Cyclic Olefin Research Articles

A biomimetic approach towards a universal slippery liquid infused surface coating

One biomimetic approach to surface passivation involves a series of surface coatings based on the slick surfaces of carnivorous pitcher plants (Nepenthes), termed slippery liquid-infused porous surfaces (SLIPS). This study introduces a simplified method to produce SLIPS using a polydopamine (PDA) anchor layer, inspired by mussel adhesion. SLIPS layers were formed on cyclic olefin copolymer, silicon, and stainless steel substrates, by first growing a PDA film on each substrate. This was followed by a hydrophobic liquid anchor layer created by functionalizing the PDA film with a fluorinated thiol. Finally, perfluorodecalin was applied to the surface immediately prior to use. These biomimetic surface functionalization steps were confirmed by several complimentary surface analysis techniques. The wettability of each surface was probed with water contact angle measurements, while the chemical composition of the layer was determined by X-ray photoelectron spectroscopy. Finally, ordering of specific chemical groups within our PDA SLIPS layer was determined via sum frequency generation spectroscopy. The hemocompatibility of our new PDA-based SLIPS coating was then evaluated by tracking FXII activation, fibrin generation time, clot morphology, and platelet adhesion to the surface. This hemocompatibility work suggests that PDA SLIPS coatings slow or prevent clotting, but the observation of both FXII activation and the presence of adherent and activated platelets at the PDA SLIPS samples imply that this formulation of a SLIPS coating is not completely omniphobic.

Photoinduced Pd‐Catalyzed Direct Sulfonylation of Allylic C−H Bonds

AbstractAllylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C−H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties. Importantly, the obtained allylic sulfones can be readily diversified into a wide range of products, thus enabling formal alkene transposition and all‐carbon quaternary center formation through the sequential C−H functionalization.

Platinum‐Catalyzed Regio‐ and Enantioselective Diboration of Unactivated Alkenes with (pin)B−B(dan)

AbstractAsymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization of the less hindered primary boronic ester is commonly achieved. Conversely, selective functionalization of the sterically less accessible secondary boronic ester remains challenging. An alternative way to control chemoselective functionalization of bis(boron) compounds is by engendering different Lewis acidity to the two boryl moieties, since reactivity would then be dictated by Lewis acidity instead of sterics. We report herein the regio‐ and enantioselective Pt‐catalyzed diboration of unactivated alkenes with (pin)B−B(dan). A broad range of terminal and cyclic alkenes undergo diboration to furnish the differentiable 1,2‐bis(boron) compounds with high levels of regio‐ and enantiocontrol, giving access to a wide variety of novel building blocks from a common intermediate. The reaction places the less Lewis acidic B(dan) group at the less hindered position and the resulting 1,2‐bisboryl alkanes undergo selective transformations of the B(pin) group located at the more hindered position. The regioselectivity of the diboration has been studied by DFT calculations and is believed to originate from the trans influence, which lowers the activation barrier for formation of the regioisomer that places the weaker electron donor [B(pin) vs B(dan)] opposite the strong electron donor (alkyl group) in the platinum complex.

Compact Plasma Ionization for Ion Mobility Spectrometry Using a 4.3 MHz Miniature Tesla Coil.

In this study, a low-cost 4.3 MHz plasma ionization source for ion mobility spectrometry (IMS), utilizing a miniaturized Tesla coil, is presented. This compact design, combined with a 3D printed cyclic olefin copolymer (COC) housing, delivers a stable and directed plasma suitable for ionization in IMS applications. The 3D printed housing ensures chemical resistance and low off-gassing, which are crucial for maintaining sample integrity. The Tesla coil produces a consistent sine wave at 4.3 MHz, and when connected to stainless steel screw electrodes it generates a stable plasma capable of ionizing analytes such as limonene, MTBE, nicotine, 2-octanone, and propofol. Measurements were conducted in both positive and negative ion modes. The results demonstrate the Tesla coil's effectiveness as a low-cost and reliable ionization source for IMS, offering comparable performance to traditional Ni63 β-emitters. This advancement in plasma ionization technology could facilitate more accessible and flexible IMS systems for diverse analytical applications. The integration of 3D printing in the development of this ionization source underscores the potential for customized, low-cost analytical instrumentation, promoting innovation in laboratory environments and commercial applications.

