CC Double Bond Research Articles

Tannic acid-grafted Polylactic acid films: A nonmigrating antibacterial packaging for chilled fresh meat

Antimicrobial packaging can prolong the shelf life of fresh food, but those active antimicrobial substances may leach into the food and affect its quality. To avoid this phenome, the CC double bond was first incorporated into the chemical structure of polylactic acid (PLLA) and tannic acid (TA) to prepare poly(L-LA-co-butyrate itaconate) (PLBI) and photoactive tannic acid (pTA). Then pTA-grafted PLBI (pTA-g-PLBI) films were fabricated using UV curing technology. Results showed that pTA was successfully grafted onto the surface of PLBI film and formed a uniform layer. The pTA-g-PLBI films exhibited good bacteriostatic effects of 86 %, 90 %, and 96 % on E. coli, P. fluorescens, and S. aureus, respectively. Additionally, pTA-g-PLBI packaging reduced the relative abundance of Shewanella, Psychrobacter, and Pseudomonas in chilled pork and delayed the deterioration of pork for more than 5 days.

Living anionic copolymerization of 1,3-pentadiene isomers with alpha-methylstyrene in the presence of 2,2-di(2-tetrahydrofuryl)propane

The synthesis of statistical copolymers of alpha-methylstyrene (AMS) and 1,3-pentadiene (PD) isomers in the presence of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) by living carbanionic polymerization was investigated in this paper. To the best of our knowledge, either AMS or PD monomer was rather difficult to homopolymerize in non-polar solvents without the help of polar additives even at high temperature due to its low ceiling temperature or relatively high electron cloud density of the conjugated CC double bond. However, the combination of RLi initiator and DTHFP regulator (0.1<DTHFP/Li < 0.5) allowed the rapid synthesis of the well-defined poly(AMS-stat-PD) with controlled molar masses (up to 32.5 kDa) and relatively narrow molecular weight distributions (1.10 < ĐMs < 1.52). Calculation of reactivity ratios by the Kelen–Tüdos method suggested that AMS copolymerized much more readily to with (Z)-1,3-pentadiene (ZP) than with (E)-1,3-pentadiene (EP) under the same conditions, whereas the EP/AMS copolymer exhibited much lower dispersity. 1H NMR results indicated that the polymer chain was found to be a mixture of 1,2-addition and 1,4-addition units, in the absence of 3,4-units. Kinetic experiments also showed that the apparent activation energy of EP/AMS copolymerization was slightly higher than that of the ZP/AMS case. To ensure complete conversion of the monomer, the feed ratio of AMS (fAMS) must be controlled to be within 0.3. In addition, the incorporation rate of AMS into the polymer chain increased with the increase in the feed ratio of AMS monomer. DSC curves showed that the Tg of the resulting copolymers increased gradually and could reach up to 25 °C (FAMS = 47). Based on the observation of the anionic statistical copolymerization behavior, an interpretation of the formation mechanism is presented here.

Multi-functional RAFT reagent to prepare fluorescent hyper-branched macromolecular probes for the detection of Fe3+ ions

Reversible addition-fragmentation chain transfer (RAFT) polymerization has the advantages of precise control, high yield, and narrow molecular weight distribution. These merits make it an ideal method for the preparation of hyper-branched fluorescent polymers (FL-HBPs). In this work, a multi-functional RAFT reagent (AVCT-NLP) was prepared for the synthesis of monodisperse FL-HBPs. Firstly, dithionate compound (CN1) containing a CC double bond was synthesized by the reaction of 4-nitrophenol with 1-(bromomethyl)-4-vinylbenzene. Subsequently, the NO2 group on CN1 was reduced to NH2, and the −Br on the 4-bromo-1,8-naphthalic anhydride was substituted to emit fluorescence. Finally, the fluorophore was introduced by the reaction of NH2 with the anhydride on the naphthalene ring to obtain AVCT-NLP which contains fluorophore, dithionate, and CC double bond in one molecule. AVCT-NLP was then used to synthesize the homopolymer (PAVCT-NLP) as both monomer and RAFT reagent. Moreover, PAVCT-NLP served as a macromolecular RAFT reagent, and hydrophilic monomer methacrylic acid (MAA) or 3-butene-1,2-diol were polymerized to obtain amphiphilic hyper-branched polymers (FL-AHBP-1, FL-AHBP-2). All the as-prepared macromolecules (PAVCT-NLP, FL-AHBP-1, and FL-AHBP-2) exhibited specific recognition and high sensitivity for Fe3+. The fluorescence quenching reached up to 74.4 %, with the limit of detection (LOD) as low as 1.82 nM. Additionally, the probe demonstrated pH stability and environmental adaptability. Due to the multi-functional structures of AVCT-NLP, it could be subjected to RAFT polymerization to obtain a monodisperse hyper-branched polymer. All polymers have a high fluorophore density and the polydispersity index (PDI) of the polymer is close to 1.00. This paper provided an effective approach for synthesizing polymer fluorescent probes with versatile structure and fluorescence properties in future applications.

