Carbon-centered Free Radicals Research Articles

Carbon Free Radical (R∙) Inactivates NF-κB for Radical Capping Therapy.

Inactivating hyperactivated transcription factors can overcome tumor therapy resistance, but their undruggable features limit the development of conventional inhibitors. Here, we report that carbon-centered free radicals (R∙) can inactivate NF-κB transcription by capping the active sites in both NF-κB and DNA. We construct a type of thermosensitive R∙ initiator loaded amphiphilic nano-micelles to facilitate intracellular delivery of R∙. At a temperature of 43°C, the generated R∙ engage in electrophilic radical addition towards double bonds in nucleotide bases, and simultaneously cap the sulfhydryl residues in NF-κB through radical chain reaction. As a result, both NF-κB nuclear translocation and NF-κB-DNA binding are suppressed, leading to a remarkable NF-κB inhibition of up to 94.1%. We have further applied R∙ micelles in a clinical radiofrequency ablation tumor therapy model, showing remarkable NF-κB inactivation and consequently tumor metastasis inhibition. Radical capping strategy not only provides a method to solve the heat-sink effect in clinic tumor hyperthermia, but also suggests a new perspective for controllable modification of biomacromolecules in cancer therapy.

Recent Advances in Molecule Synthesis Involving C-C Bond Cleavage of Ketoxime Esters.

The synthetic strategies of oxime derivatives participating in radical-type reactions have been rapidly developed in the last few decades. Among them, the N-O bond cleavage of oxime esters leading to formation of nitrogen-centered radicals triggers adjacent C-C bond cleavage to produce carbon-centered free radicals, which has been virtually used in organic synthesis in recent years. Herein, we summarized the radical reactions involving oxime N-O bond and C-C bond cleavage through this special reaction form, including those from acyl oxime ester derivatives and cyclic ketoxime ester derivatives. These contents were systematically classified according to different reaction types. In this review, the free radical reactions involving acyl oxime esters and cyclic ketoxime esters after 2021 were included, with emphasis on the substrate scope and reaction mechanism.

Distribution of environmentally persistent free radicals in size-segregated PMs emitted from residential biomass fuel combustion

Environmentally persistent free radicals (EPFRs) are considered as an emerging pollutant due to their potential environmental risks, but the distribution characteristics of particulate matters (PMs)-EPFRs from residential combustion source are poorly understood. In this study, biomass (corn straw, rice straw, pine and jujube wood) combustion was studied in lab-controlled experiments. More than 80% of PM-EPFRs were distributed in PMs with aerodynamic diameter (dae) ≤ 2.1 µm, and their concentration in fine PMs was about 10 times that in coarse PM (2.1 µm ≤ dae ≤ 10 µm). The detected EPFRs were carbon-centered free radicals adjacent to oxygen atoms or a mixture of oxygen- and carbon-centered radicals. The concentrations of EPFRs in coarse and fine PMs were positively correlated with char-EC, but the EPFRs in fine PMs exhibited a negative correlation with soot-EC (p < 0.05). The increase of PM-EPFRs signals with the increased dilution ratio during pine wood combustion was more significant than that from rice straw, which may be resulted from the interactions between the condensable volatiles and the transition metals. Our study provides useful information for better understanding the formation of combustion-derived PM-EPFRs, and will be instructive for its purposeful emissions control.

Simultaneous alleviation of acrylamide and methylimidazole accumulation in cookies by Rhizoma kaempferiae and kaempferol and potential mechanism revealed by density functional theory

The simultaneous alleviating effect of Rhizoma kaempferiae and kaempferol on accumulation of acrylamide and methylimidazole in cookies was explored. Electron paramagnetic resonance (EPR) and density functional theory (DFT) were used to investigate the potential mechanism relating to the quenching of free radicals and elimination of carbonyl intermediates. The maximum inhibition rates for acrylamide and methylimidazole were 52% and 70% (15 g/kg RK). EPR experiments showed that the HO· and carbon-centered free radicals, critical for the production of acrylamide and methylimidazole, were reduced by RK and kaempferol in a dose-dependent manner. DFT indicated that the 1-OH group of kaempferol was the most important and quenched HO· mainly via H-atom Transfer. The active carbonyl intermediates, acrylaldehyde, glyoxal, and methylglyoxal can also be reduced by RK and kaempferol, which may result from the quenching of free radicals. On the basis of these results, we suggested that RK and kaempferol exerts simultaneous alleviating effect for accumulation of acrylamide and methylimidazole by blocking free radicals-centered path and reducing active carbonyl intermediate.

