Methoxyl Groups Research Articles

A "Bottom-Up" Strategy for High-Performance Benzocyclobutene (BCB)-Subnanometer Inorganic Nanocomposites.

Developing benzocyclobutene (BCB) nanocomposites with ultra-small inorganic sizes represents a formidable challenge, although it offers great potential to produce materials with customizable structural and rich functional properties. In this study, we present a "bottom-up" design strategy for creating cross-linked benzocyclobutene (BCB) nanocomposites with highly dispersed nanodomains, such as organoalkoxysilane. This approach leverages ring-opening metathesis polymerization (ROMP) and thermally induced cycloaddition reactions to embed oligomeric silsesquioxanes, achieving a unique molecular structure with promising low-dielectric applications. The synthesis involves organoalkoxysilane and BCB as pendant groups of polynorbornenes that are covalently integrated. Additionally, the methoxyl groups of linear polymers could be further hydrolyzed under acidic conditions, and BCB groups could undergo thermal-induced ring-opening at high temperatures and Diels-Alder addition between themselves and vinyl groups, respectively. Fourier transform infrared (FTIR) spectroscopy analyses suggested the presence of ladder or network structures and high-resolution transmission electron microscopy (HRTEM) images presented the well-dispersed inorganic clusters, facilitating excellent dielectric properties with a dielectric constant (Dk) of 2.25 and a dissipation factor (Df) of 2.27 × 10-4. Compared with previously reported low-Dk materials, the cured nanocomposites also exhibited a significantly balanced enhancement of their comprehensive properties. This molecular bottom-up strategy provided a simple and universal method for constructing BCB-inorganic nanocomposites featuring a subnanometer inorganic structure, paving the way for future investigation into new classes of polymer-inorganic nanocomposites with a low Dk.

Catechol- and Phenolic Hydroxyl-Functionalized Partially Bio-Based (Co)poly(ether sulfone)s with Multifarious Applicability

A largely bio-based new bisphenol, namely, 4,4′-((3,4-dimethoxyphenyl)methylene)-bis(2-methoxyphenol) (DMBM) was synthesized by the reaction of veratraldehyde with guaiacol. DMBM and varying compositions of DMBM and bisphenol A were polycondensed with bis(4-fluorophenyl) sulfone to afford reasonably high molecular weight film-forming (co)poly(ether sulfone)s possessing built-in methoxyl groups. T10 and Tg values of (co)poly(ether sulfone)s were in the range 382–478 °C and 171–187 °C, respectively indicating their good thermal stability and the values decreased with increase in mol % incorporation of DMBM. The methoxyl groups present in (co)poly (ether sulfone)s were quantitatively de-blocked resulting in the formation of corresponding polymers possessing pendant catechol moieties and free phenolic hydroxyl groups. By virtue of the presence of these functional moieties, (co)poly(ether sulfone)s are amenable for post-polymerization modifications, and exhibited properties such as antimicrobial (23 mm against Staphylococcus aureus and 18 mm against Escherichia coli)), antioxidant (72 % scavenger of free radicals), adhesive (2.24 MPa lap shear strength) and usefulness as redox-active agent in zinc-ion batteries. These data underscore the promise of DMBM as a versatile monomer of wider utility for the synthesis of functional (co)poly(ether sulfone)s capable of expanding their applicability beyond the conventional ones.

Stepwise customizing pore environments of C2H2-selective frameworks for one-step C2H4 acquisition from ternary mixtures

One-step purification of C2H4 from ternary C2H2/C2H4/C2H6 mixture is crucial but challenging since the primary physical properties of C2H4 all fall between C2H2 and C2H6. Hence, we report an effective approach for purifying C2H4 through stepwise customizing pore environments on C2H2-selective materials. Utilizing SIFSIX-1-Cu as a prototype material, we incorporated one or two methoxyl groups onto 4,4′-bipyridine to obtain isomorphic framework SIFSIX-1-Cu-OMe and SIFSIX-1-Cu-(OMe)2 respectively. As expected, pore sizes gradually decrease, while C2H6 binding sites increase. Ultimately, the C2H6/C2H4 (10/90) selectivity gradually increases from 1.18 (SIFSIX-1-Cu) to 1.27 (SIFSIX-1-Cu-OMe) and finally to a remarkably high value of 1.79 (SIFSIX-1-Cu-(OMe)2). As anticipated, SIFSIX-1-Cu-(OMe)2 can achieve one-step acquisition of polymer-grade C2H4 (≥99.95 %) from C2H2/C2H4/C2H6 (1/90/9) mixture with high productivity of 6.82 L/kg. Furthermore, theoretical calculations indicate that the pore surface of SIFSIX-1-Cu-(OMe)2 is beneficial to preferentially capture C2H2 and C2H6, and thus realizes one-step purification of C2H4.

