Vinyl Ether Research Articles

Macrophage membrane-camouflaged pH-sensitive nanoparticles for targeted therapy of oral squamous cell carcinoma

BackgroundOral cancer is the most common malignant tumor of the head and neck, and 90% of cases are oral squamous cell carcinoma (OSCC). Chemotherapy is an important component of comprehensive treatment for OSCC. However, the clinical treatment effect of chemotherapy drugs, such as doxorubicin (DOX), is limited due to the lack of tumor targeting and rapid clearance by the immune system. Thus, based on the tumor-targeting and immune evasion abilities of macrophages, macrophage membrane-encapsulated poly(methyl vinyl ether alt maleic anhydride)-phenylboronic acid-doxorubicin nanoparticles (MM@PMVEMA-PBA-DOX NPs), briefly as MM@DOX NPs, were designed to target OSCC. The boronate ester bonds between PBA and DOX responded to the low pH value in the tumor microenvironment, selectively releasing the loaded DOX.ResultsThe results showed that MM@DOX NPs exhibited uniform particle size and typical core-shell structure. As the pH decreased from 7.4 to 5.5, drug release increased from 14 to 21%. The in vitro targeting ability, immune evasion ability, and cytotoxicity of MM@DOX NPs were verified in HN6 and SCC15 cell lines. Compared to free DOX, flow cytometry and fluorescence images demonstrated higher uptake of MM@DOX NPs by tumor cells and lower uptake by macrophages. Cell toxicity and live/dead staining experiments showed that MM@DOX NPs exhibited stronger in vitro antitumor effects than free DOX. The targeting and therapeutic effects were further confirmed in vivo. Based on in vivo biodistribution of the nanoparticles, the accumulation of MM@DOX NPs at the tumor site was increased. The pharmacokinetic results demonstrated a longer half-life of 9.26 h for MM@DOX NPs compared to 1.94 h for free DOX. Moreover, MM@DOX NPs exhibited stronger tumor suppression effects in HN6 tumor-bearing mice and good biocompatibility.ConclusionsTherefore, MM@DOX NPs is a safe and efficient therapeutic platform for OSCC.

In Situ Polymerized Quasi-Solid Electrolytes Compounded with Ionic Liquid Empowering Long-Life Cycling of 4.45 V Lithium-Metal Battery.

High-voltage resistant quasi-solid-state polymer electrolytes (QSPEs) are promising for enhancing the energy density of lithium-metal batteries in practice. However, side reactions occurring at the interfaces between the anodes or cathodes and QSPEs considerably reduce the lifespan of high-voltage LMBs. In this study, a copolymer of vinyl ethylene carbonate (VEC) and poly(ethylene glycol) diacrylate (PEGDA) was used as the framework, with a cellulose membrane (CE) as the supporting layer. Based on density functional theory calculations, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), an ionic liquid, was screened because of its lowest unoccupied molecular orbital energy level as a modifying agent for the in situ P(VECx-EGy)/Pyrz/LiTFSI@CE QSPEs synthesis. Pyr14+, with a lithiophobic alkyl chain, forms a dense positive ion shielding layer on the protruding tips of deposited lithium, facilitating uniform and smooth lithium deposition. Pyr14TFSI assists in constructing a stable solid electrolyte interphase (SEI) layer on the Li surface enriched with LiF, Li3N, and RCOOLi. The modulation of lithium deposition behavior on the anode by Pyr14TFSI ensures stable Li plating/stripping for >1500 h. A Li-Cu cell exhibits stable cycling for >200 cycles at a current density of 0.05 mA cm-2, with an average Coulombic efficiency of 92.7%. In situ polymerization ensures that P(VECx-EGy)/Pyrz/LiTFSI@CE QSPEs exhibit excellent interface compatibility with the anode and the cathode. The CR2032 button cell Li|P(VEC1-EG0.06)/Pyr0.4/LiTFSI@CE|LiCoO2 demonstrates stable cycling with a negligible capacity decay of 0.083% per cycle for >390 cycles at 25 °C and 0.2 C when using a high-voltage LiCoO2 (4.45 V) cathode. Furthermore, a 7.1 mAh pouch cell achieves stable charge-discharge cycles, confirming the pronounced stability of the as-fabricated QSPE at the interfaces of the high-voltage LiCoO2 cathode and Li anode.

