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The challenge of global climate change has drawn people's attention to the issue of carbon emissions. Reducing the use of petroleum-derived materials and increasing the use of biodegradable materials is a current focus of research, especially in the packaging materials industry. This study focused on the use of environmentally friendly plastics and waste paper as the main materials for packaging films. Poly(butylene succinate-co-lactate) (PBSL) was modified with maleic anhydride (MA) to form a biobased compatibilizer (MPBSL), which was then blended with a mixture (WPS) of waste-paper powder (WP) and silica aerogel powder (SP) to form the designed composite (MPBSL/WPS). The modification of PBSL with MA improved interfacial adhesion between PBSL and WPS. The structure, thermal, and mechanical properties, water vapor/oxygen barrier, toxicity, freshness, and biodegradability of MPBSL/WPS films were evaluated. Compared with the PBSL/WP film, the MPBSL/WPS film exhibited increased tensile strength at break of 4-13.5 MPa, increased initial decomposition loss at 5 wt% of 14-35 °C, and decreased water/oxygen permeabilities of 18-105 cm 3 /m 2 ·d·Pa. In the water absorption test, the MPBSL/WPS film displayed about 2-6 % lower water absorption than that of the PBSL/WP film. In the cytocompatibility test, both MPBSL/WPS and PBSL/WP membrane were nontoxic. In addition, compared with PBSL/WP film and the control, the MPBSL/WPS film significantly reduced moisture loss, extended the shelf life, and prevented microbial growth in vegetable and meat preservation tests. Both MPBSL/WPS and PBSL/WP films were biodegradable in a 60-day soil biodegradation test; the degradation rate was 50 % when the WP or WPS content was 40 wt%. Our findings indicate that the composites would be suitable for environmentally sustainable packaging materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Hydrogenation of alkenes is one of the most fundamental transformations in organic synthesis, and widely used in the petrochemical, pharmaceutical, and food industries. Although numerous hydrogenation methods have been developed, novel types of catalysis with new mechanisms and new hydrogen sources are still desirable. Thioxanthone (TX) is widely used in energy-transfer photoreactions, but rarely in photoredox processes. Herein we show that a catalytic amount of TfOH as a co-catalyst can tune the properties of TX to make it a photoredox catalyst with highly enhanced oxidative capability in the hydrogenation of carbonylated alkenes with the cheap petroleum industrial product p-xylene serving as the hydrogen source. Deuterium can also be introduced by this method by using D 2 O as the D source. To the best of our knowledge, this is the first example of using p-xylene as a hydrogen source., (© 2022 Wiley-VCH GmbH.)

Dual-column headspace gas chromatographic analysis with two flame-ionization detectors is a commonly used analytical technique for forensic blood ethanol quantitation. This technique is also applicable to the identification and quantitation of other volatile organic compounds such as methanol in biological samples. Compound identification by retention time is limited to those compounds with known retention times programmed into the instrument method. Historically, an early-eluting peak from an unidentified compound has been observed in both chromatograms from antemortem blood samples analyzed for ethanol concentration with this technique. The unidentified compound's retention time matches that of methanol on one column but not on the second column. This previously unidentified compound has been identified as isobutylene. The proposed source of the isobutylene contamination historically observed in antemortem blood samples collected in 10-ml gray-top blood collection tubes is the conventional rubber stopper. Isobutylene was detected in deionized water stored in each of the seven lots of 10-ml blood tubes tested; the expiration dates of the tubes tested spanned the years 2002-2022. Misidentification of isobutylene as methanol is possible when using a single-column gas chromatographic system. The presence of isobutylene in blood collected in a gray-top collection tube does not represent laboratory contamination, is not an interferent with blood ethanol quantitation, and does not affect the ethanol concentration in the blood. A 0.150 g/dl aqueous ethanol standard was stored in a gray-top tube to evaluate the potential impact of isobutylene on ethanol quantitation. The solution's average ethanol concentration measured after storage was 0.150 g/dl., (© 2021 American Academy of Forensic Sciences.)

In this study, we outline a general method for photocatalyzed difunctionalization of alkenes, a diene, alkynes, 1,3-enynes, and [1.1.1]propellane using dithiosulfonate reagents (ArSO 2 -SSR) with improved atom economy. Both "ArSO 2 -" and "-SSR" on the dithiosulfonate are transferred under mild conditions with broad substrate scope, high stereoselectivity, and complete regioselectivity. Significantly, the resulting dithiosulfonylated styrene is a general and practical nucleophilic disulfuration reagent, reacting with a variety of electrophiles efficiently. Both reactions can be conducted on gram scale, rendering the approach highly valuable., (© 2023 Wiley-VCH GmbH.)