Multifunctional Magnetic Nanoclusters Can Induce Immunogenic Cell Death and Suppress Tumor Recurrence and Metastasis.

Metastasis is the predominant cause of cancer deaths due to solid organ malignancies; however, anticancer drugs are not effective in treating metastatic cancer. Here we report a nanotherapeutic approach that combines magnetic nanocluster-based hyperthermia and free radical generation with an immune checkpoint blockade (ICB) for effective suppression of both primary and secondary tumors. We attached 2,2'-azobis(2-midinopropane) dihydrochloride (AAPH) molecules to magnetic iron oxide nanoclusters (IONCs) to form an IONC-AAPH nanoplatform. The IONC can generate a high level of localized heat under an alternating magnetic field (AMF), which decomposes the AAPH on the cluster surface and produces a large number of carbon-centered free radicals. A combination of localized heating and free radicals can effectively kill tumor cells under both normoxic and hypoxic conditions. The tumor cell death caused by the combination of magnetic heating and free radicals led to the release or exposure of various damage-associated molecule patterns, which promoted the maturation of dendritic cells. Treating the tumor-bearing mice with IONC-AAPH under AMF not only eradicated the tumors but also generated systemic antitumor immune responses. The combination of IONC-AAPH under AMF with anti-PD-1 ICB dramatically suppressed the growth of untreated distant tumors and induced long-term immune memory. This IONC-AAPH based magneto-immunotherapy has the potential to effectively combat metastasis and control cancer recurrence.

σ versus π-radical: Tuning the electronic nature of neutral carbon (I) compounds with three non-bonding electrons.

The bonding and reactivity of the hypo-coordinated compounds with one, two, and four non-bonding electrons namely, carbon-centered free radical, carbenes, and carbones were well earlier established. Here, we report stability, bonding and reactivity of compounds RCL, where R is one-electron donor group (R=CH3 (a), CHO (b), and NO2 (c)) and L is two-electron donor ligand (L=cAAC (1), CO (2), NHC (3) and PMe3 (4)), having three non-bonding electrons. The ground states of molecules exist in a doublet with a lone pair of electrons and an unpaired electron at the central carbon atom (C1). The spin hops over from π- to σ-type orbitals is observed as the π-acceptor strength of the donor ligand increases. The replacement of the methyl group by CHO and NO2 indicate that the cAAC and CHO substituted compounds gives a σ-radical except in compound 2c. These molecules show very high proton affinity and exothermic reaction energy for the hydrogen atom addition indicating dual reactivity namely, radical and lone pair reactivity.

Effects of Thermal Aging on Molar Mass of Ultra-High Molar Mass Polyethylene Fibers.

Ultra-high molar mass polyethylene (UHMMPE) is commonly used for ballistic-resistant body armor applications due to the superior strength of the fibers fabricated from this material combined with its low density. However, polymeric materials are susceptible to thermally induced degradation during storage and use, which can reduce the high strength of these fibers, and, thus, negatively impact their ballistic resistance. The objective of this work is to advance the field of lightweight and soft UHMMPE inserts used in various types of ballistic resistant-body armor via elucidating the mechanisms of chemical degradation and evaluating this chemical degradation, as well as the corresponding physical changes, of the UHMMPE fibers upon thermal aging. This is the first comprehensive study on thermally aged UHMMPE fibers that measures their decrease in the average molar mass via high-temperature size exclusion chromatography (HT-SEC) analysis. The decrease in the molar mass was further supported by the presence of carbon-centered free radicals in the polyethylene that was detected using electron paramagnetic resonance (EPR) spectroscopy. These carbon-centered radicals result from a cascade of thermo-oxidative reactions that ultimately induce C–C ruptures along the backbone of the polymer. Changes in the crystalline morphology of the UHMMPE fibers were also observed through wide-angle X-ray diffraction (WAXS), showing an increase in the amorphous regions, which promotes oxygen diffusion into the material, specifically through these areas. This increase in the amorphous fraction of the highly oriented polyethylene fibers has a synergistic effect with the thermo-oxidative degradation processes and contributes significantly to the decrease in their molar mass.