Light-Controlled Cationic RAFT Polymerization of Vinyl Ethers Using N-Arylacridinium Photocatalysts

Light-Controlled Cationic RAFT Polymerization of Vinyl Ethers Using <i>N</i>-Arylacridinium Photocatalysts

Photo‐controllable cationic homopolymerization and random copolymerization of vinyl ethers based on iridium salt photocatalyst

AbstractTemporal control of chain growth is a central challenge for photoinitiated active polymerization. In this work, we introduced an iridium salt complex‐based catalyst system to achieve fine temporal control of the chain growth process. By electrochemical analysis, compared with the pyran salt photocatalyst, it was found that the iridium salt complex could promote the chain transfer of active species to reversible addition‐fragmentation chain transfer polymerization (RAFT) reagent, thereby generating dormant species, which provided the possibility of time control of the polymerization process. Using this catalytic system, we successfully achieved homopolymerization of vinyl ethers with different substituents and random copolymerization with isobutyl vinyl ethers, which is not only pointed the way for broadening the monomer selection in the future, but also provided an innovative way to prepare new functionalized materials.

Syntheses of α-monofluoroalkyl acetophenones from fluoroalkyl carboxylic NHPI esters and silyl enol ethers by photocatalytic decarboxylative reaction

A photoredox-catalyzed decarboxylative α-monofluoroalkylation of silyl enol ethers with fluoroalkyl carboxylic N-(hydroxy)phthalimide esters has been successfully developed. Diverse functionalized α-monofluoroalkyl acetophenones were produced in modest to good yields under mild and operationally simple conditions. The developed method was further applied to synthesize antalgic and ataractic activity compound containing α-monofluoroalkyl acetophenone skeleton.

Selenoprotein I is indispensable for ether lipid homeostasis and proper myelination

Selenoprotein I (SELENOI) catalyzes the final reaction of the CDP-ethanolamine branch of the Kennedy pathway, generating the phospholipids phosphatidylethanolamine (PE) and plasmenyl-PE. Plasmenyl-PE is a key component of myelin and is characterized by a vinyl ether bond that preferentially reacts with oxidants, thus serves as a sacrificial antioxidant. In humans, multiple loss-of-function mutations in genes affecting plasmenyl-PE metabolism have been implicated in hereditary spastic paraplegia (HSP), including SELENOI. Herein, we developed a mouse model of nervous system-restricted SELENOI deficiency that circumvents embryonic lethality caused by constitutive deletion and recapitulates phenotypic features of HSP. Resulting mice exhibited pronounced alterations in brain lipid composition, which coincided with motor deficits and neuropathology including hypomyelination, elevated reactive gliosis, and microcephaly. Further studies revealed increased lipid peroxidation in oligodendrocyte lineage cells and disrupted oligodendrocyte maturation both in vivo and in vitro. Altogether, these findings detail a critical role for SELENOI-derived plasmenyl-PE in myelination that is of paramount importance for neurodevelopment.

Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force.

Hydrogen fluoride (HF) is a versatile reagent for material transformation, with applications in self-immolative polymers, remodeled siloxanes, and degradable polymers. The responsive in situ generation of HF in materials therefore holds promise for new classes of adaptive material systems. Here, we report the mechanochemically coupled generation of HF from alkoxy-gem-difluorocyclopropane (gDFC) mechanophores derived from the addition of difluorocarbene to enol ethers. Production of HF involves an initial mechanochemically assisted rearrangement of gDFC mechanophore to α-fluoro allyl ether whose regiochemistry involves preferential migration of fluoride to the alkoxy-substituted carbon, and ab initio steered molecular dynamics simulations reproduce the observed selectivity and offer insights into the mechanism. When the alkoxy gDFC mechanophore is derived from poly(dihydrofuran), the α-fluoro allyl ether undergoes subsequent hydrolysis to generate 1 equiv of HF and cleave the polymer chain. The hydrolysis is accelerated via acid catalysis, leading to self-amplifying HF generation and concomitant polymer degradation. The mechanically generated HF can be used in combination with fluoride indicators to generate an optical response and to degrade polybutadiene with embedded HF-cleavable silyl ethers (11 mol %). The alkoxy-gDFC mechanophore thus provides a mechanically coupled mechanism of releasing HF for polymer remodeling pathways that complements previous thermally driven mechanisms.