We have rationally designed a new class of alkyne-tethered oximes and applied them in an unprecedented iron-catalyzed radical relay protocol for the rapid assembly of a wide array of structurally new and interesting fused pyridines. This method shows broad substrate scope and good functional-group tolerance and enabled the synthesis of several biologically active molecules. Furthermore, the fused pyridines could be diversely functionalized through various simple transformations, such as cyclization, C-H alkylation, and a click reaction. DFT calculation studies indicate that the reactions involve cascade 1,5-hydrogen atom transfer, 5-exo-dig radical addition, and cyclization processes. Moreover, preliminary biological investigations suggest that some of the fused pyridines exhibit good anti-inflammatory activity by restoring the imbalance of inflammatory homeostasis of macrophages in a lipopolysaccharide-induced model., (© 2020 Wiley-VCH GmbH.)

Reductive elimination of alkyl-Pd II -O is a synthetically useful yet underdeveloped elementary reaction. Here we report that the combination of an H-bonding donor [PyH][BF 4 ] and AgNO 3 additive under toluene/H 2 O biphasic system can enable such elementary step to form alkyl nitrate. This results in the Pd 0 -catalyzed asymmetric carbonitratations of (Z)-1-iodo-1,6-dienes with (R)-BINAP as the chiral ligand, affording alkyl nitrates up to 96 % ee. Mechanistic studies disclose that the reaction consists of oxidative addition of Pd 0 catalyst to vinyl iodide, anion ligand exchange between I - and NO 3 - , alkene insertion and S N 2-type alkyl-Pd II -ONO 2 reductive elimination. Evidences suggest that H-bonding interaction of PyH⋅⋅⋅ONO 2 can facilitate dissociation of O 2 NO - ligand from the alkyl-Pd II -ONO 2 species, thus enabling the challenging alkyl-Pd II -ONO 2 reductive elimination to be feasible., (© 2022 Wiley-VCH GmbH.)

Herein, we report an efficient and rapid synthetic methodology to access diversely substituted oxa-cages from unactivated olefinic substrates derived from endo-norbornenes by employing Lewis acid- (BF 3  ⋅ OEt 2 ) or base (NaH)-promoted intramolecular etherification. Although both BF 3  ⋅ OEt 2 and NaH are found to be efficient for this transformation, slightly better yields and less reaction times are achieved with NaH/DMF (0.25-1 h at 100 °C) as compared to BF 3  ⋅ OEt 2 /DCM (2-3 h at 0 °C to rt). The evolution of this intramolecular cyclization was studied by time-dependent NMR studies in CDCl 3 solvent. Further, these observations are supported by infrared (IR) spectral data. It is worth mentioning that the present methodology enables a new route to assemble highly fused oxa-cage systems by choosing suitably substituted oxa-cage compounds for the olefin-metathesis sequence. The highly fused oxa-cage systems may have potential applications in high-energy-density materials (HEDMs) and supramolecular chemistry., (© 2022 Wiley-VCH GmbH.)

An unprecedented photoredox-catalyzed phosphine-mediated deoxygenation of hexafluoroacetone hydrate was established to accomplish the hydroxylpolyfluoroalkylation of electron-deficient alkenes. A range of bis(trifluoromethyl)carbinols were facilely accessed by using readily available hexafluoroacetone hydrate, instead of toxic gaseous hexafluoroacetone. A range of electron-deficient alkenes are tolerated, giving the corresponding hydro-hydroxylpolyfluoroalkylated products in moderate to high yields. Remarkable features of this synthetic strategy include operational simplicity, mild reaction conditions, excellent regioselectivity, and broad functional group tolerance. The success of this strategy relies on the delicate utilization of aldehyde/ketone-gem-diol intrinsic equilibrium, which offers an innovated open-shell pathway for the assembly of synthetically challenging polyfluoroalkylated scaffolds., (© 2022 Wiley-VCH GmbH.)

The application of Suzuki-Miyaura coupling reaction to forge the atropisomeric biaryls has seen remarkable progress but exploration of this chemistry to directly forge chiral C(aryl)-C(alkene) axis is underdeveloped. The replacement of arene substrates by alkenes intensifies the challenges in terms of reactivity, configurational atropostability of product and selectivity control. By meticulous ligand design and fine-tuning of reaction parameters, we identified a highly active 3,3'-triphenylsilyl-substituted phosphite ligand to realize arene-alkene Suzuki-Miyaura coupling of hindered aryl halides and vinyl boronates under very mild conditions. The axially chiral acyclic aryl-alkenes were generated in commendable efficiency, enantioselectivity and E/Z selectivity., (© 2022 Wiley-VCH GmbH.)

