Pub Date : 2026-03-27DOI: 10.1021/acs.chemmater.5c01499
Poonam Yadav, Ruchira Chakraborty, Kajal Rana, Somesh Kumar Jha, Sonu K. Gupta, Nishant Pandey, Ali Khan, Devashish Mehta, Dolly Jain, Monika Yadav, Nikhil Kumar Chourasiya, Vandana Dhangar, Yashwant Kumar, Prasenjit Das, Avinash Bajaj
Colorectal liver metastasis is one of the major causes of poor survival in colorectal cancer patients as it causes organ dysfunction and disrupts metabolic homeostasis. Apart from the primary tumor microenvironment (TME) challenges arising from cell proliferation, immunosuppression, and angiogenesis, premetastatic niches also represent an attractive therapeutic target for preventing liver metastasis. Here, we present the engineering of a unique, highly stable sub-100 nm three-drug-loaded nanomicelles (TDC NMs) system carrying the antiproliferative drug gemcitabine, the antiangiogenic drug combretastatin A4, and the anti-inflammatory drug dexamethasone. TDC NMs mitigate tumor progression in syngeneic, xenograft, orthotopic, and metastatic tumors. In-depth quantification of the changes in immune cells revealed that TDC NMs promote T-cell-mediated antitumor immunity, limit the infiltration of protumorigenic MDSCs, and enhance the antitumorigenic M1 population. TDC NMs could also reduce tumor progression, restore abdominal circumference, and normalize ascites fluid formation in orthotopic and metastatic colon cancer models. We further demonstrated that TDC NMs inhibit the formation of premetastatic niches by targeting MDSCs and macrophages, thereby achieving metabolic homeostasis. This study provides a promising therapeutic strategy for mitigating primary tumors and premetastatic niches and can therefore be explored further in colorectal cancer patients.
{"title":"Engineered Nanomicelles Prevent Colorectal Liver Metastasis via Inhibiting the Premetastatic Niche and Regulating the Metabolic Homeostasis","authors":"Poonam Yadav, Ruchira Chakraborty, Kajal Rana, Somesh Kumar Jha, Sonu K. Gupta, Nishant Pandey, Ali Khan, Devashish Mehta, Dolly Jain, Monika Yadav, Nikhil Kumar Chourasiya, Vandana Dhangar, Yashwant Kumar, Prasenjit Das, Avinash Bajaj","doi":"10.1021/acs.chemmater.5c01499","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01499","url":null,"abstract":"Colorectal liver metastasis is one of the major causes of poor survival in colorectal cancer patients as it causes organ dysfunction and disrupts metabolic homeostasis. Apart from the primary tumor microenvironment (TME) challenges arising from cell proliferation, immunosuppression, and angiogenesis, premetastatic niches also represent an attractive therapeutic target for preventing liver metastasis. Here, we present the engineering of a unique, highly stable sub-100 nm three-drug-loaded nanomicelles (TDC NMs) system carrying the antiproliferative drug gemcitabine, the antiangiogenic drug combretastatin A4, and the anti-inflammatory drug dexamethasone. TDC NMs mitigate tumor progression in syngeneic, xenograft, orthotopic, and metastatic tumors. In-depth quantification of the changes in immune cells revealed that TDC NMs promote T-cell-mediated antitumor immunity, limit the infiltration of protumorigenic MDSCs, and enhance the antitumorigenic M1 population. TDC NMs could also reduce tumor progression, restore abdominal circumference, and normalize ascites fluid formation in orthotopic and metastatic colon cancer models. We further demonstrated that TDC NMs inhibit the formation of premetastatic niches by targeting MDSCs and macrophages, thereby achieving metabolic homeostasis. This study provides a promising therapeutic strategy for mitigating primary tumors and premetastatic niches and can therefore be explored further in colorectal cancer patients.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"3 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-27DOI: 10.1021/acs.chemmater.5c03365
Michael A. Spencer, Nguyen Quan Dao, Taegyu Yun, Juan Forero-Saboya, German Lavygin, Raj Pandya, Marie-Liesse Doublet, Alexis Grimaud
Li-rich sulfides are promising alternatives to Li-rich oxides as intercalation materials, the latter suffering from limited cycling reversibility and copious voltage fade, all associated with the redox activity of oxygen ligands upon cycling. Although moving from oxygen to sulfur ligands alleviates some of these drawbacks, sulfides suffer from their lower redox potential, which limits the energy density. Here, we partially replace divalent sulfur ligands with monovalent chlorine and synthesize transition metal sulfochlorides Li2M1–xMnxS2Cl (with M = Ti4+ and Nb5+) crystallizing in a cation-disordered rock salt (DRX) structure. Owing to the greater electronegativity of chlorine compared to sulfur, we demonstrate an increase in the average redox potential for DRX sulfochlorides. Combining ex situ X-ray absorption spectroscopy measurements at various edges and density functional theory calculations, we demonstrate that chlorine ligands preferentially form Mn–Cl and Li–Cl bonds, while sulfur ligands preferentially coordinate the high valence d0 metals. While sulfur ligands