Preparation of a novel hyaluronic acid-based separable hydrogel microneedle with niacinamide to treat pigment deposition using solvent-free solid-state crosslinking method

With the increase in age and prolonged exposure to ultraviolet radiation, especially on the face, pigment deposition often has a negative impact on individuals physically and emotionally. In order to address this issue, a solvent-free solid-state crosslinked hyaluronic acid (HA)-based separable hydrogel microneedle (SHMN) was developed by combining the advantages of hydrogel microneedle and soluble microneedle. This microneedle could separate the needle tip from the backing within five minutes and had the advantage of slow drug release. Hydrogel microneedle tips were prepared by solid-state crosslinking method of HA and poly (methyl vinyl ether)-maleic acid (GAN) for the first time. This crosslinking method without the need for dialysis or the addition of organic solvents, making it a safer, more reliable, and significantly time-saving process compared to previous methods. The soluble material polyvinylpyrrolidone (PVP) was selected as the root and backing of the microneedle. When the microneedle penetrated the skin and contacted with interstitial fluid, the bottom of the microneedle dissolved, and the tip of hydrogel loaded with drugs was separated from the shaft. In addition, the microneedle patch has high drug loading and excellent mechanical properties, which can meet the effective treatment of skin pigmentation.

Design of sec-Benzyl Vinyl Ethers toward the Synthesis of Alternating Copolymers Composed of Vinyl Alcohol and Vinyl Ether Units.

In this work, we designed benzyl vinyl ethers carrying alkyl substituents at the benzyl position (i.e., sec-BnVEs) as bulky, reactive, and transformable monomers to realize the alternating cationic copolymerization with an alkyl vinyl ether (VE). In particular, the isopropyl substitution caused not only the bulkiness to suppress the successive propagation but also an enhancement of the vinyl group reactivity to promote crossover propagation with a less bulky VE comonomer. The isopropyl-substituted BnVE (iPr-BnVE) underwent living cationic alternating copolymerization with n-butyl VE (nBVE), and the alternating propagation was strongly suggested by the reactivity ratios. The subsequent deprotection of the sec-benzyl pendant afforded the vinyl alcohol (VA)-nBVE alternating copolymer, and the corresponding statistical copolymer was also synthesized by using the nonsubstituted monomer (BnVE) instead of iPr-BnVE. The alternating copolymer exhibited a higher glass transition temperature, which likely stems from the uniform and efficient hydrogen-bonding formation due to the periodic sequence.

Impact of open‐air processing on atmospheric pressure plasma deposition of poly(ethylene oxide) coatings for antifouling applications

AbstractAtmospheric pressure plasma deposition (APPD) of poly(ethylene oxide) (PEO)‐like antifouling coatings provides an attractive way to reduce biofouling for reliable biosensor operation. Cold atmospheric pressure plasma jets are designed to operate in open air. This paper demonstrates the impact of open‐air processing on the composition and properties of PEO‐like coatings by APPD with vinyl ether precursors. The open‐air environment inhibits polymerization as indicated by low deposition rates, oxygen incorporation in the coatings, and instability of the coatings in water. The composition and stability of the coatings improve by appropriate nozzle design and by deposition in an environment with lower air content. The resulting PEO‐like coatings are stable and antifouling for an antibody solution and inhibit adhesion of human fibroblast cells.

Synthesis and Properties of Vinyl Ether and Acrylonitrile Copolymers

AbstractThe radical copolymerizations of vinyl ethers, including ethylene glycol monovinyl ether (HEVE) and isobutyl vinyl ether (IBVE), and acrylonitrile (AN) are investigated. The reactivity ratios of comonomers are evaluated by Fineman–Ross (rHEVE = 0.032 and rAN = 1.054, and rIBVE = 0.031 and rAN = 13.984) and Kelen–Tudos (rHEVE = 0.001 and rAN = 1.036, and rIBVE = 0.032 and rAN = 13.981) methods, respectively. The conversions of HEVE and IBVE under similar conditions also support that HEVE has a higher reactivity than that of IBVE. A series of poly(HEVE‐co‐AN)s (Mn from 56 000 to 110 000) and poly(IBVE‐co‐AN)s (Mn from 52 000 to 97 000) with random sequential structure are prepared. Furthermore, the glass transitional temperatures of poly(vinyl ether‐co‐AN)s decrease with the increase of vinyl ether units in the copolymers. Thermal stability of poly(vinyl ether‐co‐AN)s is comparable, which is slightly affected by vinyl ether contents. Poly(HEVE‐co‐AN)s possess a two‐stage weight loss (one around 230 °C, and the other around 300 °C), and poly(IBVE‐co‐AN)s decompose at around 350 °C with one stage. In addition, the poly(HEVE‐co‐AN)s demonstrate a good hydrophilicity of which the average of static water contact angles decrease from 85.4° to 62.4° with the HEVE units increased from 8% to 33%.

