Solvents in crystalline materials typically exist either as structural components that stabilize the framework or as adsorbed vips that modulate properties,yet achieving their orthogonal coexistence within a single ...Solvents in crystalline materials typically exist either as structural components that stabilize the framework or as adsorbed vips that modulate properties,yet achieving their orthogonal coexistence within a single system remains challenging.This study proposes a natural mineral-inspired solvent hierarchy strategy that enables the concurrent achievement of framework stability and dynamic responsiveness in hydrogen-bonded organic frameworks(HOFs)through the orthogonal integration of structural and adsorbed solvents.We have validated the feasibility of this solvent hierarchy approach based on four model systems with progressively increasing stability and dynamism:(1)unstable HOFs containing only adsorbed solvents,(2)unstable HOFs with low-binding-energy structural solvents,(3)stable HOFs incorporating strong-fitted structural solvents,and(4)stable HOFs with structural solvents and dynamically adjustable adsorption solvents.Crystallographic and theoretical analyses reveal that the superior stability of structural solvents originates from the high-electron-density oxygen of the DMSO S═O bond,which acts as a strong hydrogen-bond acceptor,forming stable N─H…O═S bonds with amine groups.The host’s aggregation-induced emission(AIE)characteristics allow real-time optical monitoring of reversible single-crystal-to-single-crystal transformations without compromising structural integrity,demonstrating promising applications for visual water content and water leakage detection.This work not only establishes a new paradigm in solvent engineering for developing smart crystalline materials but also expands the design possibilities for functional porous frameworks.展开更多
Background:Nonsuicidal self-injury(NSSI)in adolescents with depression disorders often exhibits addictive patterns,potentially linked to serum beta-endorphin levels and neural reward responsiveness.Beta-endorphin,invo...Background:Nonsuicidal self-injury(NSSI)in adolescents with depression disorders often exhibits addictive patterns,potentially linked to serum beta-endorphin levels and neural reward responsiveness.Beta-endorphin,involved in reward processing,alongside dysregulated neural reward pathways,may reinforce self-injurious behaviors,highlighting the need to explore these mechanisms.Methods:Adolescents(aged 12-17 years)with depression disorders were divided into an NSSI group(21 subjects)and a control group(11 subjects)according to inclusion criteria.Serum beta-endorphin concentration was measured using the enzyme-linked immunosorbent assay method.The Addiction Factor Scale was used to assess addiction levels.Statistical analyses were con-ducted using SPSS 25.0.The oxygenated hemoglobin response signal was detected using functional near-infrared spectroscopy.Analyses were performed using NIRS_KIT 2.0.Results:Compared with the control group,the NSSI group exhibited lower serum beta-endorphin concentration.Additionally,85.7%of those in the NSSI group displayed addictive behaviors,and serum beta-endorphin concentration was negatively correlated with the Addiction Factor Scale score.The reward task activated channels 17,20,and 21(corresponding to the dorsolateral prefrontal cortex[PFC]and frontopolar PFC)in the gain condition and channels 20 and 21 in the loss condition.The oxygenated hemoglobin concentration of the differential waveform(Δ[oxy-Hb])of channel 12(corresponding to the frontopolar PFC)correlated positively with the Addiction Factor Scale score and negatively with the serum beta-endorphin concentration.展开更多
Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been re...Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been revealed in the past ten years,it is still unclear if the pH-responsive properties of SPBs are affected by the brush thickness.In this study,we employed the positively charged poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride(PMETAC)and negatively charged sodium poly(styrenesulfonate)(NaPSS)brushes as model systems to explore the effect of thickness on the pH-responsive properties of SPBs.The results demonstrate that the pH-responsive properties of SPBs manifest different dependences on the brush thickness.Specifically,for both PMETAC and NaPSS brushes,the pH-responsive hydration and stiffness are influenced by the thickness,and the pH-responsive wettability and adhesion are almost unaffected by the thickness.This work not only provides a clear understanding of the relationship between the brush thickness and the pH responsiveness of SPBs,but also offers a new method to control the pH-responsive properties of SPBs.展开更多
Rapid and ultrasensitive detection of pathogen-associated biomarkers is vital for the early diagnosis and therapy of bacterial infections.Herein,we developed a close-packed and ordered Au@AgPt array coupled with a cas...Rapid and ultrasensitive detection of pathogen-associated biomarkers is vital for the early diagnosis and therapy of bacterial infections.Herein,we developed a close-packed and ordered Au@AgPt array coupled with a cascade triggering strategy for surface-enhanced Raman scattering(SERS)and colorimetric identification of the Staphylococcus aureus biomarker micrococcal nuclease(MNase)in serum samples.The trimetallic Au@AgPt nanozymes can catalyze the oxidation of 3,3’,5,5’-tetramethylbenzidine(TMB)molecules to SERS-enhanced oxidized TMB(oxTMB),accompanied by the color change from colorless to blue.In the presence of S.aureus,the secreted MNase preferentially cut the nucleobase AT-rich regions of DNA sequences on magnetic beads(MBs)to release alkaline phosphatase(ALP),which subsequently mediated the oxTMB reduction for inducing the colorimetric/SERS signal fade away.Using this“on-to-off”triggering strategy,the target S.aureus can be recorded in a wide linear range with a limit of detection of 38 CFU/mL in the colorimetric mode and 6 CFU/mL in the SERS mode.Meanwhile,the MNase-mediated strategy characterized by high specificity and sensitivity successfully discriminated between patients with sepsis(n=7)and healthy participants(n=3),as well as monitored the prognostic progression of the disease(n=2).Overall,benefiting from highly active and dense“hot spot”substrate,MNase-mediated cascade response strategy,and colorimetric/SERS dual-signal output,this methodology will offer a promising avenue for the early diagnosis of S.aureus infection.展开更多
Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using si...Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using simple rotational models.AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures.In this study,we synthesized water-soluble derivatives of representative AIEgens,including tetraphenylethene(TPE),bis(N,N-dialkylamino)anthracene(BDAA),and bridged stilbene,and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity.To elucidate the origin of their viscosity responsiveness,quantum chemical calculations were conducted to analyze their potential energy surfaces(PESs).The results revealed that compared to typical molecular rotors,these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions.Notably,for TPE and BDAA derivatives,the viscosity responsiveness was found to be governed not by the activation energy barrier(ΔE_(a))based on the PES,but rather by the viscosity-dependent constraints on molecular structural changes.Furthermore,molecules possessing multiple aromatic rings or large,flexible,rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions.This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens,thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscositysensitive probes.展开更多
基金supported by the National Natural Science Foundation of China(22375002)the Anhui Provincial Natural Science Foundation(2308085Y10).
文摘Solvents in crystalline materials typically exist either as structural components that stabilize the framework or as adsorbed vips that modulate properties,yet achieving their orthogonal coexistence within a single system remains challenging.This study proposes a natural mineral-inspired solvent hierarchy strategy that enables the concurrent achievement of framework stability and dynamic responsiveness in hydrogen-bonded organic frameworks(HOFs)through the orthogonal integration of structural and adsorbed solvents.We have validated the feasibility of this solvent hierarchy approach based on four model systems with progressively increasing stability and dynamism:(1)unstable HOFs containing only adsorbed solvents,(2)unstable HOFs with low-binding-energy structural solvents,(3)stable HOFs incorporating strong-fitted structural solvents,and(4)stable HOFs with structural solvents and dynamically adjustable adsorption solvents.Crystallographic and theoretical analyses reveal that the superior stability of structural solvents originates from the high-electron-density oxygen of the DMSO S═O bond,which acts as a strong hydrogen-bond acceptor,forming stable N─H…O═S bonds with amine groups.The host’s aggregation-induced emission(AIE)characteristics allow real-time optical monitoring of reversible single-crystal-to-single-crystal transformations without compromising structural integrity,demonstrating promising applications for visual water content and water leakage detection.This work not only establishes a new paradigm in solvent engineering for developing smart crystalline materials but also expands the design possibilities for functional porous frameworks.
基金supported by the National Natural Science Foundation of China(No.82260878)Guizhou Medical University Affiliated Hospital Doctoral Research Initiation Fund Project(gyfybsky-2021-44)+3 种基金Guizhou Provincial Science and Technology Plan Project(Qiankehe Achievements LC[2022]014)High-level Innovative Talents Cultivation Program of Guizhou Province(QianKeHe[2016]5679)Province Guiyang City Science and Technology Projects,Zhu Subjects Contract([2022]4-2-5)Guizhou Science and Technology Planning Project(QianKeHe[2020]4Y198).
文摘Background:Nonsuicidal self-injury(NSSI)in adolescents with depression disorders often exhibits addictive patterns,potentially linked to serum beta-endorphin levels and neural reward responsiveness.Beta-endorphin,involved in reward processing,alongside dysregulated neural reward pathways,may reinforce self-injurious behaviors,highlighting the need to explore these mechanisms.Methods:Adolescents(aged 12-17 years)with depression disorders were divided into an NSSI group(21 subjects)and a control group(11 subjects)according to inclusion criteria.Serum beta-endorphin concentration was measured using the enzyme-linked immunosorbent assay method.The Addiction Factor Scale was used to assess addiction levels.Statistical analyses were con-ducted using SPSS 25.0.The oxygenated hemoglobin response signal was detected using functional near-infrared spectroscopy.Analyses were performed using NIRS_KIT 2.0.Results:Compared with the control group,the NSSI group exhibited lower serum beta-endorphin concentration.Additionally,85.7%of those in the NSSI group displayed addictive behaviors,and serum beta-endorphin concentration was negatively correlated with the Addiction Factor Scale score.The reward task activated channels 17,20,and 21(corresponding to the dorsolateral prefrontal cortex[PFC]and frontopolar PFC)in the gain condition and channels 20 and 21 in the loss condition.The oxygenated hemoglobin concentration of the differential waveform(Δ[oxy-Hb])of channel 12(corresponding to the frontopolar PFC)correlated positively with the Addiction Factor Scale score and negatively with the serum beta-endorphin concentration.