An efficient catalytic asymmetric [2+2] cycloaddition of allenyl imide and mono- or disubstituted alkenes is disclosed. The key feature of this method is the use of bidentate allenyl imide and weakly activated and less steric hindered alkene pair by utilizing chiral magnesium(II) complex of N,N'-dioxide, which could provide through-space dispersion interactions to orientate the arrangement of the alkene. This protocol allows the generation of a series of axially chiral cyclobutenes and four-membered ring-containing spirocycles (80 examples) in high yield (up to 99 %) with excellent enantioselectivity (up to >99 % ee), and the late-stage modification of biologically active molecules as well. Experimental studies and DFT calculations revealed that this [2+2] cycloaddition proceeded via a stepwise mechanism involving a short-lived zwitterionic intermediate. The π-π interaction between the alkenes and the amide moiety in the ligand was crucial for the enantiocontrol., (© 2022 Wiley-VCH GmbH.)

Sulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining a range of functional molecules in an increasing number of fields. Herein, we established a metal-free linkage of unactivated alkenes and sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes. An intermolecular hydride transfer process is the key step, and it occurs via overlap of the LUMO in the sulfonimidoyl cation and HOMO in the unactivated alkene, which was confirmed via control experiments with deuterated compounds. DFT calculations further demonstrated the concerted process involving formation of the S-C(sp 3 ) bond and hydride transfer. Remarkably, abundant natural products and pharmaceuticals with multiple heteroatoms and sensitive functional groups have been subjected to the current linkage reaction to achieve various sulfoximine linkages, furnishing the basis for drug discovery and drug conjugation., (© 2022 Wiley-VCH GmbH.)

Reported herein is the efficient synthesis of tetra- and tri-substituted (Z)-fluoro- and (Z)-chloro-borylalkenes by the Boron-Wittig reaction of ketones and aldehydes with bench-top stable halo-diborylmethanes. The substrate scope is broad and the Boron-Wittig reaction proceeds from a diverse range of ketones and aldehydes including biologically relevant molecules with fluoro- or chloro-diborylmethanes, providing tetra- and tri-substituted (Z)-fluoro- and (Z)-chloro-borylalkenes in good yields with high stereoselectivity. The utilities of the obtained (Z)-fluoro- and (Z)-chloro-borylalkenes are highlighted by further modifications to afford fluoroalkene derivatives or all-carbon substituted alkene., (© 2022 Wiley-VCH GmbH.)

We report herein the three-component radical addition reaction of SF 5 Cl, alkene and diazo compounds for the selective formation of α-alkyl-α-SF 5 carbonyl compounds. The three-component addition reaction proceeded through the first reaction of SF 5 radical with the diazo compound followed by the addition of the in situ generated carbon radical to alkene. The synthetic useful α-allyl-α-SF 5 carbonyl compounds were successfully prepared when allyl trimethylsilanes were used as the alkene substrates. Furthermore, the three-component adducts formed from SF 5 Cl, α-diazoacetophenones and vinyl acetates were converted into pentafluorosulfanylfurans. This transformation provided a practical and efficeint method for the synthesis of pentafluorosulfanylfurans., (© 2022 Wiley-VCH GmbH.)

The Heck reaction between N-heteroaryl halides and heterocyclic alkenes provides a convenient approach to biologically relevant α-heteroaryl functionalized heterocycles, yet reactions of this type have been challenging due to strong N-heteroaryl coordination to palladium metal, which causes catalyst poisoning. In this report, an efficient palladium-catalyzed Heck reaction between N-heteroaryl halides and heterocyclic olefins is established, leading to a variety of α-heteroaryl substituted heterocycles. The method features an unprecedented broad substrate scope and excellent functional group compatibility. The employment of a sterically bulky P, P=O ligand containing an anthryl moiety is crucial for this transformation due to the coordinative unsaturation facilitated by its steric bulkiness. The asymmetric variant of the Heck reaction is achieved with (S)-DTBM-SEGPHOS via a cationic palladium pathway, which has enabled an efficient asymmetric synthesis of (S)-nicotine and its analogues., (© 2022 Wiley-VCH GmbH.)

We report herein a modular catalytic method for the efficient enantioselective synthesis of chiral allylboronates from abundant feedstock chemicals through an asymmetric 1,1-difunctionalization of alkenes. This protocol is distinguished by its use of an inexpensive chiral catalyst, mild and convenient reaction conditions, wide substrate scope, scalability and practicality. The utility of this method is demonstrated by the rapid synthesis of key intermediates of complex drug molecules. Mechanistic studies reveal that β-H elimination is a highly regioselective step and the reversible homolysis and convergance to the lower energy pre-reductive elimination intermediate is the enantio-determining step., (© 2022 Wiley-VCH GmbH.)