Real-World Emission Characteristics of Environmentally Persistent Free Radicals in PM2.5 from Residential Solid Fuel Combustion.

Environmentally persistent free radicals (EPFRs) can induce reactive oxygen species, causing adverse health impacts, and residential fuel (biomass and coal) combustion is believed to be an important emission source for EPFRs; however, the residential emission characteristics of EPFRs are rarely studied in the real world. Here, we conducted a field campaign evaluating the presence and characteristics of EPFRs generated from residential biomass and coal burning in rural China. The emission factors (EFs) of EPFRs (with units of 1020 spins·kg-1) in PM2.5 from the combustion of crop residues (3.97 ± 0.47) were significantly higher than those from firewood (2.06 ± 0.19) and coal (2.13 ± 0.33) (p < 0.05). The EPFRs from residential solid fuel combustion were carbon-centered free radicals adjacent to oxygen atoms. The fuel type was a primary factor controlling EPFR discharge, explaining 68% of the variation in EPFR EFs. The emissions from biomass burning had higher EPFRs per particle than those from coal combustion. EPFRs had stronger relationships with carbonaceous components than with other incomplete combustion products. The EPFRs from biomass burning were mostly generated during the pyrolysis of fuels, while the EPFRs generated from coal combustion were mainly associated with refractory organic compounds. This study provides valuable information for evaluating the fates of EPFRs, promoting a better understanding of the health impacts of air pollution.

Microwave irradiation: Effect on activities and properties of polyphenol oxidase in grape maceration stage

In this work, the microwave was used to investigate the changes in activities and the possible passivation mechanism of PPO during the maceration stage of winemaking at different microwave conditions. Under the condition of microwave power 500 W, temperature 50 °C, and time 8 min, the activity of PPO decreased 0.853 U/(g·min) in grape maceration solution, having a decrease of 39.58% compared to the untreated PPO. The carbon-centred free radicals were induced in PPO solution at different microwave conditions. Besides, the changes of PPO conformational properties confirmed that microwave did affect the activity of PPO by influencing the PPO's composition, microenvironment, groups, chemical bonds, structure, and hydrolysis degree. The study will contribute to understanding the mechanism of higher extraction rate of phenols compounds in the maceration stage of winemaking by microwave irradiation.

Fast Antioxidant Reaction of Polyphenols and Their Metabolites.

The negative correlation between diets rich in fruits and vegetables and the occurrence of cardiovascular disease, stroke, cancer, atherosclerosis, cognitive impairment and other deleterious conditions is well established, with flavonoids and other polyphenols held to be partly responsible for the beneficial effects. Initially, these effects were explained by their antioxidant ability, but the low concentrations of polyphenols in tissues and relatively slow reaction with free radicals suggested that, instead, they act by regulating cell signalling pathways. Here we summarise results demonstrating that the abandonment of an antioxidant role for food polyphenols is based on incomplete knowledge of the mechanism of the polyphenol-free radical reaction. New kinetic measurements show that the reaction is up to 1000 times faster than previously reported and lowers the damaging potential of the radicals. The results also show that the antioxidant action does not require phenolic groups, but only a carbon-centred free radical and an aromatic molecule. Thus, not only food polyphenols but also many of their metabolites are effective antioxidants, significantly increasing the antioxidant protection of cells and tissues. By restoring an important antioxidant role for food polyphenols, the new findings provide experimental support for the advocacy of diets rich in plant-derived food.

Changes of lipids in noodle dough and dried noodles during industrial processing.

