CC Double Bond Research Articles

Quaternary ammonium-based and imidazolium-based gemini surfactants: A comparison study

Gemini surfactants have aroused significant attention since their discovery due to their unique properties that arise from the particular molecular structure. However, the effect of a CC double bond in the spacer has seldom been considered, and common quaternary ammonium-based gemini surfactants have seldom been compared with imidazolium-based ones. In this work, four gemini surfactants, denoted as 12–4-12, 12–4u-12, C12im-4-C12im, and C12im-4u-C12im were synthesized and characterized, and the effects of CC double bond in the spacer and hydrophilic headgroup on the fundamental properties were investigated. The results showed that imidazolium-based gemini surfactants (C12im-4-C12im and C12im-4u-C12im) have lower critical micelle concentration (cmc), greater efficiency and effectiveness in reducing surface tension, and superior ability to generate micelles compared to the corresponding quaternary ammonium-based ones, but showed comparatively lower salt resistance, foaming, and antibacterial activity. The introduction of CC in the spacer further decreased the cmc and the Gibbs free energy of micellization, and enhanced the antibacterial activity, but barely affected interfacial adsorption, the efficiency in reducing surface tension, micelle size, or foaming. None of the four gemini surfactants alone was capable of decreasing the interfacial tension to an ultra-low value. The incorporation of sodium cetanol polyoxyethylene ether carboxylate not only significantly decreased the interfacial tension (<10−2 mN·m−1), but also remarkably enhanced the salt resistance capacity up to 80,000 mg·L−1. This information may be helpful for designing new gemini surfactants tailored for different potential applications.

Geometrical Optimization and Natural Bond Orbital Analysis of Relevant Structures in the Diastereoselective Cuprate Conjugate Addition Reaction of α,β-Unsaturated Lactams using Density Functional Theory

In this study, density functional theory calculations at the wB97XD/Def2TZVPP level were performed to analyze the mechanism underlying the cuprate conjugate addition reaction of α,β-unsaturated lactams. The calculation results were well-aligned with those obtained experimentally–the keto-aminal and aldo-aminal, i.e. 2 and 1a, yield the syn- and anti-products, respectively. The diastereoselectivity reversal originates from the small differences in the structure of the reactants. The pyramidalization and C7N3C2 angle between the aminal carbon, nitrogen and carbonyl carbon are large in 2. The dihedral angle of the aminal oxygen, aminal carbon, nitrogen and carbonyl carbon, O8C7N3C2, is closer to 180º in 2 than in 1a. The NBO analysis revealed string interactions between the lone pair of N3 and carbonyl π*(O1–C2) bond. These results validate the assumption—the planarity around nitrogen in molecule 2 increases the nucleophilicity of the carbonyl oxygen, thereby driving the reaction between molecule 2 and trimethylsilyl chloride (TMSCl), which yields a siloxyiminium cation 5b and this 5b propels the syn addition of dimethylcuprate, leading to the formation of complex 7. The π(C5–C6) (HOMO) and π*(C2–N3) (LUMO) interactions in the siloxyiminium cation explain the increased C5–C6 double bond electrophilicity. The aldo-aminal 1a directly reacts with dimethylcuprate under steric control and yields the anti complex 6a, whose π character is stronger than that of the syn complex 7 and this weak π characteristics of 7 increases its stability to compensate for the trimethylsilyl disturbance. The bicyclic α,β-unsaturated lactam 8 does not contain aminal oxygen and thus remains unreactive during the cuprate conjugate addition reaction. Moreover, its pyramidalization is higher than that of the keto-aminal 2 and its dihedral angle of C8C7N3C2 is closer to 180º. Finally, a thermodynamic anti product is obtained, which is more stable than the syn- product because of less torsional strain.

Degradation of polyvinyl chloride microplastics via electrochemical oxidation with a CeO2–PbO2 anode