Molecular identification of rhamnolipids produced by Pseudomonas oryzihabitans during biodegradation of crude oil.

The ability to produce biosurfactants plays a meaningful role in the bioavailability of crude oil hydrocarbons and the bioremediation efficiency of crude oil-degrading bacteria. This study aimed to characterize the produced biosurfactants by Pseudomonas oryzihabitans during the biodegradation of crude oil hydrocarbons. The biosurfactants were isolated and then characterized by Fourier transform infrared (FTIR), liquid chromatography-mass-spectrometry (LC-MS), and nuclear magnetic resonance spectroscopy (NMR) analyses. The FTIR results revealed the existence of hydroxyl, carboxyl, and methoxyl groups in the isolated biosurfactants. Also, the LC-MS analysis demonstrated a main di-rhamnolipid (l-rhamnopyranosyll-rhamnopyranosyl-3-hydroxydecanoyl-3-hydroxydecanoate, Rha-Rha-C10-C10) along with a mono-rhamnolipid (l-rhamnopyranosyl-b-hydroxydecanoylb-hydroxydecanoate, Rha-C10-C10). In agreement with these findings, the NMR analysis confirmed the aromatic, carboxylic, methyl, sulfate moieties, and hexose sugar in the biosurfactants. The emulsion capacity of the biosurfactants decreased the surface tension of the aqueous system from 73.4 mN m-1 to around 33 mN m-1 at 200 mg L-1 as the critical micelle concentration. The emulsification capacity of the biosurfactants in the formation of a stable microemulsion for the diesel-water system at a wide range of pH (2-12), temperature (0-80°C), and salinity (2-20 g L-1 of NaCl) showed their potential use in oil recovery and bioremediation through the use of microbial enhancement. This work showed the ability of Pseudomonas oryzihabitans NC392 cells to produce rhamnolipid molecules during the biodegradation process of crude oil hydrocarbons. These biosurfactants have potential in bioremediation studies as eco-friendly and biodegradable products, and their stability makes them optimal for areas with extreme conditions.

Impact of end groups of small molecules grafted to reverse osmosis membranes on their separation and antifouling performance

In this study, surface hydroxylation and methoxylation were employed to fabricate polyamide (PA) reverse osmosis (RO) membranes with enhanced permeability and antifouling performance. Diethanolamine (DEA) and bis(2-methoxyethyl) amine (BMEA) were grafted onto PA of RO membranes, and the impact of their end groups of hydroxyls and methoxyls on PAs were investigated. Benefiting from the increased surface hydrophilicity (particularly for the DEA-grafted RO) and the tailored cross-linking structure of PA layers, both DEA- and BMEA-grafted membranes showed high water permeance (1.58-fold than the pristine RO membrane) with highly competitive NaCl rejection of 99 %. The DEA-grafted membrane exhibited the enhanced antifouling performance against both positively and negatively charged foulants, while the BMEA-grafted membrane exhibited exceptional performance against small cationic foulants. Quantum chemistry simulations reveal that hydroxyl groups grafted on PA possess a relatively low binding energy with both positively and negatively charged small foulants, whereas methoxyl groups grafted on PA exhibited an exceptionally low binding energy with positively charged small foulants, which rendered them less likely to be adsorbed onto the corresponding grafted PA and to form a loose cake layer. Our study provides new insights into design of small molecules with different end groups used for the simple and effective modification of antifouling RO membranes.