Mechanistic studies on the oxidation reaction of n-pentane

The oxidation reaction mechanism of n-pentane is investigated using density functional theory and transition state theory as a case study to elucidate the combustion characteristics of liquids with low boiling points. This study divides the oxidation reaction of n-pentane into four steps. First, n-pentane decomposes to form n-pentyl radicals C5H11 and H, CH3 and C4H9, and C2H5 and C3H7 radicals. Second, n-pentane primarily undergoes H-abstraction reactions with H, CH3, C2H5, and C3H7 radicals to form the C5H11 radicals. Subsequently, C5H11 radicals react with O2 in an addition reaction to form n-pentyl peroxy radicals ROO. Finally, ROO radical undergoes internal H-atom transfer to form hydroperoxy pentyl radicals QOOH, which then undergoes cyclization and bond scission to produce cyclic ethers, alkenes, aldehydes, OH radicals, and HO2 radicals. Results indicate that n-pentane readily decomposes into C2H5 and C3H7 radicals, with a bond dissociation energy of 367.1 KJ/mol. The H-abstraction reactions involving H and CH3 radicals have the fastest rates, which require the lowest energy barriers of 21.6 and 41.9 KJ/mol, respectively. The reaction between C5H11 and O2 is a barrierless addition reaction. The oxidation of n-pentane, which leads to the formation of 2-methyloxirane and OH radicals, exhibits the fastest reaction rate.

Electrical and Dielectrical Properties of Composites Based on Alumina and Cyclic Olefin Copolymers

Understanding the performance of polymer dielectrics at different temperatures is becoming increasingly important due to the rapid development of electric cars, electromagnetic devices, and new energy production solutions. Cyclic olefin copolymers (COCs) are an attractive material due to their low water absorption, good electrical insulation, long-term stability of surface treatments, and resistance to a wide range of acids and solvents. This work focused on the dielectric and electrical properties of cyclic olefin copolymer (COC)/Al2O3 composites over a wide range of temperature and frequency domains, from room temperature to cryogenic temperatures (around 125 K). Permittivity, electrical conductivity, and electrical modulus are given consideration. A composite of up to 50% Al2O3 mixed with COC was prepared via a conventional melt-blending method. The final samples were formed in sheets and processed using injection and extrusion moldings. It was found that formulations with Al2O3 concentrations ranging from 10 to 50% resulted in higher electrical conductivity while maintaining the viscosity of the composite at a level acceptable for polymer-processing machinery. Our data show that COC/alumina composites present substantial potential as materials for high-frequency applications, even at the regime of cryogenic temperatures.

Polyalkenamers as Drop-In Additives for Ring-Opening Metathesis Polymerization: A Promising Upcycling Paradigm.

We report a distinct strategy to upcycle waste polyalkenamers such as polybutadiene into new, performance-advantaged materials by using them as drop-in additives for ring-opening metathesis polymerization (ROMP). The polyalkenamers serve as competent chain-transfer agents in ROMPs of common classes of cyclic olefin monomers, facilitating good molecular weight control, allowing low Ru catalyst loadings, and enabling efficient incorporation of the polyalkenamer into the synthesized polymeric material. We successfully demonstrate ROMP using model polyalkenamers and translate these learnings to leverage commercial polybutadiene and acrylonitrile butadiene styrene (ABS) as chain transfer agents for ROMP copolymerizations. Critically, our strategy is shown to be highly efficient and operationally simple, quantitatively incorporating the polyalkenamer and inheriting aspects of its thermomechanical performance. Our results highlight a promising pathway for the upcycling of polyalkenamers and provide an alternative to existing deconstruction and functional upcycling strategies.

Modification of surface topographies to inhibit candida biofilm formation.

