ACS Macro LettersPub Date : 2024-11-12DOI: 10.1021/acsmacrolett.4c00520
Xuechen Zhang, Nicola Contessi Negrini, Rita Correia, Paul T. Sharpe, Adam D. Celiz, Ana Angelova Volponi
{"title":"Generating Tooth Organoids Using Defined Bioorthogonally Cross-Linked Hydrogels","authors":"Xuechen Zhang, Nicola Contessi Negrini, Rita Correia, Paul T. Sharpe, Adam D. Celiz, Ana Angelova Volponi","doi":"10.1021/acsmacrolett.4c00520","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00520","url":null,"abstract":"Generating teeth <i>in vitro</i> requires mimicking tooth developmental processes. Biomaterials are essential to support 3D tooth organoid formation, but their properties must be finely tuned to achieve the required biomimicry for tooth development. For the first time, we used bioorthogonally cross-linked hydrogels as defined 3D matrixes for tooth developmental engineering, and we highlighted how their properties play a pivotal role in enabling 3D tooth organoid formation <i>in vitro</i>. We prepared hydrogels by mixing gelatin precursors modified either with tetrazine (Tz) or norbornene (Nb) moieties. We tuned the hydrogel properties (<i>E</i> = 2–7 kPa; <i>G</i>′ = 500–1500 Pa) by varying the gelatin concentration (8% vs 12% w/V) and stoichiometric ratio (Tz:Nb = 1 vs 0.5). We encapsulated dental epithelial-mesenchymal cell pellets in a library of hydrogels and identified a hydrogel formulation that enabled successful growth kinetics and morphogenesis of tooth germs, introducing a defined tunable platform for tooth organoid engineering and modeling.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"38 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-12DOI: 10.1021/acsmacrolett.4c0066110.1021/acsmacrolett.4c00661
Kevin D. Dorfman*,
{"title":"Computational Phase Discovery in Block Polymers","authors":"Kevin D. Dorfman*, ","doi":"10.1021/acsmacrolett.4c0066110.1021/acsmacrolett.4c00661","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00661https://doi.org/10.1021/acsmacrolett.4c00661","url":null,"abstract":"<p >Self-consistent field theory (SCFT), the mean-field theory of polymer thermodynamics, is a powerful tool for understanding ordered state selection in block copolymer melts and blends. However, the nonlinear governing equations pose a significant challenge when SCFT is used for phase discovery because converging an SCFT solution typically requires an initial guess close to the self-consistent solution. This Viewpoint provides a concise overview of recent efforts where machine learning methods (particle swarm optimization, Bayesian optimization, and generative adversarial networks) have been used to make the first strides toward converting SCFT from a primarily explanatory tool into one that can be readily deployed for phase discovery.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1612–1619 1612–1619"},"PeriodicalIF":5.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-12DOI: 10.1021/acsmacrolett.4c0052010.1021/acsmacrolett.4c00520
Xuechen Zhang, Nicola Contessi Negrini, Rita Correia, Paul T. Sharpe, Adam D. Celiz* and Ana Angelova Volponi*,
{"title":"Generating Tooth Organoids Using Defined Bioorthogonally Cross-Linked Hydrogels","authors":"Xuechen Zhang, Nicola Contessi Negrini, Rita Correia, Paul T. Sharpe, Adam D. Celiz* and Ana Angelova Volponi*, ","doi":"10.1021/acsmacrolett.4c0052010.1021/acsmacrolett.4c00520","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00520https://doi.org/10.1021/acsmacrolett.4c00520","url":null,"abstract":"<p >Generating teeth <i>in vitro</i> requires mimicking tooth developmental processes. Biomaterials are essential to support 3D tooth organoid formation, but their properties must be finely tuned to achieve the required biomimicry for tooth development. For the first time, we used bioorthogonally cross-linked hydrogels as defined 3D matrixes for tooth developmental engineering, and we highlighted how their properties play a pivotal role in enabling 3D tooth organoid formation <i>in vitro</i>. We prepared hydrogels by mixing gelatin precursors modified either with tetrazine (Tz) or norbornene (Nb) moieties. We tuned the hydrogel properties (<i>E</i> = 2–7 kPa; <i>G</i>′ = 500–1500 Pa) by varying the gelatin concentration (8% vs 12% w/V) and stoichiometric ratio (Tz:Nb = 1 vs 0.5). We encapsulated dental epithelial-mesenchymal cell pellets in a library of hydrogels and identified a hydrogel formulation that enabled successful growth kinetics and morphogenesis of tooth germs, introducing a defined tunable platform for tooth organoid engineering and modeling.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1620–1626 1620–1626"},"PeriodicalIF":5.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00520","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-12DOI: 10.1021/acsmacrolett.4c00661
Kevin D. Dorfman
