Two-Dimensional Nanoarchitectonics of End-on Oligomers with Versatile Structures and Tunable Negative Differential Resistance DOI
Yongfang Li,

Lingyun Shen,

Shumu Li

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(43), P. 58973 - 58979

Published: Oct. 18, 2024

Maximizing the molecular information density requires simultaneously functionalizing distinct monomers and their coupling connections. However, current synthesis generally focuses on rather than reactions because multistep significantly escalate synthetic complexity in an exponential increase. Here, we report two-dimensional nanoarchitectures (2DNs) of end-on oligomers, with versatile structures negative differential resistance (NDR), synthesized by programmed surface-initiated step electrosynthesis based simultaneous utilization six including cross- homocouplings. The resulting vertically similar values thickness length, as crystalline 2DNs, exhibit subnanometer uniformity, ultrahigh compressive modulus 40 GPa, low-bias NDR at 0.13 V ultralow power consumption down to 0.05 nW/μm2. This highly controlled provides a unique dimension enhance structural diversity 2D nanomaterials for high-density low-power electronics.

Language: Английский

Beyond Lipids: Exploring Advances in Polymeric Gene Delivery in the Lipid Nanoparticles Era DOI Creative Commons
Chinmay M. Jogdeo, Kasturi Siddhanta,

Ashish Das

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(31)

Published: June 6, 2024

Abstract The recent success of gene therapy during the COVID‐19 pandemic has underscored importance effective and safe delivery systems. Complementing lipid‐based systems, polymers present a promising alternative for delivery. Significant advances have been made in past, with multiple clinical trials progressing beyond phase I several companies actively working on polymeric systems which provides assurance that carriers can soon achieve translation. massive advantage structural tunability vast chemical space is being leveraged to mitigate shortcomings traditional polycationic improve translatability Tailored approaches diverse nucleic acids specific subcellular targets are now designed therapeutic efficacy. This review describes polymer design improved by polyplexes covalent polymer‐nucleic acid conjugates. also offers brief note novel computational techniques design. concludes an overview current state therapies clinic as well future directions their translation clinic.

Language: Английский

Citations

15

Recent Advances in Stimuli-Responsive Self-Immolative Polymers for Drug Delivery and Molecular Imaging DOI
Yuce Li,

Jixiu Liu,

Jing He

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(9), P. 4054 - 4077

Published: April 18, 2024

Stimuli-responsive self-immolative polymers (SIPs) represent a unique class of that can undergo controlled, sequential head-to-tail depolymerization upon specific stimuli. Since their inception, they have evolved over two decades to become one the most attractive polymer types. With characteristic feature "one stimulus, multiple responses", SIPs inherently possess ability serve as chemical amplifiers, which amplify weak or biological signals. This promises higher stimulus sensitivity, greater selectivity for microenvironments, and potential generate more persistent, extensive, significant responses while consuming fewer stimuli sources. Review summarizes latest research advancements in stimuli-responsive drug delivery molecular imaging past five years. Regarding structure SIPs, we briefly overview updates self-immolation units, end-cap moieties, sequence SIPs. In terms applications, focus on possible applications disease treatment methods. Finally, provide brief perspective future directions these applications.

Language: Английский

Citations

10

Sequence-Defined Tertiary Amine-Based Oligomer Employing a Scalable, Support-Free, and Protection/Deprotection-Free Iterative Strategy DOI
Debashis Barik, Mintu Porel

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(1), P. 65 - 72

Published: Jan. 2, 2024

Sequence-defined oligomers (SDOs) with their unique monomeric sequence and customizable nature are attracting the attention of researchers globally. The structural functional diversity attainable in SDOs makes this platform promising, albeit challenges synthesis. Herein, we report design synthesis a novel class SDO by incorporating tertiary amines into backbone from commercially available inexpensive materials. Tertiary were selected due to various material biomedical applications. Even though purification amine compounds challenging, significant applications, such as pharmaceuticals, catalysts, surfactants, corrosion inhibitors, dye intermediates, polymer additives, rubber accelerators, gas treating agents, agriculture, analytical chemistry, make them fascinating. synthetic strategy that is designed here extremely efficient economical for scalable support-free, protection–deprotection chemistry-free, catalyst/template-free. Most importantly, no extra monomer required here. key reactions employed (i) transformation hydroxy group halide (ii) substitution secondary units. Including purifying processes, multigram 4-mer was completed 12–14 h. established synthesizing two different sequences SDOs. characterized 1H NMR LC-MS. tandem MS (MS/MS) experiment conducted order validate over chain. Furthermore, advanced ways: increasing chain length via attaching linker, which provides rapid method chain, postsynthetic modification other groups, including guanidine biological importance well-known fluorophore dansyl significance.

Language: Английский

Citations

4

Advanced Smart Biomaterials for Regenerative Medicine and Drug Delivery Based on Phosphoramidite Chemistry: From Oligonucleotides to Precision Polymers DOI
Bo Yang, Ting Cui, Liang Guo

et al.

Biomacromolecules, Journal Year: 2024, Volume and Issue: 25(5), P. 2701 - 2714

Published: April 12, 2024

Over decades of development, while phosphoramidite chemistry has been known as the leading method in commercial synthesis oligonucleotides, it also revolutionized fabrication sequence-defined polymers (SDPs), offering novel functional materials polymer science and clinical medicine. This review introduced evolution chemistry, emphasizing its development from oligonucleotides to creation universal SDPs, which have unlocked potential for designing programmable smart biomaterials with applications diverse areas including data storage, regenerative medicine drug delivery. The key methodologies, functions, biomedical applications, future challenges summarized this review, underscoring significance breakthroughs precisely synthesized materials.

Language: Английский

Citations

3

Tuning Copolymer Microstructure Using Ring-Opening Cross-Metathesis Polymerization DOI
Jeffrey C. Foster, Isaiah T. Dishner

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

Language: Английский

Citations

0

New Wine in Old Bottle: Crown Ether-Functionalized Digital Polymer toward Efficient MALDI-TOF MS/MS Decoding via a Classical Supramolecular Interaction DOI

Xiaoman Huang,

Zhilin Yang,

Xiaojie Yang

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(8), P. 979 - 986

Published: July 23, 2024

Digital polymers (DPs), which serve as promising molecular-level storage media, have increasingly garnered interest. Their application significantly depends on the efficiency of information writing (synthesis) and reading processes (sequencing). For reading, rational incorporation weak bonds in main chain was applied most cases order to improve readability tandem mass spectra (MS/MS), would limit length DPs, thus reducing capacity. In this study, introduction commercially available crown ether (CE) at terminus digital oligo(γ-butyrolactone)s (DOBLs) enhances predictability fidelity matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF MS/MS), improving decoding process. The use ether, leveraging a well-established supramolecular interaction with alkali cations known since 1967, offers strong affinity between ionization agents CE motifs, form selective effect desired fragments during MS. This method is particularly effective for long-chain extending up 32-mer, allows customizable fragmentation patterns. DP end presents novel efficient strategy enhancing MS/MS amplifying capacity polymers.

Language: Английский

Citations

2

Recyclable terthiophenes for synthesizing precision conjugated oligomers DOI
Hao Xu, Harrison A. Mills, Shuyang Ye

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Precision oligothiophenes were synthesized from terthiophene in an efficient manner. Interestingly, the unreacted was readily recovered and reused subsequent synthesis.

Language: Английский

Citations

2

Sequence‐Defined Synthesis Enabled by Fast and Living Anionic Monoaddition of Vinyl Monomers DOI
Kazuhiro Okamoto,

Dong‐eun Yoo,

Rikako Yoshioka

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 16, 2024

The selective monoaddition of polymerizable vinyl monomers like styrenes and methacrylates in a living manner has been achieved for the flash-flow preparation molecules defined sequence with high selectivity. We demonstrated sequence-defined synthesis multifunctional using an initiator, functionalized styrenes, diarylethylenes, various methacrylates, electrophilic trapping reagent at terminus (six-component sequential connection maximum) without any intermediate purification steps. anionic flow system described herein is active polymerization, such that styrene or methacrylate can be expanded to afford highly dispersed oligomers affecting other single units, which means unequivocal sequences were successfully inserted into internal terminal positions. methodology provides adaptable method construction new molecular spaces based on unimolecular control pinpoint functionalization.

Language: Английский

Citations

2

Complex Sequence‐Defined Heteropolymers Enable Controlled Film Growth in Layer‐By‐Layer Assembly DOI Creative Commons

Ranajit Barman,

Michel Tschopp,

Laurence Charles

et al.

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(22)

Published: Aug. 6, 2024

Abstract Digitally‐encoded poly(phosphodiesters) ( d ‐PPDE) with highly complex primary structures are evaluated for layer‐by‐layer (LbL) assembly. To be easily decoded by mass spectrometry (MS), these digital polymers contain many different monomers: 2 coding units allowing binary encryption, 1 cleavable spacer controlled MS fragmentation, and 3 tags fragment identification. These heteropolymers therefore composed of 6 motifs. Despite this strong sequence heterogeneity, it is found that they enable a LbL film formation. For instance, regular growth observed when alternating the deposition negatively‐charged ‐PPDE positively‐charged poly(allyl amine hydrochloride) (PAH). Yet, in approach, interdistance between consecutive coded layers remains relatively small, which may an issue data storage applications, especially selective decoding stored information. Using poly(sodium 4‐styrene sulfonate) (PSS) as intermediate non‐coded polyanion, shown can achieved, while still maintaining growth. Last but not least, work small molecular weight (i.e., significantly smaller than those PAH PSS) enables

Language: Английский

Citations

1

High density information storage through isotope ratio encoding DOI Creative Commons
Petra Sőregi, Márton Zwillinger,

Lajos Vágó

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14938 - 14945

Published: Jan. 1, 2024

The need for reliable information storage is on a steep rise. Sequence-defined polymers, particularly oligonucleotides, are already in use several areas, while compound mixtures also offer simple way storing information. We investigated the of set isotopologues by mixing, where stored form mass spectrometric (MS) fingerprint mixture. A small molecule with 24 non-labile and replaceable hydrogen atoms was selected as model, components covering D

Language: Английский

Citations

1