This study investigated the changes of lipids during the industrial preparation of noodle dough and dried noodles, including the hydration, sheeting, and drying processes. The results showed that industrial processing markedly influenced the stability of lipids during the preparation of dried noodles. The contents of total free fatty acids, polyunsaturated fatty acids, and free lipids were reduced, while peroxide values increased during the hydration and sheeting processes, showing the instability of lipids. The increase in lipid oxidation may have been due to the activation of lipoxygenase. Although its activity declined by 45.7% in the hydration process compared to that of the native wheat flour (198.5± 20.4 U/g/min), the residue activity should have been high enough to oxidize lipids. Interestingly, lipase activity remained relatively stable. In addition, an obvious increase of carbon-centered free radicals was observed during the entire processing. In conclusion, the industrial processing, especially the hydration process, markedly changed the lipid profile and promoted lipid oxidation during the preparation of dried noodles. PRACTICAL APPLICATION: The present study showed the positive relationship between endogenous lipid degrading enzymes and the degradation of lipids and elucidated the role of industrial processing on lipid stability in noodle dough and dried noodles. The results of the present study will also help us to understand more about the sensory quality of dried noodles during preparation, as well as to develop high quality of wheat-based food products.

Pharmacokinetics and antimalarial activities of reduction-responsive releasing dihydroartemisinin prodrug self-assembled nanoparticles in rodents

Artemisinin and its derivates (ARTs) exert antimalarial effect by virtue of unique endoperoxide bridge, which is generally considered to generate oxygen free radicals and then form carbon-centered free radicals to damage parasites. The known high level of glutathione (GSH) in parasites plays a key role in maintaining redox balance to protect parasites from oxidative stress damage, which may be a risk factor for the failure of ARTs-based combination therapy and drug resistance. Nevertheless, the highly reducing environment in cytoplasm of malaria parasites provides an available trigger for intracellular nanoparticle disassembly to responsively release drug. In this study, a reduction-responsive releasing dihydroartemisinin (DHA) prodrug (C14-SS-DHA) was synthesized by conjugating DHA and tetradecylamine (C14–NH2) with disulfide bond (–SS–) as a linker. As a control, a DHA carbon-carbon bond (–CC–) prodrug (C14-CC-DHA) was synthesized using succinic anhydride as a –CC– linker. To note, DHA prodrugs were prepared as self-assembled nanoparticles (C14-SS-DHA NPs and C14-CC-DHA NPs). The size and zeta potential of C14-SS-DHA NPs were 121 ± 1.582 nm and −29 ± 0.635 mV, and those of C14-CC-DHA NPs were 137.5 ± 0.5132 nm and −41 ± 0.377 mV, respectively. The C14-SS-DHA NPs can release DHA in a reductive media in vitro. The pharmacokinetics study showed that the area under the curve (AUC(0-t)) of plasma concentration versus time of DHA from C14-SS-DHA NPs was 20737.2 ± 6028.3 h μg L−1, which was much higher than that of C14-CC-DHA NPs (6254.5 ± 2578.8) or DHA solution (857.6 ± 103.7 h μg L−1). The pharmacodynamics study presented that the ED90 of C14-SS-DHA NPs was 3.81 ± 0.35 μmol/kg, which was lower than that of C14-CC-DHA NPs (12.70 ± 1.63 μmol/kg)) or DHA solution (17.67 ± 3.38 μmol/kg). C14-SS-DHA NPs showed significantly higher systemic exposure and better antimalarial activity in comparison with C14-CC-DHA NPs or DHA solution (P < 0.05).

Photo-Oxidative Degradation Mitigated the Developmental Toxicity of Polyamide Microplastics to Zebrafish Larvae by Modulating Macrophage-Triggered Proinflammatory Responses and Apoptosis.

Microplastics (MPs) are ubiquitous in the environment and pose substantial threats to the water ecosystem. However, the impact of natural aging of MPs on their toxicity has rarely been considered. This study found that visible light irradiation with hydrogen peroxide at environmentally relevant concentration for 90 days significantly altered the physicochemical properties and mitigated the toxicity of polyamide (PA) fragments to infantile zebrafish. The size of PA particles was reduced from ∼8.13 to ∼6.37 μm, and nanoparticles were produced with a maximum yield of 5.03%. The end amino groups were volatilized, and abundant oxygen-containing groups (e.g., hydroxyl and carboxyl) and carbon-centered free radicals were generated, improving the hydrophilicity and colloidal stability of degraded MPs. Compared with pristine PA, the depuration of degraded MPs mediated by multixenobiotics resistance was much quicker, leading to markedly lower bioaccumulation in fish and weaker inhibition on musculoskeletal development. By integrating transcriptomics and transgenic zebrafish [Tg(lyz:EGFP)] tests, differences in macrophages-triggered proinflammatory effects, apoptosis via IL-17 signaling pathway, and antioxidant damages were identified as the underlying mechanisms for the attenuated toxicity of degraded MPs. This work highlights the importance of natural degradation on the toxicity of MPs, which has great implications for risk assessment of MPs.