are redox active throughout the charge (and discharge), Mn2+ redox activity depends on the chemical composition, with Li2Ti0.5Mn0.5S2Cl showing cationic redox activity only at the end of the charge and beginning of the discharge. More dramatically, our experimental and computational results demonstrate that the S–S bond formation induces sizable changes in local coordination and partial material dissolution into the electrolyte, triggering cell corrosion and/or short formation as early as the second cycle. Through an electrolyte engineering approach, combining a Cl-scavenger molecule with a cathode electrolyte interphase former, we demonstrate that corrosion and/or shorts formation can be suppressed, and intrinsic cycling properties of sulfochloride DRX materials are investigated. Our work extends the chemical space for designing better intercalation materials, showing the unique opportunities brought by mixed anion compounds.
{"title":"Chlorine Substitution in Disordered Rock Salt Li-Rich Transition Metal Sulfides","authors":"Michael A. Spencer, Nguyen Quan Dao, Taegyu Yun, Juan Forero-Saboya, German Lavygin, Raj Pandya, Marie-Liesse Doublet, Alexis Grimaud","doi":"10.1021/acs.chemmater.5c03365","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03365","url":null,"abstract":"Li-rich sulfides are promising alternatives to Li-rich oxides as intercalation materials, the latter suffering from limited cycling reversibility and copious voltage fade, all associated with the redox activity of oxygen ligands upon cycling. Although moving from oxygen to sulfur ligands alleviates some of these drawbacks, sulfides suffer from their lower redox potential, which limits the energy density. Here, we partially replace divalent sulfur ligands with monovalent chlorine and synthesize transition metal sulfochlorides Li<sub>2</sub>M<sub>1–<i>x</i></sub>Mn<sub><i>x</i></sub>S<sub>2</sub>Cl (with M = Ti<sup>4+</sup> and Nb<sup>5+</sup>) crystallizing in a cation-disordered rock salt (DRX) structure. Owing to the greater electronegativity of chlorine compared to sulfur, we demonstrate an increase in the average redox potential for DRX sulfochlorides. Combining <i>ex situ</i> X-ray absorption spectroscopy measurements at various edges and density functional theory calculations, we demonstrate that chlorine ligands preferentially form Mn–Cl and Li–Cl bonds, while sulfur ligands preferentially coordinate the high valence d<sup>0</sup> metals. While sulfur ligands are redox active throughout the charge (and discharge), Mn<sup>2+</sup> redox activity depends on the chemical composition, with Li<sub>2</sub>Ti<sub>0.5</sub>Mn<sub>0.5</sub>S<sub>2</sub>Cl showing cationic redox activity only at the end of the charge and beginning of the discharge. More dramatically, our experimental and computational results demonstrate that the S–S bond formation induces sizable changes in local coordination and partial material dissolution into the electrolyte, triggering cell corrosion and/or short formation as early as the second cycle. Through an electrolyte engineering approach, combining a Cl-scavenger molecule with a cathode electrolyte interphase former, we demonstrate that corrosion and/or shorts formation can be suppressed, and intrinsic cycling properties of sulfochloride DRX materials are investigated. Our work extends the chemical space for designing better intercalation materials, showing the unique opportunities brought by mixed anion compounds.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"16 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-26DOI: 10.1021/acs.chemmater.5c02593
Yang Li, Rui Li, Thomas Kress, David G. Reid, Karin H. Müller, Danielle Laurencin, Christian Bonhomme, E. Alex Ossa, Chenglong Li, Robin van der Meijden, Nico Sommerdijk, Melinda J Duer
Bone mineral forms both inside and between collagen fibrils in the extracellular matrix. While the morphology of intrafibrillar bone mineral has been hypothesized to be primarily controlled by the size and shape of the restricted spaces inside collagen fibrils within which the mineral forms, what controls the architecture of the extrafibrillar mineral is still an open question. While bone mineral is primarily apatitic in composition, it also contains significant quantities of cell respiration metabolites, in particular, carbonate, citrate, and lactate. An as-yet unanswered question is what, if any, role do these metabolites collectively play in determining the 3D architecture of bone mineral. Here, we propose a composite model of bone mineral that accounts for both intra- and extrafibrillar mineral environments, and to that end, we develop apatitic materials containing citrate and lactate or carbonate that mimic the densely packed ionic environments within which bone mineral forms in vivo. We find that incorporating citrate and lactate leads to complex mineral architectures reminiscent of those in extrafibrillar bone mineral, including mineral crystal curvature. Our results suggest that metabolic acids may play an important role in building the 3D architecture of extrafibrillar bone mineral.