The rise of infections associated with indwelling medical devices is a growing concern, often complicated by biofilm formation leading to persistent infections. This study investigates a novel approach to prevent Candida albicans attachment on the surface by altering surface topography. The research focuses on two distinct surface topographies: symmetry (squares) and non-symmetry (lines), created through a direct laser photolithography process on a Cyclic olefin copolymer (COC) surface. The wettability of these patterned surfaces was then examined immediately after fabrication and plasma treatment to mimic the sterilization process of indwelling devices through UV plasma. The results reveal directional wettability in the line pattern and size-dependent wettability in both square and line patterns. Candida albicans were cultured on these surfaces to assess the efficacy of the topography in preventing biofilm formation. The study demonstrates that symmetry and non-symmetry pattern topography inhibit biofilm formation, providing a promising strategy for mitigating Candida-associated infections on medical devices. The research sheds light on the potential of surface modification techniques to enhance the biocompatibility of medical devices and reduce the risk of biofilm-related infections.

Compact THz Polarization Splitter with Large Bandwidth Based on Cascade Hexagonal Porous Two-Core PCF

ABSTRACT A novel cyclic olefin copolymer (COC)-based terahertz (THz) polarization beam splitter (PBS) employing photonic crystal fiber (PCF) with cascade hexagonal porous two-core structure is proposed. The porous two-core is achieved by replacing the original two large air holes with three layers of small air holes. The mode coupling characteristics between the even and odd modes in the x- and y-polarization directions for the proposed THz PBS are explored using the time-domain finite difference (FDTD) method. The influence of PBS structural parameters on its coupling length is investigated. Numerical analysis results indicate that the bandwidths of 227.8 GHz (ranging from 1.8970 to 2.1248 THz) and 147 GHz (ranging from 1.928 to 2.075 THz) are acquired for the x- and y-polarization fundamental modes, respectively. The highest extinction ratios (ERs) are 114.5 dB and 72.3 dB, and the minimum insertion losses (ILs) are 0.0142 dB and 0.0369 dB for the x- and y-polarization fundamental modes, respectively. Moreover, the length of the proposed PBS is merely 11.655 mm. The proposed PBS will find potential applications in polarization-diverse THz systems, including broadband line-of-sight communication, real-time security checks, and high-resolution imaging.

Unspecific Peroxygenase Catalyzes Selective Remote‐Site Functionalizations

AbstractWe describe the discovery of an unspecific peroxygenase (UPO) variant that catalyzes the remote‐site functionalization of halogenated and unsaturated hydrocarbons with high catalytic site‐specificity. UPOs are fungal heme‐thiolate biocatalysts with wide‐ranging oxidative activities, including C─H bond oxygenation, usually with limited regioselectivity. We describe here a wild‐type MroUPO, newly isolated in high yield from a previously uncharacterized strain of Marasmius rotula. This variant, MroUPO‐TN, catalyzes the selective oxygenation of a range of haloalkanes, cyclic haloalkanes and cyclic olefins to generate useful remote‐site haloketones. The regioselectivity for eight‐membered rings reaches 99% with significant enantiomeric excess. Mechanistic studies performed with deuterated substrates and 18O‐labeling experiments have revealed a synergy between intrinsic substrate properties and the highly aliphatic, heme active site. The observed selectivity offers routes to new and useful, bifunctional synthons and pharmacophores, thus providing practical ways to employ these natural and environmentally benign biocatalysts.

Hydrazine‐Catalysed Ring‐Opening Metathesis Polymerization Of Cyclobutenes

AbstractMaterials formed by the ring‐opening metathesis polymerization (ROMP) of cyclic olefins are highly valued for industrial and academic applications but are difficult to prepare free of metal contaminants. Here we describe a highly efficient metal‐free ROMP of cyclobutenes using hydrazine catalysis. Reactions can be initiated via in situ condensation of a [2.2.2]‐bicyclic hydrazine catalyst with an aliphatic or aromatic aldehyde initiator. The polymerizations show living characteristics, achieving excellent control over molecular weight, low dispersity values, and high chain‐end fidelity. Additionally, the hydrazine can be used in substoichiometric amounts relative to the aldehyde chain‐end while maintaining good control over molecular weight and low dispersity values, indicating that a highly efficient chain transfer mechanism is occurring.

