4.8 Article

Mechanochemical Regulation of a Photochemical Reaction

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 43, 页码 14073-14077

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b09628

关键词

-

资金

  1. Caltech
  2. Dow Next Generation Educator Fund

向作者/读者索取更多资源

We introduce the concept of mechano-chemically gated photoswitching. Mechanical regulation of a photochemical reaction is exemplified using a newly designed mechanophore based on a cyclopentadiene-maleimide Diels-Alder adduct. Ultrasound-induced mechanical activation of the photochemically inert mechanophore in polymers generates a diarylethene photoswitch via a retro-[4 + 2] cycloaddition reaction that photoisomerizes between colorless and colored states upon exposure to UV and visible light. Control experiments demonstrate the thermal stability of the cyclopentadiene maleimide adduct and confirm the mechanical origin of the unlocked photochromic reactivity. This technology holds promise for applications such as lithography and stress-sensing, enabling the mechanical history of polymeric materials to be recorded and read on demand.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

Article Chemistry, Multidisciplinary

Force-Dependent Multicolor Mechanochromism from a Single Mechanophore

Molly E. McFadden, Maxwell J. Robb

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

Article Multidisciplinary Sciences

A metabolic pathway for bile acid dehydroxylation by the gut microbiome

Masanori Funabashi, Tyler L. Grove, Min Wang, Yug Varma, Molly E. McFadden, Laura C. Brown, Chunjun Guo, Steven Higginbottom, Steven C. Almo, Michael A. Fischbach

NATURE (2020)

Article Chemistry, Multidisciplinary

Generation of an Elusive Permanent Merocyanine via a Unique Mechanochemical Reaction Pathway

Molly E. McFadden, Maxwell J. Robb

Summary: The discovery of a 2H-naphtho[1,2-b]pyran mechanophore that produces a permanent merocyanine dye upon mechanochemical activation is reported. The irreversible nature of the mechanically generated merocyanine is attributed to a unique reaction involving the scission of an ester C-O bond. This permanent coloration offers new opportunities for sensing, force-recording applications, and fundamental studies.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Multidisciplinary

Mechanically Triggered Release of Functionally Diverse Molecular Payloads from Masked 2-Furylcarbinol Derivatives

Xiaoran Hu, Tian Zeng, Corey C. Husic, Maxwell J. Robb

Summary: A general mechanophore platform based on masked 2-furylcarbinol derivatives is described in this study, which can spontaneously decompose under mild conditions upon liberation via a mechanically triggered reaction, resulting in the release of functionally diverse molecular cargo with adjustable release kinetics. The platform demonstrates good selectivity and control, and efficient release of various cargo molecules can be triggered by ultrasound-induced mechanical force.

ACS CENTRAL SCIENCE (2021)

Article Polymer Science

Comparison of the reactivity of isomeric 2H- and 3H-naphthopyran mechanophores

Skylar K. Osler, Molly E. McFadden, Maxwell J. Robb

Summary: This study directly compares the reactivity of two isomeric naphthopyrans in solution and solid materials, finding that the 2H-naphthopyran produces a dye with slower reversion rate. By investigating the impact of naphthopyran isomerism on the mechanochromic properties, the study lays the foundation for the development of force-responsive polymers.

JOURNAL OF POLYMER SCIENCE (2021)

Article Chemistry, Multidisciplinary

Harnessing the Power of Force: Development of Mechanophores for Molecular Release

Brooke A. Versaw, Tian Zeng, Xiaoran Hu, Maxwell J. Robb

Summary: Mechanophores, stress-sensitive molecules that release small molecules from polymers, show great promise in achieving selective and controlled release of covalently bound payloads. While the field of polymer mechanochemistry is rapidly advancing, further fundamental and technological advancements are still needed for significant impact in this research area.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Polymer Science

Quantifying Activation Rates of Scissile Mechanophores and the Influence of Dispersity

Anna C. Overholts, Molly E. McFadden, Maxwell J. Robb

Summary: Accurate and quantitative characterization of structure-mechanochemical activity relationships is crucial for understanding mechanochemical reactivity and advancing the field of polymer mechanochemistry. Ultrasound-induced mechanical activation of polymers is a common method for studying mechanophore reactivity, but traditional methods for analyzing chain scission kinetics from GPC measurements may provide misleading results. This study demonstrates the importance of spectroscopic analysis in accurately determining mechanophore activation rates, highlighting the need for a unified approach to kinetic analysis in polymer mechanochemistry.