Phytochemical characterization of selected agro-waste extracts as kinetic inhibitors in methane hydrates formation

In this study of gas hydrate inhibition, the bio-active components (phytochemicals) and the influence of functional moieties and chemical structures on selected bio-inhibitors' performance were investigated by advanced analytical techniques. The agro-waste materials of interest are: orange mesocarp (Citrus sinensis (L)) extract (OME), red onion skin (Allium cepa) extract (ROSE), kolanut tesla (Cola acuminata) extract (KTE), coconut coir dusk (Cocos nucifera) extract (CCDE) and peanut skin (Arachis hypogea) extract (PSE). A CO2-enhanced supercritical fluid extraction (SFE) technique was used to extract the bioactive components from their parent materials. After the extraction, advanced analytical techniques including FTIR, NMR and HP-TLC with densitometry were used to identify and isolate functional groups, structurally characterize and quantify the bioactive compounds in the extracts primarily focusing on phenolic acids, flavonoids and tannins. A Bruker 500MZ NMR spectrometer and a CAMAG-semi-automatic HP-TLC system were used for the structural characterization and quantification respectively. Based on the number of anti-oxidants and radicals scavenging characteristics of the individual extracts' polyphenolic and tannin components, the expected hydrates inhibition capacities of the bio-extracts are in the magnitude: CCDE > ROSE > PSE > OME > KTE. The extracts are readily biodegradable and non-toxic and therefore do not pose ecological threat unlike PVP with only 31.50% biodegradation rate and may result in serious ecological risks in offshore environments. Lastly, the numbers of hydroxyl (OH) and meth-oxyl (MeoH) groups are the principal factors that influence the bio-inhibitors performance with hydroxyl group number being more important than that of the meth-oxyl group.

Carbon-wise utilization of lignin-related compounds by synergistically employing anaerobic and aerobic bacteria

BackgroundLignin is a highly abundant but strongly underutilized natural resource that could serve as a sustainable feedstock for producing chemicals by microbial cell factories. Because of the heterogeneous nature of the lignin feedstocks, the biological upgrading of lignin relying on the metabolic routes of aerobic bacteria is currently considered as the most promising approach. However, the limited substrate range and the inefficient catabolism of the production hosts hinder the upgrading of lignin-related aromatics. Particularly, the aerobic O-demethylation of the methoxyl groups in aromatic substrates is energy-limited, inhibits growth, and results in carbon loss in the form of CO2.ResultsIn this study, we present a novel approach for carbon-wise utilization of lignin-related aromatics by the integration of anaerobic and aerobic metabolisms. In practice, we employed an acetogenic bacterium Acetobacterium woodii for anaerobic O-demethylation of aromatic compounds, which distinctively differs from the aerobic O-demethylation; in the process, the carbon from the methoxyl groups is fixed together with CO2 to form acetate, while the aromatic ring remains unchanged. These accessible end-metabolites were then utilized by an aerobic bacterium Acinetobacter baylyi ADP1. By utilizing this cocultivation approach, we demonstrated an upgrading of guaiacol, an abundant but inaccessible substrate to most microbes, into a plastic precursor muconate, with a nearly equimolar yields (0.9 mol/mol in a small-scale cultivation and 1.0 mol/mol in a one-pot bioreactor cultivation). The process required only a minor genetic engineering, namely a single gene knock-out. Noticeably, by employing a metabolic integration of the two bacteria, it was possible to produce biomass and muconate by utilizing only CO2 and guaiacol as carbon sources.ConclusionsBy the novel approach, we were able to overcome the issues related to aerobic O-demethylation of methoxylated aromatic substrates and demonstrated carbon-wise conversion of lignin-related aromatics to products with yields unattainable by aerobic processes. This study highlights the power of synergistic integration of distinctive metabolic features of bacteria, thus unlocking new opportunities for harnessing microbial cocultures in upgrading challenging feedstocks.

Thermal-Robust Phenoxyimine Titanium Catalysts Bearing Bulky Sidearms for High Temperature Ethylene Homo-/Co- Polymerizations.