A fluorescent turn-on nanosensor for selective detection of L-morphine using D-cysteine-functionalized graphene quantum dots

Here, L- and D-cysteine-functionalized graphene quantum dots (L-/D-cys-GQDs) were designed with the aim of obtaining a selective fluorescent nanosensor to detect L-morphine. Citric acid was pyrolyzed to synthesize the GQDs, which were then functionalized with chiral L- and D-cys species using a thiol-ene click reaction between sulfur group of cysteine species and CC double bonds of GQDs. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopies (XPS) provides elemental analysis data which approved the presence of sulfur and nitrogen elements of L- and D-cysteine species on the surface of GQDs. Transmission electron microscopy (TEM) showed that the particle size of the modified GQDs ranges from 2 to 4.2 nm. The results of fluorescence spectroscopy showed that upon functionalization of GQDs with L-/D-cys the fluorescence intensity decreases as a result of Forster resonance energy transfer (FRET) mechanism. Interestingly, in the presence of L-morphine, the fluorescence intensity of D-cys-GQDs was selectively turned on as the FRET mechanism is ceased between the cysteine species and GQDs. Additional tests demonstrated that this nanosensor cannot interact with other drugs like methamphetamine or ibuprofen. As a result, it can serve as a cheap and precise nanosensor for identifying low quantities of L-morphine.

A long-wavelength fluorescent probe based on carbazole with AIE characteristics for the detection of ONOO− and its application

Peroxynitrite (ONOO−) is an important reactive oxygen species, and excess ONOO− in the body can lead to a range of diseases. Addressing the need for sensitive detection ONOO−, in this work, a highly sensitivity and selectivity long-wavelength fluorescent probe (named CIS) was designed for tracking ONOO− in biological cells. Probe CIS featured carbazole as the fluorophore and the CC double bond with two electron withdrawing –CN groups as the recognition site. The probe CIS exhibited the typical aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) characteristics with the bright red fluorescent emission in high water fraction (fw ≥ 50 %) and negligible emission in low water fraction. The fluorescence emission wavelength of probe CIS is 631 nm, with a large Stokes shift (151 nm), which can sensitively detect ONOO− in DMSO: H2O (7:3, v/v) environment. Notably, the probe CIS exhibited a wide pH detection range (pH = 3–10), a low detection limit of 36.66 nM, high selectivity and minimal interference. Furthermore, probe CIS demonstrated excellent biocompatibility and low cytotoxicity, and can be used for the detection of exogenous ONOO− in 4T1 cells (Mouse breast cancer cells). These research results indicate that probe CIS has potential application prospects in the biological aspects.

Mechanistic insights on the preparation of 5-methyl-2-hexanone by hydrogenation of 5-methyl-3-hexen-2-one using Pd/Al2O3 catalysts

5-methyl-2-hexanone is used as a versatile polymerization solvent for industrial preparation processes of bulk and fine chemicals. An efficient catalyst, Pd/γ-Al2O3, is reported for the preparation of 5-methyl-2-hexanone by selective hydrogenation of 5-methyl-3-hexen-2-one. The catalyst exhibits remarkable activity and selectivity even at atmospheric pressure and low temperature (1 atm, 80 °C). The influence weight of reaction conditions on the reaction process was obtained through the Artificial Neural Network model, which were reaction pressure, reaction temperature and liquid hourly space velocity in order. The reaction kinetics and mechanism of 5-methyl-2-hexanone preparation by hydrogenation over Pd/γ-Al2O3 catalyst were investigated. The hydrogenation reaction pathway of 5-methyl-3-hexen-2-one was obtained by using Density functional theory calculations, and the mechanism of selective hydrogenation of CC double bonds and CO double bonds was revealed. A kinetic model based on the LHHW model assumption was also proposed and compared with experimental results demonstrating good predictability.