{"title":"Role of Metabolic Acids in Shaping Bone-like Apatite Architectures","authors":"Yang Li, Rui Li, Thomas Kress, David G. Reid, Karin H. Müller, Danielle Laurencin, Christian Bonhomme, E. Alex Ossa, Chenglong Li, Robin van der Meijden, Nico Sommerdijk, Melinda J Duer","doi":"10.1021/acs.chemmater.5c02593","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02593","url":null,"abstract":"Bone mineral forms both inside and between collagen fibrils in the extracellular matrix. While the morphology of intrafibrillar bone mineral has been hypothesized to be primarily controlled by the size and shape of the restricted spaces inside collagen fibrils within which the mineral forms, what controls the architecture of the extrafibrillar mineral is still an open question. While bone mineral is primarily apatitic in composition, it also contains significant quantities of cell respiration metabolites, in particular, carbonate, citrate, and lactate. An as-yet unanswered question is what, if any, role do these metabolites collectively play in determining the 3D architecture of bone mineral. Here, we propose a composite model of bone mineral that accounts for both intra- and extrafibrillar mineral environments, and to that end, we develop apatitic materials containing citrate and lactate or carbonate that mimic the densely packed ionic environments within which bone mineral forms in vivo. We find that incorporating citrate and lactate leads to complex mineral architectures reminiscent of those in extrafibrillar bone mineral, including mineral crystal curvature. Our results suggest that metabolic acids may play an important role in building the 3D architecture of extrafibrillar bone mineral.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"101 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-26DOI: 10.1021/acs.chemmater.6c00092
Yunseung Kuk, Kang Min Ok, P. Shiv Halasyamani
Despite significant advances in nonlinear optical (NLO) materials, a systematic strategy for designing mid-infrared (mid-IR) NLO oxides that simultaneously exhibit strong second-harmonic generation (SHG) efficiency and wide optical transparency remains elusive. Herein, we report two polar antiperovskite oxide materials, (Pb1.5Cd1.5)GeO5 (PCGO) and Pb3GeO5 (PGO). Structural analyses reveal that PCGO adopts a 2H-hexagonal antiperovskite structure, whereas PGO features a three-dimensional antiperovskite framework. Both materials are thermally stable up to approximately 900 °C and exhibit wide optical transparency extending into the mid-IR region (0.3–13 μm). Powder SHG measurements indicate that PCGO and PGO exhibit strong SHG efficiencies of 0.5 and 1.3 times that of AgGaS2, respectively, along with particle-size-dependent SHG responses indicative of phase-matching behavior. Further first-principles calculations reveal moderate birefringence values of 0.053 and 0.058 at 1064 nm for PCGO and PGO, respectively, corresponding to shortest phase-matching (PM) wavelengths of 737 and 776 nm. A closer structural investigation and density functional theory calculations suggest that the pronounced distortions of OPb/Cd6 and OPb6 octahedra, together with highly polarizable cations, play a dominant role in governing the SHG responses. These results highlight polar antiperovskite oxides as a promising platform for the development of next-generation mid-IR NLO materials.