A family of titanium complexes (Ti1-Ti7) with the general formula LTiCl3, supported by tridentate phenoxyimine [O-NO] ligands (L1-L7) bearing bulky sidearms, were synthesized by treating the corresponding ligands with stoichiometric amount of TiCl4. All the ligands and complexes were well characterized by 1H and 13C NMR spectroscopies, in which ortho- methoxyl groups on N-aryl moieties shifted to downfield, corroborating the successful coordination reaction. Structural optimization by DFT calculations revealed that one of the phenyl groups on dibenzhydryl moiety could form π-π stacking interaction with the salicylaldimine plane, because of which the obtained titanium complexes revealed good thermal stabilities for high-temperature polymerization of ethylene. The thermal robustness of the complexes was closely related to the strength of π-π stacking interactions, which were mainly influenced by the substituents on the dibenzhydryl moieties; Ti1, Ti4 and Ti5 emerged as the three best-performing complexes at 110 °C. With the aid of such π-π stacking interactions, the complexes were also found to be active at >150 °C, although decreased activities were witnessed. Besides homopolymerizations, complexes Ti1-Ti7 were also found to be active for the high-temperature copolymerization of ethylene and 1-octene, but with medium incorporation percentage, demonstrating their medium copolymerization capabilities.

Enzymatic hydrolysis lignin and kraft lignin from birch wood: a source of functional bio-based materials

In the pursuit of sustainable biomass utilization, this study investigates the hydrothermal treatment of birchwood and its subsequent impact on enzymatic hydrolysis lignin (EHL). Additionally, birchwood undergoes processing with NaOH (4% w/w) within a Parr reactor to precipitate lignin from the black liquor, resulting in lignin-rich substrates (LRSs) which are then subject to thorough characterization. Notably, EHL produced after hydrothermal pretreatment at 190 °C exhibits the highest lignin content at 67%, while kraft lignin (KL) obtained at 140 °C (pH 1.5) produces 65% lignin content. Among these LRSs, the KL sample produced at 190 °C (pH 4) stands out, displaying a robust aromatic skeletal structure and an abundance of methoxyl groups, primarily owing to its high purity. Furthermore, for these LRSs' it is shown that chemical configuration influences their thermal behaviour, allowing the lignin to be tailored for diverse applications, from low melting point materials to carbonaceous materials capable of withstanding temperatures exceeding 700 °C. This comprehensive understanding of the chemical, thermal, and physical attributes of LRSs not only enriches our knowledge of lignin-rich substrates but also paves the way for the development of sustainable bio-based materials, marking a step towards sustainable materials development.

New insights into greener skin healthcare protection: Lignin nanoparticles as additives to develop natural-based sunscreens with high UV protection

Despite lignin nanoparticles (LNPs) being extensively employed as assistant agents to improve the UV-blocking performance of sunscreens, there is a lack of information addressing how and to what extent the chemical and structural features of these particles relate to the improvements observed in the Sun Protection Factors (SPF) of the sunscreens. In this study, lignin oligomers were prepared by a solvothermal extraction process of five typical biomasses in a water–acetone co-solvent without noticeable degradation of the cellulose fraction. Afterward, LNPs were produced from the self-assembly of these lignin oligomers via the solvent-shifting methodology. When incorporated into the sunscreen, these had different morphologies, and exerted different UV-blocking capacities. The effects of the chemical structure and size distribution of the LNPs were systematically studied and compared to those of the original lignin oligomers. LNPs exhibited better UV-blocking ability than soluble lignin oligomers due to the more exposed chromophore on the surface. Besides, compact LNPs with conjugating CO and β-O-4 linkages, as well as the presence of the syringyl unit rich in the methoxyl group in the structures, were beneficial in boosting the UV resistance of the sunscreens. Even though smaller LNPs with higher surface area favored the UV shielding performance, LNPs with widely distributed sizes could further help decrease the UV transmittance. These findings provide an excellent basis for using lignin-derived materials as sunscreen additives and pave the way to developing new environmentally friendly materials for the cosmetic industry.

Effect of ultrasonic modification on the binding ability of pectin to anthocyanin.

