ACS Macro Letters最新文献_第6页

Kinetically Controlled Approach for One-Pot Synthesis of Poly(peptide-b-peptoid) Exhibiting Well-Defined Secondary Structure and Thermal Stability. 单锅合成具有明确二级结构和热稳定性的聚（肽-b-肽）的动力学控制方法

IF 5.1

ACS Macro Letters Pub Date : 2025-02-18 Epub Date: 2025-01-31 DOI: 10.1021/acsmacrolett.4c00823

Prabir Maity, Arjun Singh Bisht, Deepak, Raj Kumar Roy

{"title":"Kinetically Controlled Approach for One-Pot Synthesis of Poly(peptide-b-peptoid) Exhibiting Well-Defined Secondary Structure and Thermal Stability.","authors":"Prabir Maity, Arjun Singh Bisht, Deepak, Raj Kumar Roy","doi":"10.1021/acsmacrolett.4c00823","DOIUrl":"10.1021/acsmacrolett.4c00823","url":null,"abstract":"Sequence-controlled polymerization aims to bridge the gap between biopolymers and synthetic macromolecules. In a kinetically controlled approach, the inherent reactivity differences among monomers determine the primary structure or sequence of the monomers linked within the resulting copolymer chains. This report outlines a one-pot synthesis of polypeptide-b-polypeptoid by choosing a suitable pair of N-carboxy anhydride (NCA) monomers with significant reactivity differences. We have demonstrated the preparation of well-defined block copolymers, including polyproline-b-polysarcosine (PLP-b-PSar) and poly(propargyl proline)-b-polysarcosine (PLPP-b-PSar) in a single step. 1H NMR kinetic studies confirmed the sequence-controlled primary structures of these block copolymers. The NMR analysis indicated a striking reactivity ratio difference (rPLP = 925 and rPSar = 0.0014; rPLPP = 860 and rPSar = 0.0015) between the selected monomer pairs, which was crucial for a one-pot block copolymer synthesis. Notably, these sequence-controlled copolymers' secondary structures and stability were remarkably similar to those of block copolymers synthesized through conventional sequential addition methods. This further underscores the practicality of this kinetically controlled approach.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"188-194"},"PeriodicalIF":5.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143070722","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}

引用次数: 0

Diffusion of Nanosheets in Unentangled Polymer Melts

IF 5.8

ACS Macro Letters Pub Date : 2025-02-18 DOI: 10.1021/acsmacrolett.4c00535

Shiwei Sun, Kai Zhang, Sai Xu, Xinghua Shi, Jiuling Wang

引用次数: 0

Diffusion of Nanosheets in Unentangled Polymer Melts

IF 5.1

ACS Macro Letters Pub Date : 2025-02-18 DOI: 10.1021/acsmacrolett.4c0053510.1021/acsmacrolett.4c00535

Shiwei Sun, Kai Zhang, Sai Xu, Xinghua Shi* and Jiuling Wang*,

引用次数: 0

A Thienothiophene-Based Olefin-Linked Covalent Organic Framework for the Metal-Free Photocatalytic Oxidative Coupling of Amines

IF 5.1

ACS Macro Letters Pub Date : 2025-02-15 DOI: 10.1021/acsmacrolett.4c0084710.1021/acsmacrolett.4c00847

Bertha Lotsi, Aadarsh Sharma, Jared G. Doremus, Spencer T. Burton, Claudia Turro and Psaras L. McGrier*,

{"title":"A Thienothiophene-Based Olefin-Linked Covalent Organic Framework for the Metal-Free Photocatalytic Oxidative Coupling of Amines","authors":"Bertha Lotsi, Aadarsh Sharma, Jared G. Doremus, Spencer T. Burton, Claudia Turro and Psaras L. McGrier*, ","doi":"10.1021/acsmacrolett.4c0084710.1021/acsmacrolett.4c00847","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00847https://doi.org/10.1021/acsmacrolett.4c00847","url":null,"abstract":"The oxidative coupling of amines is a useful way to prepare many diverse compounds for the pharmaceutical and chemical industries. Covalent organic frameworks (COFs), a crystalline class of porous polymers, have emerged as promising heterogeneous photocatalysts that can accomplish this transformation under metal-free conditions due to their excellent photochemical stability and tunable electronic properties. Herein, we report the optoelectronic and photocatalytic properties of an olefin-linked COF containing thienothiophene (TT) and 2,4,6-trimethyl-1,3,5-triazine (TMT) units. The TT-TMT-COF exhibited a narrow band gap with extended light absorption and excellent charge separation, making it useful for the oxidative coupling of various benzylamines. The TT-TMT-COF exhibited fast reaction times, excellent recyclability, and conversions as high as ∼99%. The reactivity of TT-TMT-COF was on par or significantly better than that of a few small molecule 2,4,6-tris((E)-2-(thieno[3,2-b]thiophen-2-yl)vinyl)-1,3,5-triazine (TT-TMT) and 2,4,6-tris((E)-2-(thiophen-2-yl)vinyl)-1,3,5-triazine (Thio-TMT) homogeneous catalytic systems containing similar functional units. This work further highlights the ability of the COF to perform useful and efficient catalytic transformations in a sustainable manner.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 3","pages":"278–283 278–283"},"PeriodicalIF":5.1,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635860","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}