{"title":"Polar Antiperovskite Oxides: Promising Mid-Infrared Nonlinear Optical Materials with Strong Second-Harmonic Generation","authors":"Yunseung Kuk, Kang Min Ok, P. Shiv Halasyamani","doi":"10.1021/acs.chemmater.6c00092","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00092","url":null,"abstract":"Despite significant advances in nonlinear optical (NLO) materials, a systematic strategy for designing mid-infrared (mid-IR) NLO oxides that simultaneously exhibit strong second-harmonic generation (SHG) efficiency and wide optical transparency remains elusive. Herein, we report two polar antiperovskite oxide materials, (Pb<sub>1.5</sub>Cd<sub>1.5</sub>)GeO<sub>5</sub> (PCGO) and Pb<sub>3</sub>GeO<sub>5</sub> (PGO). Structural analyses reveal that PCGO adopts a 2H-hexagonal antiperovskite structure, whereas PGO features a three-dimensional antiperovskite framework. Both materials are thermally stable up to approximately 900 °C and exhibit wide optical transparency extending into the mid-IR region (0.3–13 μm). Powder SHG measurements indicate that PCGO and PGO exhibit strong SHG efficiencies of 0.5 and 1.3 times that of AgGaS<sub>2</sub>, respectively, along with particle-size-dependent SHG responses indicative of phase-matching behavior. Further first-principles calculations reveal moderate birefringence values of 0.053 and 0.058 at 1064 nm for PCGO and PGO, respectively, corresponding to shortest phase-matching (PM) wavelengths of 737 and 776 nm. A closer structural investigation and density functional theory calculations suggest that the pronounced distortions of OPb/Cd<sub>6</sub> and OPb<sub>6</sub> octahedra, together with highly polarizable cations, play a dominant role in governing the SHG responses. These results highlight polar antiperovskite oxides as a promising platform for the development of next-generation mid-IR NLO materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-25DOI: 10.1021/acs.chemmater.5c03021
Xiaoyan Jin,So Yeon Yun,Seong-Ju Hwang
Two-dimensional transition-metal dichalcogenide nanosheets made of MoS2 are widely studied owing to their applications as electrocatalysts and electrode materials. To specify key design parameters for optimizing catalytic performance of MoS2, we developed a soft-chemical lattice manipulation strategy to precisely tune their structural, defect, and morphological characteristics via self-assembly of the exfoliated MoS2 nanosheet with various guest cations. Most alkali-metal-restacked MoS2 nanosheets exhibit a layer-by-layer ordered intercalation structure containing water monolayers; however, self-assembly with Li+ ions led to the intercalation of thicker water bilayers, attributed to the higher hydration energy of smaller Li+ ions. Increasing the basal spacing induced a gradual phase transformation from 2H-type bulk MoS2 to 1T MoS2 structure restacked with H+ and Na+ ions and further to a highly distorted 1T′ MoS2 structure restacked with Li+ and Cs+ ions. Additionally, an increase in the guest size led to an increase in the defect concentration. The Cs+-restacked MoS2 exhibited the lowest overpotential and smallest Tafel slope for hydrogen evolution reactions. Correlating the electrocatalytic activity with structural, defect, and morphological parameters revealed that unlike interlayer spacing and crystal phase, the surface area and defect concentration are dominant factors governing the electrocatalytic performance of MoS2. This conclusion was supported by in situ Raman analysis, which indicated enhanced hydrogen adsorption and accumulation on the Cs+-restacked MoS2 surface, suggesting an efficient Volmer–Tafel reaction pathway.
{"title":"Soft-Chemical Tuning of Structural, Defect, and Morphological Properties of MoS2: Elucidating the Governing Factors of Electrocatalytic Activity","authors":"Xiaoyan Jin,So Yeon Yun,Seong-Ju Hwang","doi":"10.1021/acs.chemmater.5c03021","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03021","url":null,"abstract":"Two-dimensional transition-metal dichalcogenide nanosheets made of MoS2 are widely studied owing to their applications as electrocatalysts and electrode materials. To specify key design parameters for optimizing catalytic performance of MoS2, we developed a soft-chemical lattice manipulation strategy to precisely tune their structural, defect, and morphological characteristics via self-assembly of the exfoliated MoS2 nanosheet with various guest cations. Most alkali-metal-restacked MoS2 nanosheets exhibit a layer-by-layer ordered intercalation structure containing water monolayers; however, self-assembly with Li+ ions led to the intercalation of thicker water bilayers, attributed to the higher hydration energy of smaller Li+ ions. Increasing the basal spacing induced a gradual phase transformation from 2H-type bulk MoS2 to 1T MoS2 structure restacked with H+ and Na+ ions and further to a highly distorted 1T′ MoS2 structure restacked with Li+ and Cs+ ions. Additionally, an increase in the guest size led to an increase in the defect concentration. The Cs+-restacked MoS2 exhibited the lowest overpotential and smallest Tafel slope for hydrogen evolution reactions. Correlating the electrocatalytic activity with structural, defect, and morphological parameters revealed that unlike interlayer spacing and crystal phase, the surface area and defect concentration are dominant factors governing the electrocatalytic performance of MoS2. This conclusion was supported by in situ Raman analysis, which indicated enhanced hydrogen adsorption and accumulation on the Cs+-restacked MoS2 surface, suggesting an efficient Volmer–Tafel reaction pathway.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"9 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-25DOI: 10.1021/acs.chemmater.5c03169