Pectin was considered as a potential candidate to improve the thermal stability of anthocyanins, and the binding ability of pectin to anthocyanins was influenced by its structure. In this study, sunflower pectins, modified by ultrasound (40 kHz) for different periods of time, were prepared and used to bind with anthocyanins, extracted from purple sweet potato. Characterization and thermal stability of pectin-anthocyanin complexes were investigated. The ultrasonic modification of pectin resulted in many changes in pectin chemical structure, including degradation of neutral sugar side chains, breakage of methoxyl groups, and increased molecular flexibility. Extension of ultrasonic modification time led to greater changes in pectin chemical structure. Analysis of the binding ability, as determined by Fourier transform infrared spectroscopy and molecular dynamics simulations, revealed that the interaction between pectin and anthocyanins was driven by hydrogen bonding, electrostatic interaction, and hydrophobic interaction. Pectins with different ultrasonic modification times bound with anthocyanins to different extents, mainly resulting from an increase in the number of hydrogen bonds. According to high-performance liquid chromatographic analysis, during heating at 90 °C the stronger the binding ability of pectin and anthocyanin complex, the better was its thermal stability. Ultrasonic modification of pectin could effectively enhance its binding ability to anthocyanin. © 2023 Society of Chemical Industry.

Influence of habitat, density, lignin structure, and extraction treatment on thermal-softening properties of water-swollen wood: a study of 87 wood specimens

Abstract This study aims to reveal the diversity of thermal-softening temperatures and identify the factors that determine this temperature. To achieve this, the thermal-softening properties of the radial direction of wood were measured under water-saturated conditions for 15 softwood and 72 hardwood specimens. Wood samples were obtained from the xylarium of the Forestry and Forest Products Research Institute, Japan. A dynamic viscoelastic measurement was performed on samples with uniform heating and cooling history because the difference in cooling rate can alter in the mechanical properties of wood. The storage and loss elastic moduli increased linearly as wood density increased, regardless of the wood species. However, the thermal-softening temperature (defined in this study as the peak temperature of loss tangent) was unrelated to the density, anatomical features, species, latitude, and annual rainfall in the habitat. When the relationship between thermal-softening temperature and lignin structure was investigated, a negative correlation was observed between the thermal-softening temperature and the syringyl ratio (syringyl/(syringyl+guaiacyl)) of lignin aromatics. This indicates that the thermal-softening temperature is higher for wood species with denser lignin structures, supporting the prior research showed correlation between thermal-softening temperature and methoxyl group content of wood.

Long-lasting UV-blocking Mechanism of Lignin: Origin and Stabilization of Semiquinone Radicals.

Semiquinone (SQ) radicals play a critical role in the long-lasting UV-blocking application of lignin, while their origin and stable structure are unclear. Here, the organosolv lignin extracted from poplar (OL-P) is self-assembled into normal micelles (LNM) with more phenolic hydroxyl groups on the surface, and reverse micelles (LRM) with more methoxyl groups on the surface. After 12h UV irradiation, the SQ radical contents in LNM and LRM increase 33% and 78% respectively. The performance of LNM based sunscreen keeps upswinging due to radical stabilization of phenolic hydroxyl groups. LRM based sunscreen experiences a gradual decrease after reaching maximum UV absorbance due to the quick generation and over oxidation of SQ radicals. Density functional theory (DFT) simulations reveal that methoxyl groups in OL-P has bigger bond length and smaller bond dissociation enthalpy than phenolic hydroxyl groups, and are easy to form SQ radicals. The Gibbs free energy (ΔG) needed for SQ-quinone transformation is above 26.10kcalmol.-1 , while that for SQ-hydroquinone transformation is below -66.78kcalmol.-1 . Hydroquinone is the stable structure of SQ radicals. This work discloses the origin and stable structure of SQ radicals in lignin under UV irradiation, and provides an important guidance for its long-lasting UV-blocking application.

UV absorption enhanced polydopamine coating.

Mussel-inspired polydopamine (PDA) coatings have gained significant attention in various fields, including biomedicine, energy, detection, and UV protection, owing to their versatile and promising properties. Among these properties, UV shielding stands out as a key feature of PDA coatings. Nevertheless, the current methods for tuning the UV-shielding properties of PDA coatings are quite limited, and only rely on thickness adjustment, which might involve additional issues like color and visible light transmittance to the coating layer. In this study, we propose a facile and modular approach to enhance the UV absorption of PDA coatings by incorporating thiol-heterocycle (TH) derivatives. Both pre- and post-modification strategies can effectively impede the formation of conjugated structures within PDA, leading to enhanced UV absorption within the PDA layers. More importantly, these strategies can improve the UV absorption of PDA coatings while reducing the visible light absorption. Furthermore, this method enabled efficient regulation of the UV absorption of PDA coatings by altering the ring type (benzene ring or pyridine ring) and substituent on the ring (methoxyl group or hydrogen atom). These PDA coatings with enhanced UV absorption demonstrate great promise for applications in UV protection, antibacterial activity, wound healing and dye degradation.