Exploring the Impact of 3D Printing Parameters on the THz Optical Characteristics of COC Material.

In terahertz (THz) optical systems, polymer-based manufacturing processes are employed to ensure product quality and the material performance necessary for proper system maintenance. Therefore, the precise manufacturing of system components, such as optical elements, is crucial for the optimal functioning of the systems. In this study, the authors investigated the impact of various 3D printing parameters using fused deposition modeling (FDM) on the optical properties of manufactured structures within the THz radiation range. The measurements were conducted on 3D printed samples using highly transparent and biocompatible cyclic olefin copolymer (COC), which may find applications in THz passive optics for "in vivo" measurements. The results of this study indicate that certain printing parameters significantly affect the optical behavior of the fabricated structures. The improperly configured printing parameters result in the worsening of THz optical properties. This is proved through a significant change in the refractive index value and undesirable increase in the absorption coefficient value. Furthermore, such misconfigurations may lead to the occurrence of defects within the printed structures. Finally, the recommended printing parameters, which improve the optical performance of the manufactured structures are presented.

Modular Synthesis of gem-Difluorotetrahydrocarbazolone Scaffolds via Copper-Catalyzed Cascade Reaction of Bromodifluoroacetyl Indoles and Olefins.

A novel and efficient modular synthesis of gem-difluorotetrahydrocarbazolone scaffolds via copper-catalyzed radical cascade cyclization of bromodifluoroacetyl indoles and olefins has been reported. This operationally simple protocol provides straightforward and practical access to a series of privileged gem-difluorotetrahydrocarbazolone scaffolds from readily available starting materials, with the feature of broad functional group tolerance and mild reaction conditions. Moreover, the method could be used for the late-stage functionalization of bioactive molecules, which opens up the possibility for practical applications.

Diastereoselective Hydrodifluoromethylation of Alkenyl N-Heterocycles via Photocatalytic Radical-Polar Crossover.

A diastereoselective hydrodifluoromethylation of N-heteroaryl alkenes was successfully established. This method was applicable to an array of N-heteroaryl substrates with both cyclic and acyclic alkenes while displaying tolerance to a variety of functional groups. The conditions were also expanded to obtain hydrotrifluoromethylated products with similar results. Initial mechanistic studies suggest that the final protonation step is accessed through a radical-polar crossover process.

Triazenolysis of alkenes as an aza version of ozonolysis.

Alkenes are broadly used in synthetic applications, thanks to their abundance and versatility. Ozonolysis is one of the most canonical transformations that converts alkenes into molecules bearing carbon-oxygen motifs via C=C bond cleavage. Despite its extensive use in both industrial and laboratory settings, the aza version-cleavage of alkenes to form carbon-nitrogen bonds-remains elusive. Here we report the conversion of alkenes into valuable amines via complete C=C bond disconnection. This process, which we have termed 'triazenolysis', is initiated by a (3 + 2) cycloaddition of triazadienium cation to an alkene. The triazolinium salt formed accepts hydride from borohydride anion and spontaneously decomposes to create new C-N motifs upon further reduction. The developed reaction is applicable to a broad range of cyclic alkenes to produce diamines, while various acyclic C=C bonds may be broken to generate two separate amine units. Computational analysis provides insights into the mechanism, including identification of the key step and elucidating the significance of Lewis acid catalysis.