Nuwanthaka P. Jayaweera, Michael W. Mara, Gethmini K. Jayasekara, Taylor Harville, Ashley R. Bielinski, Shana Havenridge, Kihoon Kim, Cong Liu, Karen L. Mulfort, Alex B. F. Martinson
Few-atom metal chalcogenide clusters may be realized through the sequential infiltration of metal–organic precursors in polymer films. However, the underlying nucleation and growth mechanisms that allow for cluster synthesis with near atomic-scale precision are not fully resolved. The kinetics of the sequential infiltration synthesis (SIS) method that control the nucleation and growth mechanisms of primarily Cd4S4-core clusters within a poly(4-vinylpyridine) (P4VP) matrix are probed with in situ UV–visible absorbance spectroscopy. Density functional theory (DFT) calculations that allow simulation of the optical properties of cluster fragments further reveal the thermodynamics that guide cluster growth within the P4VP matrix. We conclude that a reactive capture mechanism for cluster nucleation and growth is dominant, although transient dimethyl cadmium adduction to the polymer backbone may contribute to cluster nucleation under shorter metal–organic purge process conditions. Grazing incidence X-ray diffraction (GI-XRD) and X-ray absorption spectroscopy (XAS) analyses further corroborate the cluster size and atom connectivity throughout the stepwise synthesis.
{"title":"Probing the Mechanism of Cadmium Sulfide Cluster Nucleation and Growth via Sequential Infiltration Synthesis","authors":"Nuwanthaka P. Jayaweera, Michael W. Mara, Gethmini K. Jayasekara, Taylor Harville, Ashley R. Bielinski, Shana Havenridge, Kihoon Kim, Cong Liu, Karen L. Mulfort, Alex B. F. Martinson","doi":"10.1021/acs.chemmater.5c03169","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03169","url":null,"abstract":"Few-atom metal chalcogenide clusters may be realized through the sequential infiltration of metal–organic precursors in polymer films. However, the underlying nucleation and growth mechanisms that allow for cluster synthesis with near atomic-scale precision are not fully resolved. The kinetics of the sequential infiltration synthesis (SIS) method that control the nucleation and growth mechanisms of primarily Cd<sub>4</sub>S<sub>4</sub>-core clusters within a poly(4-vinylpyridine) (P4VP) matrix are probed with in situ UV–visible absorbance spectroscopy. Density functional theory (DFT) calculations that allow simulation of the optical properties of cluster fragments further reveal the thermodynamics that guide cluster growth within the P4VP matrix. We conclude that a reactive capture mechanism for cluster nucleation and growth is dominant, although transient dimethyl cadmium adduction to the polymer backbone may contribute to cluster nucleation under shorter metal–organic purge process conditions. Grazing incidence X-ray diffraction (GI-XRD) and X-ray absorption spectroscopy (XAS) analyses further corroborate the cluster size and atom connectivity throughout the stepwise synthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cuprophilic interactions are increasingly recognized as key determinants in the design of functional assemblies, particularly for enhancing luminescence. However, achieving precise control of cuprophilic interactions in self-assembled, atomically precise copper nanoclusters remains challenging. Here, we present a straightforward strategy to systematically modulate cuprophilic interactions through the supramolecular self-assembly of an atomically precise Cu(I) nanocluster, [Cu6(MBID)6] (Cu6, HMBID = 2-mercaptobenzimidazole). The aggregation behavior of Cu6 is finely regulated by solvation engineering, with controlled self-assembly into well-defined hexagonal nanoplates occurring exclusively within a solvent fraction range (fw = 50–60%). This process strengthens cuprophilic interactions, thereby leading to pronounced improvements in photoelectrical properties, including luminescence and photocurrent generation. Ab initio molecular dynamics (AIMD) simulations reveal that in a 50:50 water/DMSO medium, Cu···Cu distances within Cu6 are significantly shortened, providing computational evidence for strengthened metallophilic interactions during aggregation. Complementarily, Raman spectroscopy directly tracks the evolution of Cu···Cu distances across distinct aggregation states, offering experimental confirmation of aggregation-induced reinforcement of cuprophilic interactions. Collectively, this work establishes Cu6 as a robust model for supramolecular cluster self-assembly and underscores the pivotal role of metallophilic interactions in constructing cluster-based aggregates with tunable optical properties.