Asymmetric Synthesis of Methoxylated Ether Lipids: Total Synthesis of Polyunsaturated C18:3 Omega-3 and Omega-6 MEL Triene Derivatives.

The asymmetric synthesis of polyunsaturated triene C18:3 n-3 and C18:3 n-6 methoxylated ether lipids (MEL) of the 1-O-alkyl-sn-glycerol type is described as possible structural candidates for a triene C18:3 MEL of an unknown identity found in a mixture of shark and dogfish liver oil. Their C18:3 hydrocarbon chains constitute an all-cis methylene skipped n-3 or n-6 triene framework, along with a methoxyl group at the 2'-position and R-configuration of the resulting stereogenic center. The methoxylated polyenes are attached by an ether linkage to the pro-S hydroxymethyl group of the glycerol backbone. The syntheses were based on the polyacetylene approach that involves a semi-hydrogenation of the resulting triynes. Both syntheses were started from our previously described enantio- and diastereomerically pure isopropylidene-protected glyceryl glycidyl ether, a double-C3 building block that was designed as a head group synthon for the synthesis of various types of MELs.

Effect of various aromatic compounds with different functional groups on enzymatic hydrolysis of microcrystalline cellulose and alkaline pretreated wheat straw

Low molecular aromatic compounds are detrimental to the enzymatic hydrolysis of lignocellulose. However, the specific role of their functional groups remains unclear. Here, a series of nine aromatic compounds as additives were tested to understand their effect on the hydrolysis yield of microcrystalline cellulose (MCC) and alkaline pretreated wheat straw. Based on the results, the inhibition of aldehyde groups on MCC was greater than that of carboxyl groups, whereas for the alkaline pretreated wheat straw case, the inhibitory effect of aldehyde groups was lower than that of carboxyl groups. Increased methoxyl groups of aromatic compounds reduced the inhibitory effect on enzymatic hydrolysis of both substrates. Stronger inhibition of aromatic compounds on MCC hydrolysis was detected in comparison with the alkaline pretreated wheat straw, indicating that the substrate lignin can offset the inhibition to a certain extent. Among all aromatic compounds, syringaldehyde with one aldehyde group and two methoxyl groups improved the glucan conversion of the alkaline pretreated wheat straw.

CHEMICAL PROCESSING OF AGRICULTURE WASTES INTO VANILLIN, PULP AND GLUCOSE

Agrotechnical wastes from processing herbaceous plants consist of lignin and polysaccharides, which can be processed into monomers – phenols and carbohydrates. The prospects of chemical processing of several agrotechnical waste types with a high lignin content (flax shives, sunflower seed husks and buckwheat husks) into vanillin, pulp, and glucose by oxidation and acid hydrolysis were studied. It has been shown that despite the distant phylogenetic relationship of the studied plants, their lignins have a similar structure: they contain a similar amount of methoxyl groups (10–13 wt.% per lignin) and give close yields of aromatic aldehydes upon oxidation with nitrobenzene (17–19%) and oxygen (14–16%). In general, the suitability of agrotechnical wastes for oxidation to aromatic aldehydes determines by the lignin content. Among the studied wastes, flax shives are the most promising feedstock for chemical processing into vanillin and glucose. Cellulose-containing solid residues of oxidation process are more easily hydrolyzed compared to the initial lignocellulosic biomass. The inversion of glucose oligomers during the hydrolysis of cellulose with H2SO4 is limited by the hydrolysis of the tetra- and octamers.