基金financially supported by the National Natural Science Foundation of China(Nos.22273098,52033001 and 22303032)the Key Project of Anhui Province Science and Technology Innovation Platform(No.S202305a12020030)+1 种基金the Science and Technology Program Project of Zhejiang Province,China(No.2025ZY01057)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication。
文摘Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been revealed in the past ten years,it is still unclear if the pH-responsive properties of SPBs are affected by the brush thickness.In this study,we employed the positively charged poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride(PMETAC)and negatively charged sodium poly(styrenesulfonate)(NaPSS)brushes as model systems to explore the effect of thickness on the pH-responsive properties of SPBs.The results demonstrate that the pH-responsive properties of SPBs manifest different dependences on the brush thickness.Specifically,for both PMETAC and NaPSS brushes,the pH-responsive hydration and stiffness are influenced by the thickness,and the pH-responsive wettability and adhesion are almost unaffected by the thickness.This work not only provides a clear understanding of the relationship between the brush thickness and the pH responsiveness of SPBs,but also offers a new method to control the pH-responsive properties of SPBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.:82373833,22177039,and 82304438)the National Key Research and Development Program of China(Grant No.:2021YFC2300400)Guangdong Basic and Applied Basic Research Foundation,China(Grant Nos.:2024A1515012204,2022A1515010300,and 2022A1515110618).
文摘Rapid and ultrasensitive detection of pathogen-associated biomarkers is vital for the early diagnosis and therapy of bacterial infections.Herein,we developed a close-packed and ordered Au@AgPt array coupled with a cascade triggering strategy for surface-enhanced Raman scattering(SERS)and colorimetric identification of the Staphylococcus aureus biomarker micrococcal nuclease(MNase)in serum samples.The trimetallic Au@AgPt nanozymes can catalyze the oxidation of 3,3’,5,5’-tetramethylbenzidine(TMB)molecules to SERS-enhanced oxidized TMB(oxTMB),accompanied by the color change from colorless to blue.In the presence of S.aureus,the secreted MNase preferentially cut the nucleobase AT-rich regions of DNA sequences on magnetic beads(MBs)to release alkaline phosphatase(ALP),which subsequently mediated the oxTMB reduction for inducing the colorimetric/SERS signal fade away.Using this“on-to-off”triggering strategy,the target S.aureus can be recorded in a wide linear range with a limit of detection of 38 CFU/mL in the colorimetric mode and 6 CFU/mL in the SERS mode.Meanwhile,the MNase-mediated strategy characterized by high specificity and sensitivity successfully discriminated between patients with sepsis(n=7)and healthy participants(n=3),as well as monitored the prognostic progression of the disease(n=2).Overall,benefiting from highly active and dense“hot spot”substrate,MNase-mediated cascade response strategy,and colorimetric/SERS dual-signal output,this methodology will offer a promising avenue for the early diagnosis of S.aureus infection.
基金JSPS Research Fellowships for Young Scientistssupported in part by JST SPRING,Japan(Nos.JPMJSP2106 and JPMJSP2180,Takuya Tanaka.and Yuki Sawatari.)+1 种基金MEXT/JSPS KAKENHI grants(No.23H02036,Gen-ichi Konishi)Murata Science and Education Foundation(Gen-ichi Konishi)。
文摘Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using simple rotational models.AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures.In this study,we synthesized water-soluble derivatives of representative AIEgens,including tetraphenylethene(TPE),bis(N,N-dialkylamino)anthracene(BDAA),and bridged stilbene,and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity.To elucidate the origin of their viscosity responsiveness,quantum chemical calculations were conducted to analyze their potential energy surfaces(PESs).The results revealed that compared to typical molecular rotors,these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions.Notably,for TPE and BDAA derivatives,the viscosity responsiveness was found to be governed not by the activation energy barrier(ΔE_(a))based on the PES,but rather by the viscosity-dependent constraints on molecular structural changes.Furthermore,molecules possessing multiple aromatic rings or large,flexible,rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions.This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens,thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscositysensitive probes.