{"title":"Aggregation-Mediated Cuprophilic Interactions Governing the Luminescence of a Cu6 Nanocluster","authors":"Bao-Liang Han,Pan-Pan Sun,Zhen-Nan Wu,Rishu Narwal,Vikas Tiwari,Rakesh Kumar Gupta,Tarak Karmakar,Zhi Wang,Chen-Ho Tung,Di Sun","doi":"10.1021/acs.chemmater.5c02698","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02698","url":null,"abstract":"Cuprophilic interactions are increasingly recognized as key determinants in the design of functional assemblies, particularly for enhancing luminescence. However, achieving precise control of cuprophilic interactions in self-assembled, atomically precise copper nanoclusters remains challenging. Here, we present a straightforward strategy to systematically modulate cuprophilic interactions through the supramolecular self-assembly of an atomically precise Cu(I) nanocluster, [Cu6(MBID)6] (Cu6, HMBID = 2-mercaptobenzimidazole). The aggregation behavior of Cu6 is finely regulated by solvation engineering, with controlled self-assembly into well-defined hexagonal nanoplates occurring exclusively within a solvent fraction range (fw = 50–60%). This process strengthens cuprophilic interactions, thereby leading to pronounced improvements in photoelectrical properties, including luminescence and photocurrent generation. Ab initio molecular dynamics (AIMD) simulations reveal that in a 50:50 water/DMSO medium, Cu···Cu distances within Cu6 are significantly shortened, providing computational evidence for strengthened metallophilic interactions during aggregation. Complementarily, Raman spectroscopy directly tracks the evolution of Cu···Cu distances across distinct aggregation states, offering experimental confirmation of aggregation-induced reinforcement of cuprophilic interactions. Collectively, this work establishes Cu6 as a robust model for supramolecular cluster self-assembly and underscores the pivotal role of metallophilic interactions in constructing cluster-based aggregates with tunable optical properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"9 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-25DOI: 10.1021/acs.chemmater.5c03307
Sheng Yin,Yashi Wang,Hao Guo,Shiyong Zhang
Acute liver injury (ALI) poses a severe treatment challenge due to multipathological mechanisms. Herein, cross-linked lipoic acid trisulfide nanoparticles (cLAT NPs) were developed against ALI by self-assembly and ring-opening polymerization of lipoic acid trisulfide (LAT). Upon accumulation in the liver, the cLAT NPs, owing to the polysulfide structure, highly efficiently entered into cells via thiol-mediated uptake and generated hydrogen sulfide (H2S) by intracellular glutathione (GSH)-responsive depolymerization. Concurrently, the highly biocompatible compound lipoic acid (LA) was produced, which promoted the expression of endogenous H2S-producing enzymes, such as cystathionine γ-lyase (CSE), thereby augmenting the endogenous H2S generation. Ultimately, cLAT NPs exerted hepatoprotective effects through multipathway regulation, including direct scavenging of reactive oxygen species (ROS), activation of nuclear factor erythroid 2-related factor 2 (Nrf2), and inhibition of nuclear factor kappa-B (NF-κB). Notably, a single intravenous administration of 10 mg/kg cLAT NPs ultimately achieved a 100% survival rate in the ALI mouse model, whereas the clinical drug N-acetylcysteine (150 mg/kg) yielded only a 20% survival rate. cLAT NPs provide a paradigm against ALI by multipathway regulation.