Tuning the CO2 selective adsorption performance in MOFs by incorporating functional groups on the isophthalate skeleton

By introducing functional groups into the isophthalate ligand to decorate the pore of the MOFs, gas adsorption and separation performance can be tunable. In this paper, two isostructural 2D Co-MOFs, [Co(5-MIA)(bpy)]·H2O (1) and [Co(5-EIA)(bpy)]·H2O (2) (5-H2MIA = 5-methoxyl-isophthalic acid; 5-H2EIA = 5-ethyoxyl-isophthalic acid; bpy = 4,4′-bipyridine), with different functionalized pore surfaces and channel sizes were designed and constructed. The structures and performance of the two Co-MOFs were analyzed by SCXRD, PXRD, IR, TGA, and gas sorption (CO2, C2H2, CH4, CO, and N2). Attributed to the methoxyl of isophthalate skeleton, 1a (activated 1) shows enhanced CO2 uptake over other gases. In spite of decreased pore sizes (3.49 Å) compared with 2a (4.38 Å), the CO2 uptake of 1a (43.41 cm3 g−1) is larger than that of 2a (22.39 cm3 g−1) at 298 K and 100 kPa. Compound 1 incorporates methoxyl groups into the narrow channel, and exhibits the cooperative effect of CO2-preferential due to adsorbent-adsorbate coactions and size sieving. GCMC simulation has been used to explore the adsorption coactions of CO2 and 1, and the results confirmed that the methoxyl groups in the channel are the main binding sites of CO2. At ambient temperature and 100 kPa, the IAST selectivities of CO2/C2H2 (1:1), CO2/CH4 (1:1), C2H2/CH4 (1:1), CO2/CO (1:2) and CO2/N2 (15:85) on 1a were 2.6, 39.3, 13.3, 282 and 1433, respectively. The easy activation and regeneration, excellent thermal and humidity stability, and good reusability, make 1a hopeful adsorbent for adsorption and separation of CO2.

Isotopic clumping in wood as a proxy for photorespiration in trees.

Photorespiration can limit gross primary productivity in terrestrial plants. The rate of photorespiration relative to carbon fixation increases with temperature and decreases with atmospheric [CO2]. However, the extent to which this rate varies in the environment is unclear. Here, we introduce a proxy for relative photorespiration rate based on the clumped isotopic composition of methoxyl groups (R-O-CH3) in wood. Most methoxyl C-H bonds are formed either during photorespiration or the Calvin cycle and thus their isotopic composition may be sensitive to the mixing ratio of these pathways. In water-replete growing conditions, we find that the abundance of the clumped isotopologue 13CH2D correlates with temperature (18-28 °C) and atmospheric [CO2] (280-1000 ppm), consistent with a common dependence on relative photorespiration rate. When applied to a global dataset of wood, we observe global trends of isotopic clumping with climate and water availability. Clumped isotopic compositions are similar across environments with temperatures below ~18 °C. Above ~18 °C, clumped isotopic compositions in water-limited and water-replete trees increasingly diverge. We propose that trees from hotter climates photorespire substantially more than trees from cooler climates. How increased photorespiration is managed depends on water availability: water-replete trees export more photorespiratory metabolites to lignin whereas water-limited trees either export fewer overall or direct more to other sinks that mitigate water stress. These disparate trends indicate contrasting responses of photorespiration rate (and thus gross primary productivity) to a future high-[CO2] world. This work enables reconstructing photorespiration rates in the geologic past using fossil wood.

Highly oxidized flavones in Artemisia species – structure revisions and improved UHPLC-MSn analysis

In course of our studies of the aerial parts of Artemisia abrotanum the major methoxyflavonol could be isolated. However, by NMR structural analysis it became obvious that the substitution pattern in ring B differs from reports for casticin (2). The position of methoxyl and hydroxyl groups are interchanged, i.e., the major flavone is actually chrysosplenetin (1). Three structures in A. abrotanum and A. frigida had to be revised. Use of pyridine-d5 instead of DMSO‑d6 made the resolution of the B-ring 1H and 13C NMR signals possible and enabled correct structural assignment by 2D NMR experiments.Results from NMR structure elucidation for A. abrotanum were confirmed by LC-PDA-ESI-MSn analysis when a PFP (pentafluorophenyl) stationary phase with an optimized gradient elution was applied for separation of 1 and 2 instead of a corresponding C-18 phase. Electrospray mass spectrometry (positive and negative mode) with subsequent fragmentation (ESI-MSn) revealed distinctive mass spectral features of both compounds, especially at MS4 level. Several Artemisia extracts including A. annua were analysed on the PFP phase for the presence of 1 and 2.