As an emerging organic pollutant, microplastics (MPs) pose a serious threat to the water environment and human health. Effective water treatment processes are urgently needed to remove MPs from the aquatic environment. Herein, an electrocatalytic oxidation system with a CeO2-modified PbO2 anode (marked as CeO2–PbO2) was proposed for the degradation of polyvinyl chloride microplastics (PVC-MPs). When the CeO2 concentration in the electrodeposition solution was 0.005 M, the obtained CeO2–PbO2 electrode had the best electrocatalytic activity due to its denser structure, higher oxygen evolution potential, and more active sites. After 6 h of electrolysis, the weight loss of PVC-MPs at the CeO2–PbO2-0.005 anode was 38.67%, greatly higher than 16.67% at the pristine PbO2 anode. To explore the degradation mechanism of PVC-MPs, the surface morphologies, elemental states, and functional groups of PVC-MPs were compared before and after electrochemical treatment, and the formed intermediates were identified. Experimental results revealed that the PVC backbones were broken, the CC double bonds were oxidized or oxidatively cleaved into small molecules, and the dechlorination reaction occurred in the electrochemical oxidation process. As a result, the particle size of the PVC-MPs decreased significantly, lots of cracks appeared and many small pieces were formed on the surface of the PVC-MPs.

Uncovering heterogeneity of anacardic acids from pistachio shells: A novel approach for structural characterization.

Anacardic acids (AnAs) are important secondary metabolites that occur primarily in plants of the Anacardiaceae family, such as pistachio (Pistacia vera L.). Some AnAs have been associated with health benefits, and the position of the CC double bonds is a crucial feature of these metabolites. Herein, we propose a new strategy based on RPLC separation and detection by ESI-MS/MS, preceded by an epoxidation reaction. The procedure was applied to the green extracts of lignified pistachio shells, and a mixture of AnAs bearing alkyl chains 13:0, 15:0, and 17:1 emerged as prevailing. As positional isomers of AnA 15:1 (Δ8 and Δ6) and AnAs 17:1 (Δ10 and Δ8) were identified for the first time, their discovery paves the way to the systematic study of their potential health-beneficial effects. The developed method was validated and applied to quantify AnAs in pistachio ethanolic extract, showing contents higher than 10mg/ 100g of biomass.

Molecular ionization potentials of triglycerides and mechanism analysis of streamer discharge in vegetable insulating oil

With the enhancement of social awareness of environmental protection, scholars have gradually began to focus their research on vegetable-oil-based insulating fluid. In this work, we calculated the ionization potential of triglyceride molecules in vegetable oil (VO), analyzed the mechanism of charge generation, and explained the cause of fast streamer discharge in VO based on the distribution characteristics of ionization potential. Some interesting results were obtained. The position of CC on the triglyceride branch chain can affect the ionization potential of triglycerides. Specially, the CC at the Sn-2 position can significantly reduce the ionization potential of glycerol molecules. The ionization of unsaturated triglycerides is mainly caused by the electron loss of carbon atoms in the CC double bond; the formation of negative ions mainly rely on ester groups and their nearby atoms to capture electrons. In VO, low ionization potential molecules are predominantly present, and their presence results in a lower breakdown voltage and easy formation of the fast streamer discharge. We anticipate that our research can provide theoretical support for the application research of vegetable insulating fluid.

Montmorillonite Catalyzed Synthesis of Novel Steroid Dimers.

The reactions of sterols (androst-5-en-3β-ol-17-one, diosgenin, and cholesterol) and their tosylates with hydroquinone aimed at the synthesis of O,O-1,4-phenylene-linked steroid dimers were studied. The reaction course strongly depended on the conditions used. The study has shown that the major reaction products are the elimination products and unusual steroid dimers resulting from the nucleophilic attack of the hydroquinone C2 carbon atom on the steroid C3 position, followed by an intramolecular addition to the C5-C6 double bond. A different reaction course was observed when montmorillonite K10 was used as a catalyst. The reaction of androst-5-en-3β-ol-17-one under the promotion of this catalyst afforded the O,O-1,4-phenylene-linked steroid dimer in addition to the disteroidal ether. The formation of the latter compound was suppressed by using 3-tosylate as a substrate instead of the free sterol. The reactions of androst-5-en-3β-ol-17-one tosylate and cholesteryl tosylate with hydroquinone catalyzed by montmorillonite K10 carried out under optimized conditions afforded the desired dimers in 31% and 67% yield, respectively.

Pushing measurements and interpretation of VCD spectra in the IR, NIR and visible ranges to the detectability and computational complexity limits

(R)-Limonene VCD and IR absorption spectra for neat liquid samples are considered from 900 to 16,000 cm−1, using mostly data by Nafie et al. up to 10,000 cm−1 and from previous investigations of the Brescia group. New VCD data are recorded in the merely overtone and combination region between 1800 and 2400 cm−1 and for the Δn= 6 overtone CH-stretching region above 15,000 cm−1. The GVPT2 anharmonic DFT calculations permit satisfactory interpretation of the fundamental + overtone/combination of deformation modes in the mid-IR up to 3500 cm−1. The GVPT2 approach is also used for the first CH-stretching overtone regions together with their combination with deformation modes up to 9000 cm−1. Then the local-mode approach developed within the DFT protocol is employed in all the CH-stretching regions (fundamental + overtones) and is found to satisfactorily account for the observed spectra, justifying the constant VCD pattern observed for all overtones. On the basis of the local-mode model the components of the bisignate VCD spectrum are attributed to the stretchings of the axial and equatorial CH bonds in α-position with respect to the ring CC double bond.