{"title":"Computational Phase Discovery in Block Polymers","authors":"Kevin D. Dorfman","doi":"10.1021/acsmacrolett.4c00661","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00661","url":null,"abstract":"Self-consistent field theory (SCFT), the mean-field theory of polymer thermodynamics, is a powerful tool for understanding ordered state selection in block copolymer melts and blends. However, the nonlinear governing equations pose a significant challenge when SCFT is used for phase discovery because converging an SCFT solution typically requires an initial guess close to the self-consistent solution. This Viewpoint provides a concise overview of recent efforts where machine learning methods (particle swarm optimization, Bayesian optimization, and generative adversarial networks) have been used to make the first strides toward converting SCFT from a primarily explanatory tool into one that can be readily deployed for phase discovery.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"71 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Interfacial Pickering Emulsion Polycondensation for Degradable Nanocomposites","authors":"Yaming Cheng, Jingman Xie, Yanju Lu, Wangmao Tian, Tong Wu, Fengqi Chen, Wei Gao, Yu Jin, Liang Yuan* and Baoxia Wang*, ","doi":"10.1021/acsmacrolett.4c0064710.1021/acsmacrolett.4c00647","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00647https://doi.org/10.1021/acsmacrolett.4c00647","url":null,"abstract":"<p >Pickering emulsion polymerization is a practical method to fabricate functional composite materials. However, most reported systems proceed homogeneously within the stabilized monomer phase and create nondegradable chemical bonds. Here, interfacial Pickering emulsion polycondensation between aromatic aldehydes and polymercaptans is developed using sustainable cellulose nanoparticles as the stabilizer. When sulfonated cellulose nanocrystals (S-CNCs) were utilized, they also catalyzed the polycondensation to produce the oxidatively degradable S,S-acetal groups on the polymer chains. The influence of monomer and cellulose structures on the polymerization behavior and composite properties were compared.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 11","pages":"1605–1611 1605–1611"},"PeriodicalIF":5.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-08DOI: 10.1021/acsmacrolett.4c00675
Mizhi Xu, Banruo Huang, Haley K. Beech, Patrick T. Getty, Juan Manuel Urueña, Craig J. Hawker
{"title":"Efficient Cross-Linking through C–H Bond Insertion of Unfunctionalized Commodity Materials Using Diazirine-Containing Polymers","authors":"Mizhi Xu, Banruo Huang, Haley K. Beech, Patrick T. Getty, Juan Manuel Urueña, Craig J. Hawker","doi":"10.1021/acsmacrolett.4c00675","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00675","url":null,"abstract":"The synthesis and application of multifunctional diazirine-containing polymers for on-demand cross-linking of unfunctionalized commodity polymers through C–H bond insertion is demonstrated. While small-molecule diazirine cross-linkers have seen important applications such as plastic compatibilization and photopatterning, the high degree of functionalization of polymer-based diazirine cross-linkers offers promise for enhanced compatibility based on polymer blending and increased efficiency due to controllable multivalency. As a demonstrative example, unfunctionalized linear poly(<i>n</i>-butyl acrylate) (P<i>n</i>BA) can be cross-linked using various polymeric cross-linkers with diazirine contents as low as 0.8 wt % in 1 min under photochemical conditions. With gel fractions up to 95%, tunable rheological behavior is observed with increasing cross-linker loadings, consistent with a transition from entangled branched polymers to a cross-linked network. Moreover, the synthetic stability of the diazirine units can be exploited to prepare diazirine-containing polymers based on a variety of different backbones, from vinyl copolymers to poly(dimethylsiloxane) (PDMS), which allows successful photopatterning using a commercial 3D printer.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"42 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Interfacial Pickering Emulsion Polycondensation for Degradable Nanocomposites","authors":"Yaming Cheng, Jingman Xie, Yanju Lu, Wangmao Tian, Tong Wu, Fengqi Chen, Wei Gao, Yu Jin, Liang Yuan, Baoxia Wang","doi":"10.1021/acsmacrolett.4c00647","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00647","url":null,"abstract":"Pickering emulsion polymerization is a practical method to fabricate functional composite materials. However, most reported systems proceed homogeneously within the stabilized monomer phase and create nondegradable chemical bonds. Here, interfacial Pickering emulsion polycondensation between aromatic aldehydes and polymercaptans is developed using sustainable cellulose nanoparticles as the stabilizer. When sulfonated cellulose nanocrystals (S-CNCs) were utilized, they also catalyzed the polycondensation to produce the oxidatively degradable S,S-acetal groups on the polymer chains. The influence of monomer and cellulose structures on the polymerization behavior and composite properties were compared.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"34 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-08DOI: 10.1021/acsmacrolett.4c0067510.1021/acsmacrolett.4c00675
Mizhi Xu, Banruo Huang, Haley K. Beech, Patrick T. Getty, Juan Manuel Urueña and Craig J. Hawker*,