{"title":"Cross-Linked Lipoic Acid Trisulfide Nanoparticles against Acute Liver Injury by Multipathway Regulation","authors":"Sheng Yin,Yashi Wang,Hao Guo,Shiyong Zhang","doi":"10.1021/acs.chemmater.5c03307","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03307","url":null,"abstract":"Acute liver injury (ALI) poses a severe treatment challenge due to multipathological mechanisms. Herein, cross-linked lipoic acid trisulfide nanoparticles (cLAT NPs) were developed against ALI by self-assembly and ring-opening polymerization of lipoic acid trisulfide (LAT). Upon accumulation in the liver, the cLAT NPs, owing to the polysulfide structure, highly efficiently entered into cells via thiol-mediated uptake and generated hydrogen sulfide (H2S) by intracellular glutathione (GSH)-responsive depolymerization. Concurrently, the highly biocompatible compound lipoic acid (LA) was produced, which promoted the expression of endogenous H2S-producing enzymes, such as cystathionine γ-lyase (CSE), thereby augmenting the endogenous H2S generation. Ultimately, cLAT NPs exerted hepatoprotective effects through multipathway regulation, including direct scavenging of reactive oxygen species (ROS), activation of nuclear factor erythroid 2-related factor 2 (Nrf2), and inhibition of nuclear factor kappa-B (NF-κB). Notably, a single intravenous administration of 10 mg/kg cLAT NPs ultimately achieved a 100% survival rate in the ALI mouse model, whereas the clinical drug N-acetylcysteine (150 mg/kg) yielded only a 20% survival rate. cLAT NPs provide a paradigm against ALI by multipathway regulation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"112 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-24DOI: 10.1021/acs.chemmater.5c02981
Adam Berlie,Emma K. Gibson,Ian P. Silverwood,Vainius Skukauskas
Understanding the active site dynamics and redox behavior of copper species in zeolite catalysts is critical for advancing the understanding of catalytic methane-to-methanol conversion. These catalysts are also used for the selective catalytic reduction of NOx in diesel engines. Here, we present the first application of muon spin spectroscopy (μSR) to study transition metal-exchanged SSZ-13 (Cu-SSZ-13) zeolites and highlight the potential of μSR. This technique reveals unique insights into the local magnetic and electronic environments of Cu species, inaccessible via conventional spectroscopies. Temperature-dependent transverse field μSR measurements show a clear conversion of paramagnetic muonium (Mu0) to diamagnetic muon (Mu+) states, with distinct differences between Cu-loaded and pure SSZ-13 systems. This transformation is thermally activated, with Arrhenius analysis yielding activation energies of ∼3.3–5 meV, consistent with ionization processes of shallow donor states. Longitudinal field measurements confirm 2D muonium diffusion within Cu-SSZ-13 and support a model where muonium reacts with mono(μ-oxo)dicopper species, inducing comproportionation (2Cu2+ → 2Cu1.5+). DFT simulations validate this mechanism, reproducing the experimentally determined hyperfine coupling constants. At low temperatures (≤25 K), μSR also detects the onset of static magnetism in Cu clusters, consistent with Cu(II)-based multinuclear motifs. These results establish μSR as a powerful, underutilized probe for catalytic systems and provide compelling evidence for a multistep oxidation mechanism involving the initial reduction of Cu centers prior to methanol formation. This approach opens new avenues for real-time, local investigation of redox-active catalytic materials.
{"title":"Muons Provide Insights into the Mechanisms of Catalysis in Copper-Loaded Zeolites","authors":"Adam Berlie,Emma K. Gibson,Ian P. Silverwood,Vainius Skukauskas","doi":"10.1021/acs.chemmater.5c02981","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02981","url":null,"abstract":"Understanding the active site dynamics and redox behavior of copper species in zeolite catalysts is critical for advancing the understanding of catalytic methane-to-methanol conversion. These catalysts are also used for the selective catalytic reduction of NOx in diesel engines. Here, we present the first application of muon spin spectroscopy (μSR) to study transition metal-exchanged SSZ-13 (Cu-SSZ-13) zeolites and highlight the potential of μSR. This technique reveals unique insights into the local magnetic and electronic environments of Cu species, inaccessible via conventional spectroscopies. Temperature-dependent transverse field μSR measurements show a clear conversion of paramagnetic muonium (Mu0) to diamagnetic muon (Mu+) states, with distinct differences between Cu-loaded and pure SSZ-13 systems. This transformation is thermally activated, with Arrhenius analysis yielding activation energies of ∼3.3–5 meV, consistent with ionization processes of shallow donor states. Longitudinal field measurements confirm 2D muonium diffusion within Cu-SSZ-13 and support a model where muonium reacts with mono(μ-oxo)dicopper species, inducing comproportionation (2Cu2+ → 2Cu1.5+). DFT simulations validate this mechanism, reproducing the experimentally determined hyperfine coupling constants. At low temperatures (≤25 K), μSR also detects the onset of static magnetism in Cu clusters, consistent with Cu(II)-based multinuclear motifs. These results establish μSR as a powerful, underutilized probe for catalytic systems and provide compelling evidence for a multistep oxidation mechanism involving the initial reduction of Cu centers prior to methanol formation. This approach opens new avenues for real-time, local investigation of redox-active catalytic materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-24DOI: 10.1021/acs.chemmater.6c00482