Photoisomerization of heptamethine cyanine (Cy7) dyes: A theoretical study

In this study, density functional theory (DFT) combined with time-dependent (TD) DFT calculations were employed to investigate the photoisomerization reaction kinetics of two near infrared (NIR) heptamethine cyanine (Cy7-NH3 and Cy7-SO3) dyes in the ground singlet state and the first excited singlet state. We found that the photoisomerization of the ground state all-trans Cy7 molecules results in at least one mono-cis and one all-cis species that demonstrate redshifted emission, in agreement with recently published transient state excitation modulation spectroscopy and fluorescence correlation spectroscopy measurements. The transition states were estimated for a whole photoisomerization pathway for both the ground singlet and first excited singlet state potential energy surfaces. We have found that all-cis isomers of the studied Cy7 dyes can be achieved through a sequential two-step photoisomerization within the excited singlet state potential energy surface, along the double CC bond adjacent to edge group (leading to mono-cis isomer 1) and along the double CC bond adjacent to the central-chain group (leading to mono-cis isomer 2). Computations show that all-trans→ mono-cis isomer 1→all-cis kinetics is limited by the first trans→ mono-cis isomer 1 stage, while the all-trans→ mono-cis isomer 2→all-cis pathway is limited by the second mono-cis isomer 2→all-cis stage. Accounting for the fact that mono-cis isomer 2 demonstrates red-shifted emission compared to the all-trans form and that this mono-cis isomer 2 is reachable through the energetically favorable all-trans→ mono-cis isomer 2 stage, we concluded that the experimentally observed red-shifted emission by Cy7-NH3 and Cy7-SO3 should be assigned to the formation of mono-cis isomer 2 species. If the all-cis isomer is populated through the double-step photoisomerization it can also be considered as a source of red-shifted emission. However, as follows from our simulations, the all-cis isomer is kinetically intricate to achieve compared to the mono-cis isomer 2.

2-Styryl-quinoline-4-carboxylic acids: Synthesis, characterization, and investigation of their optical properties and antimicrobial activity

Styrylquinoline-based fluorophores 1–10 were synthesized via Knoevenagel and Pfitzinger reactions. The molecules were fully characterized and studied for the impact of their substitution patterns (A-D) on their optical and bioactivity properties. With exception of nitro substituted compounds 9-D and 10-D, all compounds were fluorescent in solution with a significant solvatochromic behavior measured in toluene, dioxane, tetrahydrofurane, ethyl acetate, dichloromethane, dimethylformamide, dimethylsulfoxide, acetonitrile, isopropanol, and methanol. The maximum wavelength of their emission ranged from 408 to 539 nm. Additionally, there was a significant variation in the photoluminescence (PL) quantum yield concerning different solvent polarities. The PL quantum yields ranged from small values, such as 1.7 % in methanol for compound 1-A, to good PL quantum yields, such as 44.4 % in dioxane for 7-C. For comparison, the quantum yield of 7-C in methanol was 3.3 %, a total range variation of 41.1 %. 4-B and 5-B with O-acetyl groups at ortho and at para position to the CC double bond, respectively, presented an interesting acidochromism with a redshift of about 102 nm in their emission bands along with a visible emitted color change from blue to green. In addition, the antimicrobial activity for all compounds and the theoretical mechanism of action of the more significant bioactive compounds were investigated. In inverse virtual screening studies, the enzymes Dehydrosqualene synthase and Squalene synthase were indicated as putative biological targets for 3-B and 4-B. Molecular docking indicated the amino acid residues critical for interaction in bacteria and fungi.