引用次数: 0

A Thienothiophene-Based Olefin-Linked Covalent Organic Framework for the Metal-Free Photocatalytic Oxidative Coupling of Amines 用于胺类无金属光催化氧化偶联的噻吩基烯烃连接共价有机框架

IF 5.8

ACS Macro Letters Pub Date : 2025-02-15 DOI: 10.1021/acsmacrolett.4c00847

Bertha Lotsi, Aadarsh Sharma, Jared G. Doremus, Spencer T. Burton, Claudia Turro, Psaras L. McGrier

{"title":"A Thienothiophene-Based Olefin-Linked Covalent Organic Framework for the Metal-Free Photocatalytic Oxidative Coupling of Amines","authors":"Bertha Lotsi, Aadarsh Sharma, Jared G. Doremus, Spencer T. Burton, Claudia Turro, Psaras L. McGrier","doi":"10.1021/acsmacrolett.4c00847","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00847","url":null,"abstract":"The oxidative coupling of amines is a useful way to prepare many diverse compounds for the pharmaceutical and chemical industries. Covalent organic frameworks (COFs), a crystalline class of porous polymers, have emerged as promising heterogeneous photocatalysts that can accomplish this transformation under metal-free conditions due to their excellent photochemical stability and tunable electronic properties. Herein, we report the optoelectronic and photocatalytic properties of an olefin-linked COF containing thienothiophene (TT) and 2,4,6-trimethyl-1,3,5-triazine (TMT) units. The TT-TMT-COF exhibited a narrow band gap with extended light absorption and excellent charge separation, making it useful for the oxidative coupling of various benzylamines. The TT-TMT-COF exhibited fast reaction times, excellent recyclability, and conversions as high as ∼99%. The reactivity of TT-TMT-COF was on par or significantly better than that of a few small molecule 2,4,6-tris((E)-2-(thieno[3,2-b]thiophen-2-yl)vinyl)-1,3,5-triazine (TT-TMT) and 2,4,6-tris((E)-2-(thiophen-2-yl)vinyl)-1,3,5-triazine (Thio-TMT) homogeneous catalytic systems containing similar functional units. This work further highlights the ability of the COF to perform useful and efficient catalytic transformations in a sustainable manner.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"24 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143417990","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}

引用次数: 0

Helical Poly(quioxaline-2,3-diyl)-Based Poly(carboxylic acid)s as a Chiroptical Chemosensor for Detection and Quantification of Small Enantiomeric Imbalances of Chiral Amines in Water

IF 5.1

ACS Macro Letters Pub Date : 2025-02-14 DOI: 10.1021/acsmacrolett.4c0081410.1021/acsmacrolett.4c00814

Tomonori Yamawaki, Takuma Kuroda, Takeshi Yamamoto, Yuuya Nagata and Michinori Suginome*,

{"title":"Helical Poly(quioxaline-2,3-diyl)-Based Poly(carboxylic acid)s as a Chiroptical Chemosensor for Detection and Quantification of Small Enantiomeric Imbalances of Chiral Amines in Water","authors":"Tomonori Yamawaki, Takuma Kuroda, Takeshi Yamamoto, Yuuya Nagata and Michinori Suginome*, ","doi":"10.1021/acsmacrolett.4c0081410.1021/acsmacrolett.4c00814","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00814https://doi.org/10.1021/acsmacrolett.4c00814","url":null,"abstract":"Achiral dynamic helical polymers, poly(quinoxaline-2,3-diyl)s (P1 and P2) bearing achiral carboxylic acid side chains, i.e., carboxymethoxymethyl (in P1) and carboxyethoxymethyl (in P2), with different polymerization degrees were synthesized. They exhibited induced circular dichroism (ICD) in the presence of chiral amines such as 1-phenylethylamine and nicotine, 1,2-amino alcohols such as valinol, leucinol, and prolinol, and the basic amino acid, arginine, in response to the induction of right- or left-handed helical conformation. The efficiency of helix induction depends on the compatibility of the structures of amines and polymers, with no clear structural correlation. The highly sensitive and formulated nature of ICD with the helical polymer-based poly(carboxylic acid)s allowed their use as CD-based sensors to detect and quantify minute imbalances of the enantiomeric excess of chiral molecules. We determined 0.2%–0.6% ee in the commercially available 1-phenylethylamine from three different suppliers, which have the label of “dl” or no indication of enantiopurity using P1 as a chemosensor.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 3","pages":"272–277 272–277"},"PeriodicalIF":5.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635859","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}