Thermal degradation of (2R, 3R)-dihydromyricetin in neutral aqueous solution at 100 ℃

In the field of thermal degradation of flavonoids, current studies mainly focused on flavonols. However, the thermal degradation of dihydroflavonols in aqueous solution has received limited attention compared to flavonols. The single C2-C3 bonds of dihydroflavonols, which differs from the C2-C3 double bond in flavonols, may cause different degradation mechanisms. Dihydromyricetin (DMY) is a typical dihydroflavonol with six hydroxyl groups, and possesses various health effects. We explored the thermal degradation of DMY in neutral aqueous solution (pH 7) at 100 ℃. Ultra-performance liquid chromatography combined with photodiode array and electrospray ionization quadrupole-time-of-flight tandem mass spectrometric detection (UPLC-PDA-ESI-QTOF–MS/MS) provided suitable platform for exploring DMY degradation pathways, and negative ion mode was applied. Thermal treatment led to a decline in DMY level with time, accompanied by the appearance of various degradation products of DMY. Degradation mechanisms of DMY included isomerization, oxidation, hydroxylation, dimerization and ring cleavage. The pyrogallol-type ring B of DMY might be initially oxidized into ortho-quinone, which could further attack another DMY to form dimers. In addition, hydroxylation is likely to occur at C-2, C-3 of DMY or DMY dimers, which then further yields ring-cleavage products via breakage of the O1-C2 bond, C2-C3 bond, or C3-C4 bond. The 3-hydroxy-5-(3,3,5,7-tetrahydroxy-4-oxochroman-2-yl) cyclohexa-3,5-diene-1, 2-dione (m/z 333.0244) and unknown compound m/z 435.0925 were annotated as key intermediates in DMY degradation. Four phenolic acids, including 3,4,5-trihydroxybenzoic acid (m/z 169.0136, RT 1.4 min), 2,4,6-trihydroxyphenylglyoxylic acid (m/z 197.0084, RT 1.7 min), 2-oxo-2-(2,4,6-trihydroxyphenyl) acetaldehyde (m/z 181.0132, RT 2.4 min), and 2,4,6-trihydroxybenzoic acid (m/z 169.0139, RT 2.5 min) were identified as the major end products of DMY degradation. In addition, 5-((3,5dihydroxyphenoxy) methyl)-3-hydroxycyclohexa-3,5-diene-1,2-dione (m/z 261.0399, RT 11.7 min) and unidentified compound with m/z 329.0507 (RT 1.0 min) were also suggested to be end products of DMY degradation. These results provide novel insights on DMY stability and degradation products. Moreover, the heat treatment of DMY aqueous solution was found to gradually reduce the antioxidant activities of DMY, and even destroy the beneficial effect of DMY on the gut microbiota composition.

Inhibition of AKR1Cs by liquiritigenin and the structural basis

In vivo and in vitro studies have confirmed that liquiritigenin (LQ), the primary active component of licorice, acts as an antitumor agent. However, how LQ diminishes or inhibits tumor growth is not fully understood. Here, we report the enzymatic inhibition of LQ and six other flavanone analogues towards AKR1Cs (AKR1C1, AKR1C2 and AKR1C3), which are involved in prostate cancer, breast cancer, and resistance of anticancer drugs. Crystallographic studies revealed AKR1C3 inhibition of LQ is related to its complementarity with the active site and the hydrogen bonds net in the catalytic site formed through C7–OH, aided by its nonplanar and compact structure due to the saturation of the C2C3 double bond. Comparison of the LQ conformations in the structures of AKR1C1 and AKR1C3 revealed the induced-fit conformation changes, which explains the lack of isoform selectivity of LQ. Our findings will be helpful for better understanding the antitumor effects of LQ on hormonally dependent cancers and the rational design of selective AKR1Cs inhibitors.

Pushing the Upper Limit of Nucleophilicity Scales by Mesoionic N-Heterocyclic Olefins.