Sunlight degradation of tetracycline by Z-type BiOI/g-C3N4 photocatalyst synthesized via a simple two-step process: Response surface methods, degradation pathways, toxicity evaluation

A method combining grinding and hydrothermal treatments was utilized to densely load three-dimensional BiOI onto two-dimensional g-C3N4, thereby preparing a BiOI/g-C3N4 photocatalyst with a Z-type heterojunction. Under varying climatic conditions throughout the year, 10%BiOI/g-C3N4 photocatalyst degraded 92.26 % of tetracycline (TC) under sunlight exposure in summer (sunny days) in 150 min, whereas it only degraded 47.33 % of TC under sunlight exposure in winter (cloudy days). The degradation parameters for TC by 10%BiOI/g-C3N4 were optimized using Response surface methods, establishing the optimal conditions for TC degradation (pollutant concentration of 10.94 mg/L, catalyst dosage of 31.34 mg, pH of 4.02), resulting in a degradation efficiency of 95.63 % for TC under the specified conditions. Employing HPLC-MS/MS and 3D EEM techniques, the degradation of TC primarily occurs due to the cleavage of its CC double bonds and CN bonds triggered by free radical attacks, and small molecular acids are produced during the degradation process. The impacts of TC solution treatment on plants were investigated, and the oxidative stress indicators MDA, SOD, POD, and CAT were assessed. The results demonstrated a decrease in all four indicators in plants cultured in TC degradation product solution, further affirming the applicability of 10%BiOI/g-C3N4 in practical scenarios.

Multiple effects of relative humidity on heterogeneous ozonolysis of cooking organic aerosol proxies from heated peanut oil emissions

The exposure to cooking organic aerosols (COA) is closely related to people's daily lives. Despite extensive investigations into COA's model compounds like oleic acid, the intricacies of heterogeneous ozonolysis of real COA and the effects of ambient conditions like humidity remain elusive. In this work, the ozonolysis of COA proxies from heated peanut oil emissions was investigated using diffuse reflectance infrared Fourier transform (DRIFTS) spectroscopy, and proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). We found that humidity hinders the reaction between ozone and CC double bonds due to the competitive adsorption of water and ozone on COA. Although visible light has little influence on the ozonolysis of COA in the absence of humidity, the ozonolytic CO production is significantly promoted by visible light in the presence of humidity. It may be attributed to the formation of water-derived reactive oxygen species (ROS, mainly HO•) from the photosensitization of polycyclic aromatic hydrocarbons (PAHs) in COA. We also found that humidity can enhance the depolymerization of carboxylic acid dimers and hydrolysis of intrinsic acetals in the COA. Moreover, humidity promotes the release of VOCs during both the dark and light ozonolysis of COA. This work reveals the important roles of humidity-responsive and photo-responsive components in COA during its ozonolysis, and the change in VOC release may guide the control of human VOC exposure in indoor air.

Efficient removal of Basic Violet 16 by a multistage oxygen enhanced liquid glow discharge plasma system: Mechanism and roles of reactive species quantified by machine learning

A multistage oxygen enhanced Liquid Glow Discharge Plasma reactor (LGDP/multistage oxygen, LGDP/M-O2) was designed to improve the removal efficiency of organic dyes in wastewater. As a result of the multistage oxygen system, the degradation rate constant of Basic Violet 16 (BV16) was enhanced by approximately 18 times, the decolorization rate of BV16 was 97.39 % in 4 min, and the removal rate of TOC was 33.32 % in 10 min. Detailed study of how the system works to help break down pollutants. The reactive species series of experiments showed that multistage oxygen injection strongly promoted reactive species production and utilization. Meanwhile, a machine learning model to quantify the contribution of reactants was proposed. Machine learning indicated the dominating contribution of reactive oxygen species (63.89 %) and reactive chlorine species (21.92 %) in the degradation of BV16. In addition, the transformation intermediates during the degradation of BV16 were monitored. Accordingly, three possible degradation pathways of BV16 in the LGDP/M-O2 system were proposed, i.e., benzene ring substitution of hydroxyl groups, hydroxyl addition of C=C double bond, and halogenation of benzene rings. This study demonstrates the importance of the LGDP/M-O2 system for organic dye removal from wastewater.