UVB photoirradiation of aloe vera - Formation of free radicals, singlet oxygen, superoxide, and induction of lipid peroxidation

Aloe vera whole leaf extracts are incorporated into a wide variety of topically applied commercial products. Aloe vera whole leaf extracts contain anthraquinones, which can generate reactive oxygen species (ROS) upon UVA light irradiation. In this study, the phototoxicity of two Aloe vera whole leaf extracts, Aloe A and Aloe B, were examined. The Aloe B extract was prepared by treating the Aloe A extract with activated carbon (1%, wt/wt) and filtration to remove the Aloe latex components, including the anthraquinones. UVB irradiation of the Aloe vera whole leaf extracts induced lipid peroxidation in the presence of a lipid, methyl linoleate. The amounts of lipid peroxides formed were higher in the Aloe B, which contained lower amounts of anthraquinones than Aloe A. Sodium azide inhibited and deuterium oxide enhanced the formation of lipid peroxides by Aloe B, suggesting that singlet oxygen was involved in the mechanism. When superoxide dismutase was incorporated prior to irradiation, lipid peroxidation was inhibited, indicating that superoxide was produced during the photoirradiation of Aloe B. In addition, electron spin resonance (ESR) spectroscopy was also used to investigate the generation of free radicals by the UVB photoirradiated Aloe B. ESR measurements indicated that the UVB photoirradiation of Aloe B produced carbon-centered free radicals. These results suggested that, as with the exposure to UVA light, the exposure of Aloe vera whole leaf extracts to UVB light can also generate ROS and induce lipid peroxidation.

Carbon Nanotube/Epoxy Composites for Improved Fire Safety

Pristine carbon nanotubes (CNTs) were treated to make them rich in carbon-centered free radicals. CNTs with various contents of carbon-centered free radicals were characterized by transmission elec...

Light-Enhanced Antibacterial Activity of Graphene Oxide, Mainly via Accelerated Electron Transfer.

Before graphene derivatives can be exploited as next-generation antimicrobials, we must understand their behavior under environmental conditions. Here, we demonstrate how exposure to simulated sunlight significantly enhances the antibacterial activity of graphene oxide (GO) and reveal the underlying mechanism. Our measurements of reactive oxygen species (ROS) showed that only singlet oxygen (1O2) is generated by GO exposed to simulated sunlight, which contributes only slightly to the oxidation of antioxidant biomolecules. Unexpectedly, we find the main cause of oxidation is light-induced electron-hole pairs generated on the surface of GO. These light-induced electrons promote the reduction of GO, introducing additional carbon-centered free radicals that may also enhance the antibacterial activities of GO. We conclude that GO-mediated oxidative stress mainly is ROS-independent; simulated sunlight accelerates the transfer of electrons from antioxidant biomolecules to GO, thereby destroying bacterial antioxidant systems and causing the reduction of GO. Our insights will help support the development of graphene for antibacterial applications.

Poly(ethylene glycol)/β-cyclodextrin covalent gel networks: host matrices for studying radical processes in plant extract–riboflavin systems following UV irradiation