A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2 Et)2 , which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2 (20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2 (20 °C)=sN (N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles.

Towards ductile and high barrier poly(L-lactic acid) ultra-thin packaging film by regulating chain structures for efficient preservation of cherry tomatoes

The irreconcilable paradox between barrier performance and ductility is a “stumbling block” restricting the development of poly(L-lactic acid) (PLLA) films in the packaging industry. In this work, we reported the fabrication of an ultra-thin PLLA-based film with barrier properties and ductility by adjusting the polarity and conformational behavior of the polymer chains. Firstly, a novel unsaturated poly(L-lactic acid-co-butyrate itaconate) P(LA-BI) copolymer containing CC double bonds was synthesized using melt polycondensation. The results reveal that the addition of 60 % of P(LA-BI) enables PLLA film to achieve an elongation at a break of 83.6 % due to P(LA-BI) containing partially branched structures, which resulted in the polymer chains being arranged more in a high-energy gg conformer. Meanwhile, because of the large number of CO polar groups in P(LA-BI), PLLA/P(LA-BI)60 film show CO2 and O2 permeability coefficients (CDP and OP) of 1.8 and 0.45 × 10−8 g·m·m−2·h−1·Pa−1 respectively, which means that it has excellent gas barrier properties. Moreover, PLLA/P(LA-BI)60 film shows a 33.3 % increase in CO2/O2 ratio and an excellent ultraviolet (UV) barrier performance compared to neat PLLA. Preservation results suggested that the CO2 and O2 levels within the package could be regulated by varying the amount of P(LA-BI) added. Among them, PLLA/P(LA-BI)40 film generated a more desirable CO2 and O2 atmosphere for cherry tomatoes preservation, which was reflected by the delaying of senescence, discoloration, and decay, inhibition of oxidative cell damage through reduced malondialdehyde production, and maintenance of nutritional and flavor substances in cherry tomatoes. This PLLA-based film offers the advantages of operational simplicity, environmental friendliness, and inexpensive cost, making it great promising for food preservation and other applications requiring barrier properties and ductility.

Shock tube experiments and kinetic modeling of ignition of unsaturated [formula omitted] methyl esters

Ignition delay times (IDTs) of methyl crotonate (MC), methyl 3-butanoate (MB3D), and methyl methacrylate (MMA), were systematically measured to explore the influences of the position of unsaturated CC double bond and the structure of alkyl chain on ignition characteristics of unsaturated C5 methyl esters. Experiments were performed at 1108–1783 K and 4–16 atm with the equivalance ratio ranging from 0.25 to 2 in a shock tube. Reactivities of three unsaturated esters are similar: their IDTs increase with decreasing temperature and increasing equivalence ratio but are less sensitive to pressure. To gain the insight into differences in kinetics during fuel ignition, the literature MC, MB3D and MMA models were evaluated and the MMA model was updated. Sensitivity and reaction pathway analyses show that the hydrogen-abstraction, unimolecular decomposition, and radical addition reactions are important in controlling MC ignition. However, only hydrogen-abstraction and radical addition reactions show the significance during MB3D and MMA ignitions. Furthermore, the impact of saturation was also explored. The saturated methyl esters have slightly longer IDTs than MC, MB3D, and MMA under fuel-lean conditions with T> 1350 K, because the unsaturated methyl esters are the key intermediates and the hydrogen-abstraction reactions dominate the consumption of saturated esters.

Synthesis of UV rapid curing silicone coatings via photoinitiated thiol-ene click polymerization for pressure-sensitive adhesive

UV-curable silicone pressure-sensitive adhesive (SPSA) is composed of silicone rubber and silicone resin. Generally, the CC double bond in acryloyloxy group provides a photocurable group for SPSA. However, oxygen inhibition of acryloyloxy group block the degree of cure and CC double bond conversion of SPSA during the photopolymerization. Therefore, efficient photocurable groups for UV curing SPSA is particularly important to be developed. Thiol-ene click polymerizations have been widely used in photocrosslinked polymers due to the rapid efficiency of reactions. In this study, sulfhydryl functionalized silicone resin (SFSR) and methacrylate functionalized amino silicone rubber (MFASR) were synthesized to prepare a SPSA via photoinitiated thiol-ene click polymerization. The double bond in MSASR and sulfhydryl in SFSR were characterized by FT-IR spectroscopy and 1H NMR spectroscopy. The double bond conversion of SPSA was calculated after polymerization. The cohesion of SPSA was improved by SFSR, while the crosslinking degree was improved by thiol-ene. The loop tack of SPSA with 50 wt% SFSR was 9.01 N, and the 180° peel strength was 11.37 N/25 mm. The SPSA maintained good bonding adhesion to steel at various temperature.