Application of atmospheric cold plasma for zearalenone detoxification in cereals: Kinetics, mechanisms, and cytotoxicity analysis

IntroductionZearalenone (ZEN) is one of the most widely contaminated mycotoxins in world, posing a severe threat to human and animal health. Atmospheric cold plasma (ACP) holds great penitential in mycotoxin degradation. ObjectivesThis study aimed to investigate the degradation efficiency and mechanisms of ACP on ZEN as well as the cytotoxicity of ZEN degradation products by ACP. Additionally, this study also investigated the degradation efficiency of ACP on ZEN in cereals and its effect on cereal quality. MethodsThe degradation efficiency and products of ZEN by ACP was analyzed by HPLC and LC-MS/MS. The human normal liver cells and mice were employed to assess the cytotoxicity of ZEN degradation products. The ZEN artificially contaminated cereals were used to evaluate the feasibility of ACP detoxification in cereals. ResultsThe results showed that the degradation rate of ZEN was 96.18 % after 30-W ACP treatment for 180 s. The degradation rate was dependent on the discharge power, and treatment time and distance. Four major ZEN degradation products were produced after ACP treatment due to the oxidative destruction of CC double bond, namely C18H22O7 (m/z = 351.19), C18H22O8 (m/z = 367.14), C18H22O6 (m/z = 335.14), and C17H20O6 (m/z = 321.19). L02 cell viability was increased from 52.4 % to 99.76 % with ACP treatment time ranging from 0 to 180 s. Mice results showed significant recovery of body weight and depth of colonic crypts as well as mitigation of glomerular and liver damage. Additionally, ACP removed up to 50.55 % and 58.07 % of ZEN from wheat and corn. ConclusionsThis study demonstrates that ACP could efficiently degrade ZEN in cereals and its cytotoxicity was significantly reduced. Therefore, ACP is a promising effective method for ZEN detoxification in cereals to ensure human and animal health. Future study needs to develop large-scale ACP device with high degradation efficiency.

A synergistic dispersion strategy for high volume fraction slurry and high performance silicon nitride sintered components in digital light processing (DLP)-based vat photopolymerization

The digital light processing (DLP)-based vat photopolymerization enables the fabrication of intricate silicon nitride (Si3N4) components. However, challenges still persist in producing low-defect and high-performance ceramic parts at lower volume fractions. In this study, a new block copolymer was employed for the modification of Si3N4 powders. The rheological behavior, dispersant mechanism, curing properties, printing performance of green body, mechanical properties and Weibull modulus of the sintered sample were systematically investigated. The results indicated that the modifier characterized by the long molecular chains and CC double bonds adhered successfully to the surface of Si3N4 particles through hydrogen bonding, and the viscosity reduction effect of this modifier was ten times lower than that of the reported KH560 modifier. Besides, the synergistic dispersion effect achieved via the combination of the long chain modifier with a small molecular dispersant, facilitates the preparation of a 60 vol% (80.74 wt%) Si3N4 slurry. Subsequently, the tightly bonded interlayer of the green body and the complex Si3N4 sintered components with different volume fractions, high consistency and superb mechanical performance (the strength of 865.87 ± 54.35 MPa and the Weibull modulus of 18.49) were fabricated. These findings highlight the promising potential of the proposed modification approach for advancing the fabrication of high volume fraction and high-performance Si3N4 components.

Analyzing moisture diffusion in the interface between rubber-modified asphalt and aggregate: A 3D study considering multiple influencing factors

Moisture erosion is inevitable at the interface between rubber-modified asphalt and aggregate. When moisture penetrates the interface through diffusion, it causes varying degrees of damage. In this study, molecular simulation technology was used to simulate the moisture diffusion interface considering multiple influencing factors. The radial distribution function (RDF), mean square displacement (MSD), and relative concentration profile (RCP) were calculated to evaluate the moisture diffusion direction. Density functional theory was employed to measure the interaction between rubber-modified asphalt components and H2O molecules, and the moisture-damaged areas were analyzed using crystal orbital populations, which can obtain three-dimensional (3D) diffusion mechanism. The results demonstrated that the remaining free H+ ions interacted with the aromatic ring and CC (double bond) in the rubber. Under the effects of multiple factors such as loading and temperature conditions, moisture permeates the rubber-modified asphalt and aggregate interface, resulting in overall degradation of the composition. Furthermore, the hydrogen atoms in the free OH- groups attract the more polar heteroatoms surrounding them.