Synthesis of Unsymmetrical 1,6-Dicarbonyl Compounds through Photocatalytic One-Pot Tandem Three-Component Reaction.

Unsymmetrical 1,6-dicarbonyl compounds are useful building blocks in organic synthesis. However, the synthetic methods are limited. Herein we report a three-component one-pot reaction for the synthesis of unsymmetrical 1,6-diketones. This reaction utilizes sulfides as radical precursors and enol ethers as building blocks. It takes advantage of photocatalysis and Lewis acid catalysis. Its synthetic utility was demonstrated in the modification of biorelevant compounds.

Metal-Free, Photoinitiated Cationic Terpolymerization of Vinyl Ethers, Oxiranes, and Ketones: Simultaneous Control of Monomer Sequence and Molecular Weight by the Formation of Long-Lived Propagating Species

Metal-Free, Photoinitiated Cationic Terpolymerization of Vinyl Ethers, Oxiranes, and Ketones: Simultaneous Control of Monomer Sequence and Molecular Weight by the Formation of Long-Lived Propagating Species

Interaction of Cyclodextrins with Amphiphilic Alternating Cooligomers Possessing the Dense Triazole Backbone.

The interaction of cyclodextrins (CDs) with structure-controlled polymers is expected to provide significant insights into macromolecular recognition. However, the interaction of CDs with structure-controlled polymers has been an underexamined issue of investigation. Herein, alternating amphiphilic cooligomers (oligoCnAH, where n denotes the carbon number of alkyl groups; n = 4, 8, and 12) were synthesized by copper(I)-catalyzed azide-alkyne cycloaddition polymerization of heterodimers of 4-azido-5-hexynoic acid (AH) derivatives carrying N-alkylamide and t-butyl (tBu) ester side chains, followed by hydrolysis of the tBu ester, to study the interaction of CDs with oligoCnAH by 1H NMR, nuclear Overhauser effect spectroscopy, and pulse-field-gradient spin-echo NMR. These NMR studies indicated that αCD interacted with oligoC4AH, αCD and βCD interacted with oligoC8AH, and all CDs interacted with oligoC12AH. Based on the equilibrium models proposed, the binding constants were evaluated for the binary mixtures, which showed interaction. Comparing the interactions of the CDs/oligoC12AH binary mixtures with those of the binary mixtures of CDs and alternating copolymers of sodium maleate and dodecyl vinyl ether (polyC12M), it is concluded that oligoC12AH forms less stable micelles than does polyC12M presumably because of the lower molecular weight, the hydrophilic amide groups in the side chain, and the longer interval between neighboring C12 groups in oligoC12AH.

Hyperbranched Poly(vinyl ether ester)s with Structure-Dependent Intrinsic Fluorescence: Synthesis, Properties, and Applications

Hyperbranched Poly(vinyl ether ester)s with Structure-Dependent Intrinsic Fluorescence: Synthesis, Properties, and Applications

Superhydrophobic anticorrosive fluoroethylene vinyl ether coating nanocomposited with metal-organic framework derived ferrite nanocapsules and MXene

Superhydrophobic anticorrosive fluoroethylene vinyl ether coating nanocomposited with metal-organic framework derived ferrite nanocapsules and MXene

Expanded Azahelicenes with Large Dissymmetry Factors.