The photophysics of protonated cytidine and hemiprotonated cytidine base pair: A computational study.

We here study the effect that a lowering of the pH has on the excited state processes of cytidine and a cytidine/cytidine pair in solution, by integrating time-dependent density functional theory and CASSCF/CASPT2 calculations, and including solvent by a mixed discrete/continuum model. Our calculations reproduce the effect of protonation at N3 on the steady-state infrared and absorption spectra of a protonated cytidine (CH+ ), and predict that an easily accessible non-radiative deactivation route exists for the spectroscopic state, explaining its sub-ps lifetime. Indeed, an extremely small energy barrier separates the minimum of the lowest energy bright state from a crossing region with the ground electronic state, reached by out-of-plane motion of the hydrogen substituents of the CC double bond, the so-called ethylenic conical intersection typical of cytidine and other pyrimidine bases. This deactivation route is operative for the two bases forming an hemiprotonated cytidine base pair, [CH·C]+ , the building blocks of I-motif secondary structures, whereas interbase processes play a minor role. N3 protonation disfavors instead the nπ* transitions, associated with the long-living components of cytidine photoactivated dynamics.

Design of novel phenothiazine-based push-pull photoinitiators for visible light with high activity, good solubility and low migration

Using phenothiazine as electron donor group, four novel visible light photoinitiators (10-methyl-phenothiazine-2-yl) (phenyl)methanone (MPO), (10-methyl-phenothiazine-2,8-diyl) bis(phenylmethanone) (MPBO), (E)-1-(10-methyl-phenothiazine-2-yl)-3-phenylprop-2-en-1-one (MPPO) and (2E,2′E)-1,1′-(10-methyl-phenothiazine-2,8-diyl) bis(3-phenylprop-2-en-1-one) (MPBPO) with D-A structure were synthesized by one-step method. The effect of conjugated structure and CC bond on the photophysical properties, solubility and migration ratio was discussed. With the degree of conjugation and the number of CC bond increases, the maximum absorption wavelength redshifted from 385 nm (MPO) to 414 nm (MPBO) and 400 nm (MPPO) to 430 nm (MPBPO) respectively. The charge transfer between the two-component photoinitiator system (Iod as co-initiator) can significantly improve the photopolymerization efficiency, the final CC double bond conversion can reach to 80 %, and the drying time of coatings was within 5–20 s. Moreover, all MPO, MPBO, MPPO and MPBPO have good solubility in different solvents and monomers. In addition, MPO, MPBO, MPPO and MPBPO shown low migration ratio and low cytotoxicity performance.

Optimization and Impurity Control Strategy for Lithocholic Acid Production Using Commercially Plant-Sourced Bisnoralcohol.

In this study, lithocholic acid (LCA) was prepared using commercially available plant-sourced bisnoralcohol (BA), and the overall yield of the product was 70.6% for five steps. To prevent process-related impurities, the isomerizations of catalytic hydrogenation in the C4-C5 double bond and reduction of the 3-keto group were optimized. The double bond reduction isomerization was improved (5β-H:5α-H = 97:3) using palladium-copper nanowires (Pd-Cu NWs) instead of Pd/C. The reduction of the 3-keto group was 100% converted to a 3α-OH product by 3α-hydroxysteroid dehydrogenase/carbonyl reductase catalysis. Moreover, the impurities during the optimization process were comprehensively studied. Compared with the reported synthesis methods, our developed method significantly improved the isomer ratio and overall yield, affording ICH-grade quality of LCA, and it is more cost-effective and suitable for large-scale production of LCA.

Discovery of novel pyridinones as MGAT2 inhibitors for the treatment of metabolic disorders

Inhibition of monoacylglycerol transferase 2 (MGAT2) has recently emerged as a potential therapeutic strategy for the treatment of metabolic diseases such as obesity, diabetes and non-alcoholic steatohepatitis (NASH). Metabolism studies with our clinical lead (1) suggested variability in in vitro glucuronidation rates in liver microsomes across species, which made projection of human doses challenging. In addition, the observation of deconjugation of the C3-C4 double bond in the dihydropyridinone ring of 1 in solution had the potential to complicate its clinical development. This report describes our lead optimization efforts in a novel pyridinone series, exemplified by compound 33, which successfully addressed both of these potential issues.