Chi Wang,Guohong Tang,Kexin Huang,Yuhang Du,Jinsong Wei,Baojun Chen,Zhiyu He,Wei Huang
BaGa4Se7 is a promising infrared nonlinear optical (NLO) crystal, offering significant potential for mid-infrared applications. To further optimize its performance and explore new functional materials, we introduced Mg into the BaGa4Se7 lattice, successfully synthesizing a series of novel quaternary solid-solution NLO crystals. It confirms that the synthesized polycrystalline materials retain the same structure as the BaGa4Se7 crystal. Notably, Mg ions are incorporated into the crystal lattice by occupying two distinct cationic sites: the Ba2+ and Ga3+ sites. In the initial polycrystalline state, Mg preferentially occupies the Ba sites. During the subsequent slow, near-equilibrium single-crystal growth process, thermodynamic stability becomes the dominant factor governing Mg distribution. This leads to a redistribution of Mg ions: some Mg2+ ions that originally occupied the Ba sites are expelled toward the tail end of the growing crystal. In the main body of the crystal, a more stable and optimized occupancy pattern is established, where Mg2+ occupies both Ba and Ga sites in a specific equilibrium ratio. Remarkably, when this occupancy ratio reaches approximately 1:1, corresponding to the composition of Ba0.95Mg0.1Ga3.95Se7, the crystal demonstrates a significantly enhanced second-harmonic generation (SHG) response. Its SHG intensity at the fundamental wavelength of 1.064 μm is measured to be 1.86 times that of pure BaGa4Se7, while maintaining a high optical transmittance of up to 75% across the measured spectral range. This indicates a successful balance between enhancing the nonlinear optical coefficient and preserving excellent optical quality. However, as the Mg concentration is further increased, the substitution of Ga sites by Mg becomes dominant. This excessive substitution disrupts the optimal structural arrangement and charge balance, resulting in concurrent degradation of both nonlinear optical performance and overall optical properties. Our findings conclusively demonstrate that the nonlinear optical performance of BaGa4Se7 can be finely tuned and optimized through trace Mg substitution, highlighting the critical role of precise dopant control and site occupancy in developing next-generation high-performance infrared NLO materials.
{"title":"Mg Substitution in BaGa4Se7: Synthesis, Structure, and Property Modulation","authors":"Chi Wang,Guohong Tang,Kexin Huang,Yuhang Du,Jinsong Wei,Baojun Chen,Zhiyu He,Wei Huang","doi":"10.1021/acs.chemmater.6c00482","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00482","url":null,"abstract":"BaGa4Se7 is a promising infrared nonlinear optical (NLO) crystal, offering significant potential for mid-infrared applications. To further optimize its performance and explore new functional materials, we introduced Mg into the BaGa4Se7 lattice, successfully synthesizing a series of novel quaternary solid-solution NLO crystals. It confirms that the synthesized polycrystalline materials retain the same structure as the BaGa4Se7 crystal. Notably, Mg ions are incorporated into the crystal lattice by occupying two distinct cationic sites: the Ba2+ and Ga3+ sites. In the initial polycrystalline state, Mg preferentially occupies the Ba sites. During the subsequent slow, near-equilibrium single-crystal growth process, thermodynamic stability becomes the dominant factor governing Mg distribution. This leads to a redistribution of Mg ions: some Mg2+ ions that originally occupied the Ba sites are expelled toward the tail end of the growing crystal. In the main body of the crystal, a more stable and optimized occupancy pattern is established, where Mg2+ occupies both Ba and Ga sites in a specific equilibrium ratio. Remarkably, when this occupancy ratio reaches approximately 1:1, corresponding to the composition of Ba0.95Mg0.1Ga3.95Se7, the crystal demonstrates a significantly enhanced second-harmonic generation (SHG) response. Its SHG intensity at the fundamental wavelength of 1.064 μm is measured to be 1.86 times that of pure BaGa4Se7, while maintaining a high optical transmittance of up to 75% across the measured spectral range. This indicates a successful balance between enhancing the nonlinear optical coefficient and preserving excellent optical quality. However, as the Mg concentration is further increased, the substitution of Ga sites by Mg becomes dominant. This excessive substitution disrupts the optimal structural arrangement and charge balance, resulting in concurrent degradation of both nonlinear optical performance and overall optical properties. Our findings conclusively demonstrate that the nonlinear optical performance of BaGa4Se7 can be finely tuned and optimized through trace Mg substitution, highlighting the critical role of precise dopant control and site occupancy in developing next-generation high-performance infrared NLO materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"219 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：