Expanded azahelicenes, as heteroanalogues of helically chiral helicenes, hold significant potential for chiroptical materials. Nevertheless, their investigation and research have remained largely unexplored. Herein, we present the facile synthesis of a series of expanded azahelicenes NHn (n=1-5) consisting of 11, 19, 27, 35, and 43 fused rings, mainly by Suzuki coupling followed by Bi(OTf)3 -mediated cyclization of vinyl ethers. The structures of NH2, NH3 and NH4 were confirmed through X-ray crystallography analysis, and their (P)- and (M)- enantiomers were also isolated with chiral high performance liquid chromatography. The enantiomers exhibit large absorption (abs) and luminescence (lum) dissymmetry factors, with |gabs |max =0.044; |glum |max =0.003 for NH2, |gabs |max =0.048; |glum |=0.014 for NH3, and |gabs |max =0.043; |glum |max =0.021 for NH4, which are superior to their respective all-carbon analogues.

Expanded Azahelicenes with Large Dissymmetry Factors

AbstractExpanded azahelicenes, as heteroanalogues of helically chiral helicenes, hold significant potential for chiroptical materials. Nevertheless, their investigation and research have remained largely unexplored. Herein, we present the facile synthesis of a series of expanded azahelicenes NHn (n=1–5) consisting of 11, 19, 27, 35, and 43 fused rings, mainly by Suzuki coupling followed by Bi(OTf)3‐mediated cyclization of vinyl ethers. The structures of NH2, NH3 and NH4 were confirmed through X‐ray crystallography analysis, and their (P)‐ and (M)‐ enantiomers were also isolated with chiral high performance liquid chromatography. The enantiomers exhibit large absorption (abs) and luminescence (lum) dissymmetry factors, with |gabs|max=0.044; |glum|max=0.003 for NH2, |gabs|max=0.048; |glum|=0.014 for NH3, and |gabs|max=0.043; |glum|max=0.021 for NH4, which are superior to their respective all‐carbon analogues.

Unraveling the Potential of Vinyl Ether as an Ethylene Surrogate in Heteroarene C─H Functionalization via the Spin-Center Shift.

Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to its nature as a highly flammable gas. Herein, a strategic use of easily handled vinyl ether is reported as a latent ethylene surrogate achieved via a spin-center shift (SCS) pathway, enabling the successful three-component reaction that bridges heteroarenes and various coupling partners, including sulfinates, thiols, and phosphine oxides. Through a photoredox catalytic process, α-oxy radicals are generated by combining various radicals with phenyl vinyl ether, which are subsequently added to N-heteroarenes. Subsequently, the radical-mediated SCS pathway serves as the driving force for C─O bond cleavage, effectively engaging the phenoxy group as a leaving group. In addition, by broadening the utility of the method, a valuable synthon is provided for efficient C─H vinylation of N-heteroarenes following sulfonyl group elimination. This approach not only enriches the toolbox of synthetic methodology but also provides a more streamlined alternative, circumventing the challenges associated with direct ethylene gas usage. The versatility of the method, particularly evident in late-stage functionalizations of medicinally relevant molecules and peptides, underscores its capability to produce invaluable three-component compounds and vinylated N-heteroarene derivatives.

Toward Lung Ventilation Imaging Using Hyperpolarized Diethyl Ether Gas Contrast Agent.

Hyperpolarized 129 Xe gas was FDA-approved as an inhalable contrast agent for magnetic resonance imaging of a wide range of pulmonary diseases in December 2022. Despite the remarkable success in clinical research settings, the widespread clinical translation of HP 129 Xe gas faces two critical challenges: the high cost of the relatively low-throughput hyperpolarization equipment and the lack of 129 Xe imaging capability on clinical MRI scanners, which have narrow-bandwidth electronics designed only for proton (1 H) imaging. To solve this translational grand challenge of gaseous hyperpolarized MRI contrast agents, here we demonstrate the utility of batch-mode production of proton-hyperpolarized diethyl ether gas via heterogeneous pairwise addition of parahydrogen to ethyl vinyl ether. An approximately 0.1-liter bolus of hyperpolarized diethyl ether gas was produced in 1 second and injected in excised rabbit lungs. Lung ventilation imaging was performed using sub-second 2D MRI with up to 2×2 mm2 in-plane resolution using a clinical 0.35 T MRI scanner without any modifications. This feasibility demonstration paves the way for the use of inhalable diethyl ether as a gaseous contrast agent for pulmonary MRI applications using any clinical MRI scanner.