引用次数: 0

Scaling Behavior of Entanglement Dynamics in Polyelectrolyte Solutions: Insights from High-Frequency Rheometry

IF 5.8

ACS Macro Letters Pub Date : 2025-02-13 DOI: 10.1021/acsmacrolett.4c00722

Yahya Rharbi

{"title":"Scaling Behavior of Entanglement Dynamics in Polyelectrolyte Solutions: Insights from High-Frequency Rheometry","authors":"Yahya Rharbi","doi":"10.1021/acsmacrolett.4c00722","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00722","url":null,"abstract":"Entanglement dynamics in polyelectrolyte solutions remain a challenging topic, particularly in capturing the entire dynamic spectrum, from single entanglement relaxation (τe) to reptation time (τrep), and aligning these observations with scaling predictions in the semidilute entangled (SE) and fully entangled (FE) neutral regimes. Using piezo compressional and classic rotational rheometry, we investigate the scaling behaviors of key viscoelastic properties over several decades of time scales in ten million Mw cationic polyacrylamide solutions. Specific viscosity (ηsp) and τrep scale as predicted within Fuoss, SE, and FE regimes, defining crossover concentrations between these regimes (Ce and CD). More importantly, τe, the rubbery plateau width (τrep/τe), and the high-frequency modulus (Ge) scale as C–1.14±0.02, C1.25±0.07, and C1.32±0.05, aligning with SE prediction in the early SE regime before transitioning to neutral scaling of C–2.7±0.14, C3.1±0.15, and C2.35±0.07 at an intermediate concentration between Ce and CD labeled CDe. These results indicate that electrostatic interactions affect single entanglements and reptation differently, leading to a transition to neutral behavior at CDe for the former and at CD for the latter.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"59 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402013","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}

引用次数: 0

Retraction of “Temperature-Controlled Star-Shaped Cellulose Nanocrystal Assemblies Resulting from Asymmetric Polymer Grafting” 撤回 "不对称聚合物接枝产生的温控星形纤维素纳米晶体组装 "一文

IF 5.1

ACS Macro Letters Pub Date : 2025-02-13 DOI: 10.1021/acsmacrolett.4c0078710.1021/acsmacrolett.4c00787

Fangbo Lin, Fabrice Cousin, Jean-Luc Putaux and Bruno Jean*,

引用次数: 0

Retraction of “Temperature-Controlled Star-Shaped Cellulose Nanocrystal Assemblies Resulting from Asymmetric Polymer Grafting”

IF 5.8

ACS Macro Letters Pub Date : 2025-02-13 DOI: 10.1021/acsmacrolett.4c00787

Fangbo Lin, Fabrice Cousin, Jean-Luc Putaux, Bruno Jean

引用次数: 0

Scaling Behavior of Entanglement Dynamics in Polyelectrolyte Solutions: Insights from High-Frequency Rheometry

IF 5.1

ACS Macro Letters Pub Date : 2025-02-13 DOI: 10.1021/acsmacrolett.4c0072210.1021/acsmacrolett.4c00722

Yahya Rharbi*,

{"title":"Scaling Behavior of Entanglement Dynamics in Polyelectrolyte Solutions: Insights from High-Frequency Rheometry","authors":"Yahya Rharbi*, ","doi":"10.1021/acsmacrolett.4c0072210.1021/acsmacrolett.4c00722","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00722https://doi.org/10.1021/acsmacrolett.4c00722","url":null,"abstract":"Entanglement dynamics in polyelectrolyte solutions remain a challenging topic, particularly in capturing the entire dynamic spectrum, from single entanglement relaxation (τe) to reptation time (τrep), and aligning these observations with scaling predictions in the semidilute entangled (SE) and fully entangled (FE) neutral regimes. Using piezo compressional and classic rotational rheometry, we investigate the scaling behaviors of key viscoelastic properties over several decades of time scales in ten million Mw cationic polyacrylamide solutions. Specific viscosity (ηsp) and τrep scale as predicted within Fuoss, SE, and FE regimes, defining crossover concentrations between these regimes (Ce and CD). More importantly, τe, the rubbery plateau width (τrep/τe), and the high-frequency modulus (Ge) scale as C–1.14±0.02, C1.25±0.07, and C1.32±0.05, aligning with SE prediction in the early SE regime before transitioning to neutral scaling of C–2.7±0.14, C3.1±0.15, and C2.35±0.07 at an intermediate concentration between Ce and CD labeled CDe. These results indicate that electrostatic interactions affect single entanglements and reptation differently, leading to a transition to neutral behavior at CDe for the former and at CD for the latter.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 3","pages":"259–264 259–264"},"PeriodicalIF":5.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635856","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}

引用次数: 0