framework and influencing the spatial configuration of organic cations and inorganic anions.These changes lead to distinct crystallization behaviors,resulting in different physical properties for compounds 1 and 2.This work contributes to the development of multifunctional materials based on halogen regulation in mixed-cation OIHPs.展开更多
Ferroelastic materials have rich properties,which have important applications in memory devices,multifunctional devices and novel controllable devices,but few ferroelastic crystals based on metal coordination complexe...Ferroelastic materials have rich properties,which have important applications in memory devices,multifunctional devices and novel controllable devices,but few ferroelastic crystals based on metal coordination complexes have been reported.Herein,we have introduced coligands in the structure to obtain a ferroelastic complex{Mn[(i-Pr)_(3)PO](dca)_(2)}(1),[dca=N(CN)_(2)^(−),(i-Pr_(3)PO)=triisopropylphosphine oxide],with a new topology(3,5)-connected binodal network.The dca ligands of 1 show two different bonding modes,μ-1,5-andμ-1,3,5-bridging,to form a 3D structure.Stimulation by high temperature leads to more intense molecular motion and greater symmetry changes,thus producing a high-temperature(390 K)ferroelastic phase transition with the Aizu symbol mmmF2/m.The full elastic constants of 1 were calculated using density functional theory to describe the Young’s modulus,shear modulus and Poisson’s ratio,and the results indicate that 1 is a ductile material.In addition,1 emits blue light under excitation at 380 nm.This provides new ideas for the exploration and design of molecular ferroelastic materials with elaborate structures and excellent properties.展开更多
Since severe acute respiratory syndrome coronavirus-2(SARS-CoV-2)-specific T cells have been found to play essential roles in host immune protection and pathology in patients with coronavirus disease 2019(COVID-19),th...Since severe acute respiratory syndrome coronavirus-2(SARS-CoV-2)-specific T cells have been found to play essential roles in host immune protection and pathology in patients with coronavirus disease 2019(COVID-19),this study focused on the functional validation of T cell epitopes and the development of vaccines that induce specific T cell responses.A total of 120 CD8^(+)T cell epitopes from the E,M,N,S,and RdRp proteins were functionally validated.Among these,110,15,6,14,and 12 epitopes were highly homologous with SARS-CoV,OC43,NL63,HKU1,and 229E,respectively;in addition,four epitopes from the S protein displayed one amino acid that was distinct from the current SARS-CoV-2 variants.Then,31 epitopes restricted by the HLA-A2 molecule were used to generate peptide cocktail vaccines in combination with Poly(I:C),R848 or poly(lactic-co-glycolic acid)nanoparticles,and these vaccines elicited robust and specific CD8^(+)T cell responses in HLA-A2/DR1 transgenic mice as well as wild-type mice.In contrast to previous research,this study established a modified DC-peptide-PBL cell coculture system using healthy donor PBMCs to validate the in silico predicted epitopes,provided an epitope library restricted by nine of the most prevalent HLA-A allotypes covering broad Asian populations,and identified the HLA-A restrictions of these validated epitopes using competitive peptide binding experiments with HMy2.CIR cell lines expressing the indicated HLA-A allotype,which initially confirmed the in vivo feasibility of 9-or 10-mer peptide cocktail vaccines against SARS-CoV-2.These data will facilitate the design and development of vaccines that induce antiviral CD8^(+)T cell responses in COVID-19 patients.展开更多
基金supported by the National Natural Science Foundation of China(22275033)the Natural Science Foundation of Jiangsu Province(JSNSF)(BK20230810).
文摘Organic-inorganic hybrid perovskites(OIHPs)offer precise control over material properties through the substitution of organic cations and halogens.In this study,two OIHPs,[(C_(6)H_(10)P)(n-BA)]Sb_(2)X_(9)([C_(6)H_(10)P]^(+)=[Me_(3)PCH_(2)CH_(2)CH_(3)]+,[n-BA]+=n-butylamine cation,X=I(1),Br(2)),were synthesized by varying halogens within a mixed-cation system.The halogen substitution induced a shift from compound 1,which remains stable without phase transitions,to compound 2,which undergoes a ferroelastic phase transition(mmmF2/m).Compound 1 crystallizes in the non-centrosymmetric Pca2_(1) space group and demonstrates a second harmonic generation(SHG)response,while compound 2 displays elasticity in nanoindentation tests.Halogen substitution alters Sb—X bond lengths,inducing structural distortions in the inorganic framework and influencing the spatial configuration of organic cations and inorganic anions.These changes lead to distinct crystallization behaviors,resulting in different physical properties for compounds 1 and 2.This work contributes to the development of multifunctional materials based on halogen regulation in mixed-cation OIHPs.
基金supported by the National Natural Science Foundation of China(22275033)supported by the Big Data Computing Center of Southeast University.
文摘Ferroelastic materials have rich properties,which have important applications in memory devices,multifunctional devices and novel controllable devices,but few ferroelastic crystals based on metal coordination complexes have been reported.Herein,we have introduced coligands in the structure to obtain a ferroelastic complex{Mn[(i-Pr)_(3)PO](dca)_(2)}(1),[dca=N(CN)_(2)^(−),(i-Pr_(3)PO)=triisopropylphosphine oxide],with a new topology(3,5)-connected binodal network.The dca ligands of 1 show two different bonding modes,μ-1,5-andμ-1,3,5-bridging,to form a 3D structure.Stimulation by high temperature leads to more intense molecular motion and greater symmetry changes,thus producing a high-temperature(390 K)ferroelastic phase transition with the Aizu symbol mmmF2/m.The full elastic constants of 1 were calculated using density functional theory to describe the Young’s modulus,shear modulus and Poisson’s ratio,and the results indicate that 1 is a ductile material.In addition,1 emits blue light under excitation at 380 nm.This provides new ideas for the exploration and design of molecular ferroelastic materials with elaborate structures and excellent properties.
基金This work was supported by the National Nature Science Foundation of China(82041006)the COVID-19 Emergency Research Fund of Zhejiang University of China(2020XGZX021).
文摘Since severe acute respiratory syndrome coronavirus-2(SARS-CoV-2)-specific T cells have been found to play essential roles in host immune protection and pathology in patients with coronavirus disease 2019(COVID-19),this study focused on the functional validation of T cell epitopes and the development of vaccines that induce specific T cell responses.A total of 120 CD8^(+)T cell epitopes from the E,M,N,S,and RdRp proteins were functionally validated.Among these,110,15,6,14,and 12 epitopes were highly homologous with SARS-CoV,OC43,NL63,HKU1,and 229E,respectively;in addition,four epitopes from the S protein displayed one amino acid that was distinct from the current SARS-CoV-2 variants.Then,31 epitopes restricted by the HLA-A2 molecule were used to generate peptide cocktail vaccines in combination with Poly(I:C),R848 or poly(lactic-co-glycolic acid)nanoparticles,and these vaccines elicited robust and specific CD8^(+)T cell responses in HLA-A2/DR1 transgenic mice as well as wild-type mice.In contrast to previous research,this study established a modified DC-peptide-PBL cell coculture system using healthy donor PBMCs to validate the in silico predicted epitopes,provided an epitope library restricted by nine of the most prevalent HLA-A allotypes covering broad Asian populations,and identified the HLA-A restrictions of these validated epitopes using competitive peptide binding experiments with HMy2.CIR cell lines expressing the indicated HLA-A allotype,which initially confirmed the in vivo feasibility of 9-or 10-mer peptide cocktail vaccines against SARS-CoV-2.These data will facilitate the design and development of vaccines that induce antiviral CD8^(+)T cell responses in COVID-19 patients.