MACROMOLECULES (2022)

Article Polymer Science

Incorporation of a Tethered Alcohol Enables Efficient Mechanically Triggered Release in Aprotic Environments

Corey C. Husic, Xiaoran Hu, Maxwell J. Robb

Summary: This study presents a new design of mechanophore polymer container that can release chemical payloads efficiently in non-proton solvent environments. The design incorporates a tethered primary alcohol and an intramolecular hydrogen bonding interaction between the alcohol and the carbonyl oxygen of a carbonate, reducing the activation energy for carbonate fragmentation and enabling molecular release. This design expands the application range of mechanically triggered release.

ACS MACRO LETTERS (2022)

Article Chemistry, Multidisciplinary

Mechanical Force Enables an Anomalous Dual Ring-Opening Reaction of Naphthodipyran

Molly E. McFadden, Skylar K. Osler, Yan Sun, Maxwell J. Robb

Summary: Multimodal mechanophores can distinguish between different stress states through color changes. In this study, we covalently linked polymer chains to naphthodipyran and generated the dual ring-opened dimerocyanine product with unique near-infrared absorption properties using mechanical force.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Infectious Diseases

Isolation, Identification, Sequence Analysis, and Pathogenicity of a CIAV Strain from Aegypius monachus

Mingrong Yin, Zhipeng Tang, Xiaoran Hu, Yuyan Li, Longzong Guo, Xiaolong Sun, Shuang Chang, Peng Zhao, Yixin Wang

Summary: A cluster of artificially bred vultures in a zoo in Shandong Province, China exhibited emaciation and mortality, suggesting the presence of an immunosuppressive pathogen. Nucleic acid testing confirmed the presence of chicken infectious anemia virus (CIAV) in the dead vulture tissue. The isolated CIAV strain, SDTY2021-TJ, showed high pathogenicity in SPF chickens, causing significant mortality and immunosuppressive effects.

TRANSBOUNDARY AND EMERGING DISEASES (2023)

Article Polymer Science

Validation of an Accurate and Expedient Initial Rates Method for Characterizing Mechanophore Reactivity

Molly E. McFadden, Anna C. Overholts, Skylar K. Osler, Maxwell J. Robb

Summary: Understanding the relationship between structure and mechanochemical reactivity is crucial for designing new stimuli-responsive polymers. In this study, we validate an initial rates method that accurately determines rate constants for ultrasound-induced mechanochemical transformations. The experimental results support the effectiveness of this method in deconvoluting the kinetics of specific mechanophore activation from nonspecific chain scission.

ACS MACRO LETTERS (2023)

Article Chemistry, Multidisciplinary

Force-Triggered Atropisomerization of a Parallel Diarylethene to Its Antiparallel Diastereomers

Xuancheng Fu, Boyu Zhu, Xiaoran Hu

Summary: This paper presents a mechanical approach to induce atropisomerization in a parallel diarylethene molecule, resulting in distinct chemical reactivity of its antiparallel diastereomers. Under ultrasound-induced force field, a congested parallel diarylethene mechanophore in (R(a), S(a)) configuration with mirror symmetry is atropisomerized to antiparallel diastereomers with C(2) symmetry. The obtained stereochemistry-converted material exhibits symmetry-allowed reactivity towards conrotatory photocyclization.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

Article Polymer Science

Mechanochemical reactivity of a multimodal 2H-bis-naphthopyran mechanophore

Skylar K. Osler, Molly E. McFadden, Tian Zeng, Maxwell J. Robb

Summary: Multi-modal mechanophores that react under mechanical force to produce unique absorption properties are of interest for force-sensing polymer design. In this study, a 2H-bis-naphthopyran mechanophore was investigated for its reactivity in generating thermally stable mono- and bis-merocyanine products upon mechanical activation. The force-mediated ester bond scission reaction followed by intramolecular hydrogen bonding plays a role in locking one merocyanine subunit in the open form, leading to the formation of an unusual trans merocyanine isomer. Unexpectedly, density functional theory calculations suggest a thermally reversible retro-cyclization reaction that may explain the mechanochemical generation of this isomer.

POLYMER CHEMISTRY (2023)

Article Chemistry, Multidisciplinary

5-Aryloxy substitution enables efficient mechanically triggered release from a synthetically accessible masked 2-furylcarbinol mechanophore

Tian Zeng, Xiaoran Hu, Maxwell J. Robb

Summary: In this study, a new mechanophore platform based on a masked 2-furylcarbinol derivative was reported, which efficiently releases phenol and arylamine payloads following mechanical activation. This platform incorporates a 5-aryloxy group as an electron-rich substituent to accelerate molecular release.

CHEMICAL COMMUNICATIONS (2021)

Article Chemistry, Multidisciplinary

Designing naphthopyran mechanophores with tunable mechanochromic behavior

Brooke A. Versaw, Molly E. McFadden, Corey C. Husic, Maxwell J. Robb

CHEMICAL SCIENCE (2020)

暂无数据