CGC-Scandium-Mediated Copolymerization of Ethylene with Amine-Functionalized Cyclic Olefins

CGC-Scandium-Mediated Copolymerization of Ethylene with Amine-Functionalized Cyclic Olefins

Research on the dynamics and mechanism of thermal cracking of coal-based endothermic hydrocarbon fuels

Thermal cracking of endothermic hydrocarbon fuels (EHF) plays an important role in the endothermic process when the fuel temperature exceeds the supercritical temperature. To gain a deeper understanding of the thermal cracking behavior of EHF, this work discusses the thermal cracking law and reaction mechanism of coal-based EHF at different temperatures through static thermal cracking experiments, and establishes a total molecular reaction dynamics model containing 34 species and 24-step reactions based on product distribution. The results show that in the temperature range of 450℃ to 500℃, the gas phase yield of the fuel increases linearly from 8% to 56%, and the conversion rate reaches up to 96.1%. The kinetic reaction of thermal cracking conforms to the primary kinetic equation, the cracking rate constant k is between 1.08×10-4~7.92×10-4s-1, the activation energy Ea=184.47±11.5kJ∙mol-1, and the precursor factor lnA=21.61±3.0. Gas phase products include hydrogen, methane, ethane, ethylene, propane and butane. Liquid phase products include paraffins, alkyldecahydronaphthalenes and aromatic hydrocarbons. As the cracking depth increases, the degree of fuel branching first increases and then decreases, up to 0.33. Paraffins and alkyldecahydronaphthalenes are gradually converted into olefins, cyclic olefins, benzene, naphthalene, indene, fluorene and pyrene and other compounds. Based on the product distribution, the reaction mechanism of thermal cracking of coal-based EHF is speculated to include single-molecule β-cracking, bimolecular F-S-S, intramolecular H-transfer, cyclization and isomerization mechanisms.

Generation of alkene radical cation for thioxanthone-TfOH complex-catalyzed intramolecular cyclization using a photoredox catalysis strategy

Photo catalysis has comprehensively become a powerful tool in organic synthesis, and organic molecules are thriving as catalyst. The thioxanthone-TfOH complex (9-HTXTF) as photoredox catalyst with high oxidative capacity can be applied in single electron reduction of alkene affording alkene radical anion as a key intermediate. To transform this intermediate from radical anion to radical cation, a well-designed strategy is proposed with N-arylacrylamides as substrate. Based on its single electron transfer (SET) with 9-HTXTF*, N-radical cation is generated and then transformed to alkene radical cation by intramolecular conjugated system. By using this photoredox catalysis strategy, we developed a 9-HTXTF-catalyzed photochemical cyclization of alkenes, which further expands the applications of this catalyst. The entire cyclization is metal-free and without sacrificing agents, which conforms to atom economy and environmental friendliness.

Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams.

The direct nucleophilic addition of amides to unfunctionalized alkenes via photoredox catalysis represents a facile approach towards functionalized alkylamides. Unfortunately, the scarce nucleophilicity of amides and competitive side reactions limit the utility of this approach. Herein, we report an intramolecular photoredox cyclization of alkenes with β-lactams in the presence of an acridinium photocatalyst. The approach uses an intramolecular nucleophilic addition of the β-lactam nitrogen atom to the radical cation photogenerated in the linked alkene moiety, followed by hydrogen transfer from the hydrogen atom transfer (HAT) catalyst. This process was used to successfully prepare 2-alkylated clavam derivatives.

Bioactive modification of cyclic olefin copolymer (COC) film surfaces by hyaluronic acid and chitosan for enhanced cell adhesion

Cyclic olefin copolymer (COC) has recently emerged as an attractive material in biomedical fields for its high purity, excellent stability and chemical resistance, particularly in applications of microfluidic chips, prefilled syringes and bone regeneration. However, the high hydrophobicity of COC has inhibited the adhesion of cells and biological macromolecules, such as proteins, etc., significantly limiting its broader applications. In this study, we propose a new method to modify COC surfaces by sequential coating with polydopamine (PDA) followed by hyaluronic acid (HA) or O-carboxymethyl chitosan (CMC), while comparing the impacts of the positively charged HA and negatively charged CMC on protein adsorption and cell adhesion. FTIR and XPS measurements confirmed the successful modification on COC films, resulting in surfaces with highly increased hydrophilicity, anti-oxidative properties, and improved protein adsorption. Moreover, negatively charged HA, with signal transduction capabilities showed a greater effect in promoting cell adhesion. Thus, we present a straightforward strategy for enhancing the hydrophilicity of COC surfaces, offering new insights into COC modification and potential biomedical applications.