{"title":"Efficient Cross-Linking through C–H Bond Insertion of Unfunctionalized Commodity Materials Using Diazirine-Containing Polymers","authors":"Mizhi Xu, Banruo Huang, Haley K. Beech, Patrick T. Getty, Juan Manuel Urueña and Craig J. Hawker*, ","doi":"10.1021/acsmacrolett.4c0067510.1021/acsmacrolett.4c00675","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00675https://doi.org/10.1021/acsmacrolett.4c00675","url":null,"abstract":"<p >The synthesis and application of multifunctional diazirine-containing polymers for on-demand cross-linking of unfunctionalized commodity polymers through C–H bond insertion is demonstrated. While small-molecule diazirine cross-linkers have seen important applications such as plastic compatibilization and photopatterning, the high degree of functionalization of polymer-based diazirine cross-linkers offers promise for enhanced compatibility based on polymer blending and increased efficiency due to controllable multivalency. As a demonstrative example, unfunctionalized linear poly(<i>n</i>-butyl acrylate) (P<i>n</i>BA) can be cross-linked using various polymeric cross-linkers with diazirine contents as low as 0.8 wt % in 1 min under photochemical conditions. With gel fractions up to 95%, tunable rheological behavior is observed with increasing cross-linker loadings, consistent with a transition from entangled branched polymers to a cross-linked network. Moreover, the synthetic stability of the diazirine units can be exploited to prepare diazirine-containing polymers based on a variety of different backbones, from vinyl copolymers to poly(dimethylsiloxane) (PDMS), which allows successful photopatterning using a commercial 3D printer.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 11","pages":"1598–1604 1598–1604"},"PeriodicalIF":5.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00675","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-07DOI: 10.1021/acsmacrolett.4c00640
Ying Wang, Zihao Meng, Zhenyang Luo, Zhiqiang Song, Bo Du, Yongsheng Zhang, Pengjin Ye, Linling Li, Yucheng He, Ye Sha
{"title":"Quantitative Examination and Mechanistic Insights of Polymer Chain Conformation Confined in Nanopores by Time-Resolved Fluorescence Resonance Energy Transfer","authors":"Ying Wang, Zihao Meng, Zhenyang Luo, Zhiqiang Song, Bo Du, Yongsheng Zhang, Pengjin Ye, Linling Li, Yucheng He, Ye Sha","doi":"10.1021/acsmacrolett.4c00640","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00640","url":null,"abstract":"The conformational studies of polymers confined at the nanoscale remain challenging and controversial due to the limitations of characterization techniques. In this study, we utilized the high sensitivity of time-resolved fluorescence resonance energy transfer (<i>tr</i>FRET) and a site-specific dye-labeling strategy to characterize the conformation of polymer chains confined in anodic aluminum oxide (AAO) nanopores. This strategy introduced a fluorescent donor (carbazole) and acceptor (anthracene) at the center of poly(butyl methacrylate) (PBMA) chains grown by atom transfer radical polymerization (ATRP). By quantitatively analyzing fluorescence decay through the Förster mechanism and the Drake–Klafter–Levitz (DKL) formalism, we can determine both the energy transfer efficiency and the spatial distribution of the dyes. This analysis revealed that the PBMA chains, with a molecular weight of 40 kDa, maintained their bulk-like conformation even when confined within nanopores as small as 10 nm in diameter. This study is the first to demonstrate the use of <i>tr</i>FRET for investigating chain conformation in confined polymer systems, which can be generalized to other polymer types and polymer topologies in different confined geometries.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"35 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Macro LettersPub Date : 2024-11-07DOI: 10.1021/acsmacrolett.4c00591
Zihan Zhang, Jacquelyn E. Blum, Rui Guo, Christopher J. Kloxin, Jeffery G. Saven, Darrin J. Pochan
{"title":"Liquid Crystal Behavior of Uniform Short Rods Made from Computationally Designed Parallel Coiled Coil Building Blocks","authors":"Zihan Zhang, Jacquelyn E. Blum, Rui Guo, Christopher J. Kloxin, Jeffery G. Saven, Darrin J. Pochan","doi":"10.1021/acsmacrolett.4c00591","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00591","url":null,"abstract":"Parallel, homotetrameric coiled coils were computationally designed using 29 amino acid peptides. These parallel coiled coils, called “bundlemers”, have <i>C</i><sub>2</sub> symmetry, with all N-termini displayed from one end of the nanoparticle and all C-termini from the opposite end. This anisotropic display of the peptide termini allowed for the functionalization of two sets of nanoparticles with either maleimide or thiol functionality at the N-terminal region of the constituent peptides. The thiol-Michael conjugation reaction between the N-terminal end of complementary bundlemer nanoparticles formed monodisperse, rigid bundlemer dimer, called “dibundlemer”, rods. The constituent, individual bundlemer nanoparticles were characterized with small-angle X-ray scattering (SAXS), Förster resonance energy transfer (FRET), and circular dichroism (CD) spectroscopy to confirm the parallel assembly of the coiled coils, consistent with the computational design. The dibundlemer rods were characterized with SAXS to reveal the uniform dibundlemer nature of the rods. Optical birefringence is observed in concentrated samples of the rods, with polarized optical microscopy (POM) revealing a nematic liquid crystalline behavior.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"64 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}