Degradation products of aflatoxin M1 (AFM1) formed by high voltage atmospheric cold plasma (HVACP) treatment

Cold plasma technology is a novel non-thermal technology that has shown promising results for food decontamination and improving food safety. This study is a continuation of a previous investigation of the treatment of AFM1-contaminated skim and whole milk samples by HVACP. Previous research has shown HVACP is effective in degrading aflatoxin M1 (AFM1) in milk. The goal of this study is to identify the degradation products of AFM1 after HVACP treatment in pure water. An HVACP direct treatment at 90 kV using modified air (MA65: 65% O2, 30% CO2, 5% N2) was performed for up to 5 min at room temperature on a 5.0 mL water sample in a Petri dish artificially contaminated with 2 μg/mL of AFM1. The degradants of AFM1 were analyzed and their molecular formulae were elucidated by using high-performance liquid-chromatography time-of-flight mass spectrometry (HPLC−TOF-MS). Three main degradation products were observed and based on mass spectrometric fragmentation pathways, chemical structures for the degradation products were tentatively assigned. According to the structure–bioactivity relationship of AFM1, the bioactivity of the AFM1 samples treated with HVACP was reduced due to the disappearance of the C8–C9 double bond in the furofuran ring in all of the degradation products.

Selective hydrogenation of carbon–carbon double bond catalyzed by FLP-MOFs

Selective hydrogenation of CC double bond in α, β-unsaturated carbonyl compounds is of great significance in the production of fine chemicals, and the design and preparation of hydrogenation catalysts with high selectivity is the key to realize the industrialization of this reaction. Controlling and adjusting the steric hindrance between substrate molecules and active center of catalysts is an effective strategy to achieve high selectivity. In this work, the spatially hindered “Frustrated Lewis pairs” (FLPs) was used as the active component and metal-organic frameworks (MOFs) materials with a certain window size were used as the catalyst support. We designed and synthesized a heterogeneous hydrogenation catalyst B(C6F5)3/DO-MIL-101 by immobilizing FLP onto metal-organic frameworks (MIL-101). Characterizations and catalytic performance tests revealed that the catalytically active species B(C6F5)3/DO was confined in MIL-101 nanocavities via Cr–O coordination bond. The resulting B(C6F5)3/DO-MIL-101 catalyst not only realized the recycling of FLP, but also showed excellent catalytic activity and high selectivity in the selective hydrogenation of CC double bond in α, β-unsaturated carbonyl ketones. It should be noted that the steric hindrance between FLP and substrate molecules, as well as the shape selectivity of MOFs nanocages, are the principal factors for the high selectivity of the catalyst.

GC-MS of some Amaryllidaceae alkaloids of homolycorine type.

Gas chromatography-mass spectrometry (GC-MS) is the most frequently applied technique for analysis of Amaryllidaceae alkaloids in plant extracts. These compounds, known for their potent bioactivities, are a distinctive chemotaxonomic feature of the Amaryllidoideae subfamily (Amaryllidaceae). The Amaryllidaceae alkaloids of homolycorine type with a C3-C4 double bond generally show molecular and diagnostic ions at the high mass region with low intensity in EIMS mode leading to problematic identification in complex plant extracts. Eleven standard homolycorine-type alkaloids (isolated and identified by 1D and 2D nuclear magnetic resonance) were subjected to separation with gas chromatography and studied with electron impact mass spectrometry including single quadropole (GC-EIMS), tandem (GC-EIMS/MS), and high resolution (GC-HR-EIMS) detectors, as well as with chemical ionisation mass spectrometry (GC-CIMS). Alkaloid fractions from two Hippeastrum species and Clivia miniata were subjected to GC-EIMS and GC-CIMS for alkaloid identification. GC-EIMS in combination with GC-CIMS provided significant structural information for homolycorine-type alkaloids with C3-C4 double bond facilitating their unambiguous identification. Based on the obtained typical fragmentation, other eleven homolycorine-type compounds were identified in extracts from two Hippeastrum species by parallel GC-EIMS, GC-CIMS and LC-ESI/ToF/MS and in extracts from Clivia miniata by GC-EIMS. GC-MS can be successfully applied for identification of new and known homolycorine-type alkaloids, as well as for chemotaxonomical and chemoecological studies, among others within the Amaryllidoideae subfamily.