Finding new, biocompatible matrices that allow us to model the generation of free radicals is of utmost importance for balancing the harmful and beneficial effects of the latter. In this respect, we report here the simultaneous encapsulation of the radical source and the antioxidant agent in a polyethylene glycol/β-cyclodextrin (PEG/β-CD) covalent gel network. We used electron paramagnetic resonance spectroscopy to evaluate the scavenging action of plant extracts (purple loosestrife, comfrey, milfoil, horsetail, thyme, carob, green coffee) embedded in PEG/β-CD gels. Free radicals were generated in situ by UV irradiation of riboflavin co-embedded in the gels. Prior to this, the extracts were characterized in what concerns their antioxidant activity, and their major polyphenolic constituents were quantified by liquid chromatography-electrospray ionization-tandem mass spectrometry. Purple loosestrife showed the highest antioxidant capacity, followed by comfrey and milfoil. Using the 5,5-dimethyl-1-pyrroline N-oxide spin trap, we have demonstrated that the gel-embedded extracts effectively scavenge the reactive carbon-centered free radicals generated in gel. The PEG/β-CD gels have been shown to be a valuable alternative matrix for the encapsulation of plant active principles having antioxidant activity. Moreover, co-encapsulation of the radical source transforms these gels into a controlled environment in which free radical processes can be tailored.

Repurposing the anti-malarial drug artesunate as a novel therapeutic agent for metastatic renal cell carcinoma due to its attenuation of tumor growth, metastasis, and angiogenesis.

Despite advances in the development of molecularly targeted therapies, metastatic renal cell carcinoma (RCC) is still incurable. Artesunate (ART), a well-known anti-malarial drug with low toxicity, exhibits highly selective anti-tumor actions against various tumors through generation of cytotoxic carbon-centered free radical in the presence of free iron. However, the therapeutic efficacy of ART against metastatic RCC has not yet been fully elucidated. In the analysis on a dataset from The Cancer Genome Atlas (TCGA) (n = 469) and a tissue microarray set from Samsung Medical Center (n = 119) from a cohort of patients with clear cell RCC (ccRCC), up-regulation of transferrin receptor 1 (TfR1), which is a well-known predictive marker for ART, was correlated with the presence of distant metastasis and an unfavorable prognosis. Moreover, ART exerted potent selective cytotoxicity against human RCC cell lines (Caki-1, 786-O, and SN12C-GFP-SRLu2) and sensitized these cells to sorafenib in vitro, and the extent of ART cytotoxicity correlated with TfR1 expression. ART-mediated growth inhibition of human RCC cell lines was shown to result from the induction of cell cycle arrest at the G2/M phase and oncosis-like cell death. Furthermore, ART inhibited cell clonogenicity and invasion of human RCC cells and anti-angiogenic effects in vitro in a dose-dependent manner. Consistent with these in vitro data, anti-tumor, anti-metastatic and anti-angiogenic effects of ART were also validated in human 786-O xenografts. Taken together, ART is a promising novel candidate for treating human RCC, either alone or in combination with other therapies.

Ultraviolet-B radiation applied to detached peach fruit: A study of free radical generation by EPR spin trapping

In peaches, phenolic compounds are the major sources of antioxidants, and cyanidin-3-O-glucoside is the main anthocyanin present, above all in the skin. Anthocyanin content has been shown to increase after UV-B irradiation, which may be very harmful for all biological organisms due to the induction of the generation of reactive oxygen species (ROS). Peach fruits (cv. ‘Suncrest’) were exposed during post-harvest to supplemental ultraviolet-B radiation. A spin-trapping technique was used to monitor the generation of free radicals under UV-B, and 5-(diethoxy-phosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO) was used as the spin trap. The flesh of peaches was essentially unaffected by the treatment, whereas the skin was responsive at the end of the treatment, accumulating ascorbate, flavonoids, cyanidin-3-O-glucoside, and showing a higher antioxidant activity. The levels of stable free radicals were also lower at the end of treatment. Carbon-centred radicals contributed the most to the total amounts of free radicals, whereas hydroxyl radicals and oxygen-centred free radicals contributed minimally. The carbon-centred free radical identified was the same as the one obtained after irradiation of authentic cyanidin-3-O-glucoside. During UV-B treatment cyanidin-3-O-glucoside increased and was capable of radicalization protecting the other organic molecules of the cell from oxidation. ROS, among which hydroxyl radicals, were thus maintained to minimal levels. This ability of cyanidin-3-O-glucoside displayed the mechanism underlined the tolerance to UV-B irradiation indicating that shelf life can be prolonged by the presence of anthocyanins. Thus, UV-B technique results a good approach to induce antioxidant production in peach fruits increasing their nutraceutical properties.

Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ≪ [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed.