ACS Polymers Au

Conventional cryopreservation solutions rely on the addition of organic solvents such as DMSO or glycerol, but these do not give full recovery for all cell types, and innovative cryoprotectants may address damage pathways which these solvents do not protect against. Macromolecular cryoprotectants are emerging, but there is a need to understand their structure-property relationships and mechanisms of action. Here we synthesized and investigated the cryoprotective behavior of sulfoxide (i.e., "DMSO-like") side-chain polymers, which have been reported to be cryoprotective using poly(ethylene glycol)-based polymers. We also wanted to determine if the polarized sulfoxide bond (S+O- character) introduces cryoprotective effects, as this has been seen for mixed-charge cryoprotective polyampholytes, whose mechanism of action is not yet understood. Poly(2-(methylsulfinyl)ethyl methacrylate) was synthesized by RAFT polymerization of 2-(methylthio)ethyl methacrylate and subsequent oxidation to sulfoxide. A corresponding N-oxide polymer was also prepared and characterized: (poly(2-(dimethylamineoxide)ethyl methacrylate). Ice recrystallization inhibition assays and differential scanning calorimetry analysis show that the sulfoxide side chains do not modulate the frozen components during cryopreservation. In cytotoxicity assays, it was found that long-term (24 h) exposure of the polymers was not tolerated by cells, but shorter (30 min) incubation times, which are relevant for cryopreservation, were tolerated. It was also observed that overoxidation to the sulfone significantly increased the cytotoxicity, and hence, these materials require a precision oxidation step to be deployed. In suspension cell cryopreservation investigations, the polysulfoxides did not increase cell recovery 24 h post-thaw. These results show that unlike hydrophilic backboned polysulfides, which can aid cryopreservation, the installation of the sulfoxide group onto a polymer does not necessarily bring cryoprotective properties, highlighting the challenges of developing and discovering macromolecular cryoprotectants.

Toru Ishibe

Natalia Gonzalez-Martinez

Panagiotis G. Georgiou

Kathryn A. Murray

Matthew I. Gibson

Synthesis of Poly(2-(methylsulfinyl)ethyl methacrylate) via Oxidation of Poly(2-(methylthio)ethyl methacrylate): Evaluation of the Sulfoxide Side Chain on Cryopreservation

通过氧化聚(2-(甲硫基)乙基甲基丙烯酸酯)合成聚(2-(甲磺酰基)乙基甲基丙烯酸酯):评估亚砜侧链对玻璃化保存的影响

Application of protective polymer coatings to enhance the biostability of DNA-based nanomaterials (DONs) has become common practice in in vitro and in vivo experiments. While the functional effect of these coatings is obvious, a detailed molecular picture of what is protected and for how long remains unclear. Additionally, the use of the oligolysine-1kPEG protective polymer has been limited due to aggregation issues. In this study, we evaluated the colloidal stability, structural integrity, and functional preservation of DONs coated with oligolysine (K)-1k/5kPEG block copolymers. Dynamic light scattering and transmission electron microscopy were employed to assess colloidal stability before and after degradation. A FRET-based assay was developed to monitor the directionality of degradation, while quantitative PCR measured the protection of functional DNA handles, crucial for the design of ligand-functionalized DONs. Our results show that K10-1kPEG, while prone to aggregation, can offer similar protection against nucleases as K10-5kPEG, provided buffer conditions are carefully chosen. Maintaining the colloidal, structural, and functional stability before and after nuclease exposure supports DON applications, particularly at the biointerface. These insights provide valuable guidelines for selecting the most effective protection strategy and enhancing DON functionality across diverse biological environments.

Hugo J. Rodríguez-Franco

Pauline B. M. Hendrickx

Maartje M. C. Bastings

Tailoring DNA Origami Protection: A Study of Oligolysine-PEG Coatings for Improved Colloidal, Structural, and Functional Integrity

定制DNA折纸保护：寡聚赖氨酸-PEG涂层对改善胶体、结构和功能完整性的研究

Chemoenzymatic polymerization (CEP) using enzymes as catalysts is gaining attention as an environmentally friendly method for synthesizing polypeptides. This method proceeds under mild conditions in aqueous solvents and leverages the substrate specificity of enzymes, allowing polymerization reactions to occur without the need to protect reactive side-chain functional groups. However, the monomers used must have esterified C-termini, such as amino acids or oligopeptides. In this study, we used l-lysine (Lys-OH) as a model example and performed one-pot CEP with papain without isolating the esterified lysine. Esterification of Lys-OH was achieved by using hydrochloric acid as a catalyst in ethanol, and one-pot polymerization resulted in poly-l-lysine (polyLys) with a peak top degree of polymerization (DP) of 6 and a maximum DP of 18, with a 31% conversion from the nonesterified lysine. The obtained polyLys was all α-linked, demonstrating that regioselective polymerization was successfully achieved even with one-pot CEP.

Kayo Terada

Kousuke Tsuchiya

Alexandros Lamprou

Keiji Numata

Chemoenzymatic Synthesis of Poly-<scp>l</scp>-lysine via Esterification with Alcohol in One-Pot

通过一锅法酯化醇实现聚-L-赖氨酸的化学酶促合成

Itaconates available from renewable resources constitute a group of monomers that are used in several types of polymerizations. Their use in free-radical polymerizations (FRPs) is still limited due to the low propagation rate coefficients resulting in low polymerization rates and the occurrence of depropagation which is responsible for limited monomer conversion. Since FRP is considered very robust with few requirements concerning monomer purity, it is still interesting to investigate how itaconate FRP may become feasible. For this reason, copolymerizations of itaconates with other monomers well-suited for FRP are considered. In particular, copolymerization with acrylates appears to be interesting because the propagation rate of these monomers is high and depropagation is not operative at common polymerization temperatures. Copolymerizations of dibutyl and dicyclohexyl itaconate with butyl acrylate were performed to determine the copolymerization reactivity ratios required for tailoring copolymer composition. To limit the number of experiments, copolymerizations were carried out until high conversion and consumption of the individual monomers was obtained from 1H NMR spectroscopy and quantitative size-exclusion chromatography.

Marco Drache

Brunette Audree Tameno Kouanwo

Jan Christoph Namyslo

Sacha Pérocheau Arnaud

Tobias Robert

Sabine Beuermann

Reactivity Ratios of Biobased Dialkyl Itaconate Radical Polymerizations Derived from In-Line NMR Spectroscopy and Size-Exclusion Chromatography

基于在线核磁共振波谱和尺寸排阻色谱的生物基二烷基衣康酸酯自由基聚合反应性比率

Programmable synthesis of polymer nanoparticles prepared by polymerization-induced self-assembly (PISA) mediated by reversible addition–fragmentation chain-transfer (RAFT) dispersion polymerization with specified diameter is achieved in an automated flow-reactor platform. Real-time particle size and monomer conversion is obtained via inline spatially resolved dynamic light scattering (SRDLS) and benchtop nuclear magnetic resonance (NMR) instrumentation. An initial training experiment generated a relationship between copolymer block length and particle size for the synthesis of poly(N,N-dimethylacrylamide)-b-poly(diacetone acrylamide) (PDMAm-b-PDAAm) nanoparticles. The training data was used to target the product compositions required for synthesis of nanoparticles with defined diameters of 50, 60, 70, and 80 nm, while inline NMR spectroscopy enabled rapid acquisition of kinetic data to support their scale-up. NMR and SRDLS were used during the continuous manufacture of the targeted products to monitor product consistency while an automated sampling system collected practically useful quantities of the targeted products, thus outlining the potential of the platform as a tool for discovery, development, and manufacture of polymeric nanoparticles.

Peter M. Pittaway

Kudakwashe E. Chingono

Stephen T. Knox

Elaine Martin

Richard A. Bourne

Olivier J. Cayre

Nikil Kapur

Jonathan Booth

Robin Capomaccio

Nicholas Pedge

Nicholas J. Warren

Exploiting Online Spatially Resolved Dynamic Light Scattering and Flow-NMR for Automated Size Targeting of PISA-Synthesized Block Copolymer Nanoparticles

利用在线空间分辨动态光散射和流动核磁共振实现PISA合成嵌段共聚物纳米粒子的自动化尺寸调控

Erick Gabriel Ribeiro dos Anjos

Tayra Rodrigues Brazil

Mirabel Cerqueira Rezende

Juliano Marini

Uttandaraman Sundararaj

Luiz Antonio Pessan

Fabio Roberto Passador

Tuning the Morphology of Immiscible Polymer Blend-Based Hybrid Nanocomposite for Improving Microwave Absorption Response

调节不相容聚合物共混基杂化纳米复合材料的形貌以提高微波吸收响应

Abbreviation	ACS Polym. Au
Journal Impact	4.55
Quartiles(Global)	POLYMER SCIENCE(Q1)

Publication Information	Publisher: American Chemical Society，Publishing cycle: ，Journal Type: journal，Open Access Journals: Yes
Basic data	Year of publication: 2023，Proportion of original research papers: 95.16%，Self Citation Rate:， Gold OA Rate: 43.04%
Journal Fees	$3500Details
Average review cycle	11 weeks

ACS Polymers Au

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Synthesis of Poly(2-(methylsulfinyl)ethyl methacrylate) via Oxidation of Poly(2-(methylthio)ethyl methacrylate): Evaluation of the Sulfoxide Side Chain on Cryopreservation

Tailoring DNA Origami Protection: A Study of Oligolysine-PEG Coatings for Improved Colloidal, Structural, and Functional Integrity

Chemoenzymatic Synthesis of Poly-l-lysine via Esterification with Alcohol in One-Pot

Reactivity Ratios of Biobased Dialkyl Itaconate Radical Polymerizations Derived from In-Line NMR Spectroscopy and Size-Exclusion Chromatography

Exploiting Online Spatially Resolved Dynamic Light Scattering and Flow-NMR for Automated Size Targeting of PISA-Synthesized Block Copolymer Nanoparticles

Tailoring DNA Origami Protection: A Study of Oligolysine-PEG Coatings for Improved Colloidal, Structural, and Functional Integrity

Chemoenzymatic Synthesis of Poly-l-lysine via Esterification with Alcohol in One-Pot

Tuning the Morphology of Immiscible Polymer Blend-Based Hybrid Nanocomposite for Improving Microwave Absorption Response

Reactivity Ratios of Biobased Dialkyl Itaconate Radical Polymerizations Derived from In-Line NMR Spectroscopy and Size-Exclusion Chromatography

Exploiting Online Spatially Resolved Dynamic Light Scattering and Flow-NMR for Automated Size Targeting of PISA-Synthesized Block Copolymer Nanoparticles