Three anionic surfactants for corrosion inhibition in cobalt CMP: Research on validity and mechanism

Inhibitors are introduced into the slurry to avoid excessive metal corrosion during the chemical mechanical polishing (CMP) process. The anti-corrosion effect of surfactants in CMP was not investigated systematically in past studies. In this paper, three eco-friendly anionic surfactants, potassium laurate, potassium oleate, and dodecyl benzenesulfonic acid, were studied in depth as cobalt CMP inhibitors. Electrochemical experiments demonstrated that the three inhibitors act as anodic inhibitors. Static etching tests and surface morphology analysis proved that they can effectively inhibit the corrosion rate of cobalt and improve surface morphology. XPS results demonstrated that the inhibitor reduces corrosion by inhibiting cobalt oxidation. DFT calculations demonstrated that inhibitors adsorb on the cobalt surface through the O atoms in hydrophilic groups, while the CC double bond and benzene ring can significantly enhance the adsorption. Molecular dynamics simulations showed that the inhibitors are adsorbed on the cobalt surface in parallel. Additionally, all three surfactants improved the solution's wettability on cobalt. This report provides critical insights into the corrosion inhibition specific to cobalt CMP and offers an approach to realize the multi-functionality of a single agent in slurries.

The effect of the unsaturation degree on the gas-phase autoignition of methyl oleate and methyl linoleate: Experimental and modeling study

As the product of transesterification between various oils and alcohols, biodiesel exhibits characteristics of renewability and a wide range of raw materials. The ignition delay times (IDTs) of methyl oleate (MEOLE) and methyl linoleate (MLINO), the primary constituents of biodiesels, were measured in a heated rapid compression machine (RCM) to investigate the impact of CC double bond on the reactivity and autoignition characteristics. The experiment was conducted under two pressures of 8 bar and 10 bar at an equivalence ratio of 0.3–0.8 and a temperature range of 800–1000 K. The qualitative investigation unveiled the influence of compressed pressure, equivalence ratio, and oxygen mole fraction on the IDT of MEOLE and MLINO under varying compressed temperatures. Besides, a comparison of the IDTs for two fuels with different unsaturation degrees under identical conditions revealed that MEOLE exhibited greater reactivity at low temperatures compared to MLINO, while the increase in unsaturation degree can moderate and enhance reactivity at high temperatures. Moreover, three kinetic models in the literature were validated against the newly measured IDTs. The results indicate that the detailed lumped kinetic model exhibits better predictive capacity compared to other models, but it still underestimates the reactivity of MEOLE and MLINO within the investigated temperature range. Subsequently, the detailed kinetic model was optimized based on sensitivity analysis, resulting in excellent agreement between the predicted values of the optimized model and experimental data. Furthermore, accurate predictions were made regarding the relative reactivity changes of MEOLE and MLINO with temperature. Finally, different types of experimental data in the literature were employed to validate the optimized model, yielding satisfactory results.

Targeting dihydroceramide desaturase 1 (Des1): Syntheses of ceramide analogues with a rigid scaffold, inhibitory assays, and AlphaFold2-assisted structural insights reveal cyclopropenone PR280 as a potent inhibitor

Dihydroceramide desaturase 1 (Des1) catalyzes the formation of a CC double bond in dihydroceramide to furnish ceramide. Inhibition of Des1 is related to cell cycle arrest and programmed cell death. The lack of the Des1 crystalline structure, as well as that of a close homologue, hampers the detailed understanding of its inhibition mechanism and difficults the design of new inhibitors, thus making Des1 a strategic target. Based on previous structure-activity studies, different ceramides containing rigid scaffolds were designed. The synthesis and evaluation of these compounds as Des1 inhibitors allowed the identification of PR280 as a better Des 1 inhibitor in vitro (IC50 = 700 nM) than GT11 and XM462, the current reference inhibitors. This cyclopropenone ceramide was obtained in a 6-step synthesis with a 24 % overall yield. The highly confident 3D structure of Des1, recently predicted by AlphaFold2, served as the basis for conducting docking studies of known Des1 inhibitors and the ceramide derivatives synthesized by us in this study. For this purpose, a complete holoprotein structure was previously constructed. This study has allowed a better knowledge of key ligand-enzyme interactions for Des1 inhibitory activity. Furthermore, it sheds some light on the inhibition mechanism of GT11.

Nicotiana alkaloids-intervened phospholipid ozonolysis at the air-water interface

Cigarette nicotiana alkaloids associated with lung and cardiovascular diseases attack enormous attention. However, the mechanism at the molecular level between nicotiana alkaloids and phospholipid ozonolysis remains elusive. Herein, we investigated the interfacial ozonolysis of a hung droplet containing 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) intervened by nicotiana alkaloids (4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone, NNK; rac-N′-nitrosonornicotine, NNN; nicotine; and (R,S)-N-nitrosoanasabine, NAT) and followed by on-line mass spectrometry analysis. NNK and NNN showed an acceleration on the interfacial ozonolysis, while nicotine and NAT inhibited this chemistry. Such acceleration/inhibition on POPG ozonolysis was positively correlated with nicotiana alkaloid concentrations. The reaction rate constants suggested that the ozonolysis of lung phospholipids exposed to cigarette smoke at the air-water interface occurred rapidly. A possible mechanism of the hydrophilic/oleophilic nature of nicotiana alkaloids mediating the packing density of POPG was proposed. NNK and NNN with a hydrophilic nature inserted into the POPG monolayer loosed the packing, but nicotine and NAT with an oleophilic nature let the POPG closely pack and shield the CC double bonds exposed to ozone (O3). These results gain the knowledge of nicotiana alkaloids mediated phospholipid ozonolysis at the molecule level and provide a method for online interfacial reaction studies associated with elevated indoor pollutants on public health.

Photo-oxidative aromatization and photo-rearrangement of 2, 4-diaryl-5-oxohexahydroquinolines

Various 2,4-bisaryl substituted 5-oxohexahydroquinolines were synthesized and the electronic effects of 2- and 4-substitutions on the photochemical behaviors of these compounds were investigated. UV light irradiation of these compounds resulted in the occurrence of two types of photoreactions; oxidative normal photo-oxidation and photo-rearranged reactions. In both reactions, the aromatization of the heterocyclic 1,4-dihydropyridine ring to the pyridine ring was observed. The photochemical results indicated the involvement of the radical intermediate, responsible for the aryl ring migration and the occurrence of the photo-rearrangement reaction. The partial synergistic effect of the capto-dative radical stabilization of the involved radical intermediate was supported by the results of the experimental works and the DFT-computational studies. X-ray crystal structure analysis of two of 5-oxohexahydroquinoline compounds indicated that i). The C4-aryl ring occupies the pseudo-axial position of the twisted-boat conformation of the heterocyclic dihydropyridine ring and, ii). Owing to the steric ortho-repulsion, the C2-aryl ring has a non-planar orientation concerning the attached CC double bond of the heterocyclic ring. These observations were in good agreement with the data of the DFT-computational studies and the X-ray crystal structure analysis.

Divergent Chemo- and Biocatalytic Route to 16β-Methylcorticoids: Asymmetric Synthesis of Betamethasone Dipropionate, Clobetasol Propionate, and Beclomethasone Dipropionate.

16β-Methylcorticoids are among the most important glucocorticoid steroids for the treatment of various dermatological disorders, respiratory infections, and other allergic reactions elicited during inflammatory responses of the human body. Betamethasone dipropionate, clobetasol propionate, and beclomethasone dipropionate are particularly noteworthy for their synthetic intractability. Despite five decades of research, these 16β-methylcorticoids have remained challenging synthetic targets owing to insurmountable issues of reactivity, selectivity, and cost efficiency associated with all previously explored strategies. We herein report our practicability-oriented strategy toward the unified stereoselective synthesis of 16β-methylcorticoids in 12.6-14.0 % overall yield from commercially available 9α-hydroxyandrost-4-ene-3,17-dione (9α-OH-AD). In this approach, the chiral C16β-Me and C17α-OH groups of the corticosteroid D ring were installed via a substrate-controlled diastereo- and enantioselective Mn-catalyzed oxidation-reduction hydration of Δ4,9(11),16 -triene-3,20-dione. The C1-C2 double bond of the corticosteroid A ring was constructed using an unprecedented engineered 3-ketosteroid-Δ1 -dehydrogenase (MK4-KstD)-catalyzed regioselective Δ1 -dehydrogenation of Δ4,9(11) -diene-3,21-dione. This strategy provides a general method and a key precursor for the divergent synthesis of a variety of glucocorticoids and related steroidal drugs.