We report a novel asymmetric radical cyclization of alkenes via stereospecific homolytic substitution of sulfinamides. This reaction produces a variety of cyclic sulfinamides with excellent stereocontrol. The protocol features broad functional group tolerance, high product diversity, and easy accessibility to feedstocks, and outlines a new pathway for the synthesis of chiral cyclic sulfinamides., (© 2022 Wiley-VCH GmbH.)

We herein report the preparation of solid and salt-stabilized silylzinc pivalates from the corresponding silyllithium reagents via transmetalation with Zn(OPiv) 2 . These resulting organosilylzinc pivalates show enhanced air and moisture stability and unique reactivity in the silylative difunctionalization of alkenes. Thus, a practical chelation-assisted nickel-catalyzed regioselective alkyl and benzylsilylation of alkenes has been developed, which provides an easy method to access alkyl silanes with broad substrate scope and wide functional group compatibility. Kinetic experiments highlight that the OPiv-coordination is crucial to improve the reactivity of silylzinc pivalates. Furthermore, late-stage functionalizations of druglike molecules and versatile modifications of the products illustrate the synthetical utility of this protocol., (© 2022 Wiley-VCH GmbH.)

Palladium-catalysed diastereoselective hydroesterification of alkenes assisted by the coordinative hydroxyl group in the substrate afforded a variety of chiral γ-butyrolactones bearing two stereocenters. Employing the carbonylation-lactonization products as the key intermediates, the route from the alkenes with single chiral center to chiral THF-fused bicyclic γ-lactones containing three stereocenters was developed., (© 2021 Wiley-VCH GmbH.)

In the context of new scaffolds obtained by photochemical reactions, Paternò-Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich alkenes to give oxetanes are described. A comprehensive study has then been carried out on the reaction of aromatic ketones with fluorinated alkenes. Depending on the substitution pattern at the oxetane ring, a metathesis reaction is described as a minor side process to give mono fluorinated alkenes. Overall, this last reaction corresponds to a photo-Wittig reaction and yield amid isosteres. In order to explain the uncommon regioselectivity of the Paternò-Büchi reaction with these alkenes, electrostatic-potential derived charges (ESP) have been determined. In a second computational study, the relative stabilities of the typical 1,4-diradical intermediates of the Paternò-Büchi reaction have been determined. The results well explain the regioselectivity. Further transformations of the oxetanes or previous functionalization of the fluoroalkenes open perspectives for oxetanes as core structures for biologically active compounds., (© 2021 Wiley-VCH GmbH.)

[Display omitted] • Pine needles lignocellulosic active paper incorporated with nanozeolite was fabricated. • The lignocellulosic paper showed improved water vapor transmission rate. • The lignocellulosic paper showed high ethylene scavenging properties. • Active pine needle based paper suitable for fresh produce active packaging. • Studies indicated valorization of pine needles biomass into paper fabrication. The pines needle falls approximately 2–3 ha−1 year−1 on the forest floors resulting in a considerable amount of lignocellulosic biowaste. The present study aimed to develop pine needles based lignocellulosic active paper and investigate the effect of 5, 20, and 30% (v/w) nano zeolite addition on the physical, mechanical, and microstructural property of the papers. The developed papers were characterized by scanning electron microscope, transmission electron microscope, Fourier transform infrared spectrometer, and X-ray diffraction. As the zeolite concentration was increased from 5% to 30% in the paper, enhanced water permeability was seen from 5.18 ± 0.34 - 3.88 ± 0.33 g/cm2/day (PN/ZL 30% paper). The addition of 5% zeolite increased the tensile and burst strength from 19.53 ± 3.53 Nm/g and 3.63 ± 0.23 kg/cm2, respectively. The porosity was increased from 340 ± 20 to 1170 ± 60, and Cobb value increased from 338.3 ± 1.5- 406.7 ± 1.5 g/m2. The alterations in terms of surface microstructure in the paper with 20, 30% zeolite were noticed whereas XRD illustrated the high compatibility among the lignocellulosic network of pines and zeolite. The pine needle paper with 30% zeolite possessed remarkable ethylene scavenging properties (62%), opening a way to valorize pine needle waste for food packaging application. [ABSTRACT FROM AUTHOR]

The redox-neutral dicarbofunctionalization of tri- and tetrasubstituted olefins to form a variety of (hetero)cyclic compounds under photoinduced palladium catalysis is described. This cascade reaction process was used to couple styrenes or acryl amides with a broad range of highly decorated olefins tethered to aryl or alkyl bromides (>50 examples). This procedure enables one or two contiguous all-carbon quaternary centers to be formed in a single step. The products could be readily diversified and applied in the synthesis of a bioactive oxindole analogue., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Summary: The object of this study is the manufacturing processes and fluorinated ethylene propylene (FEP) contents on the cell performance of the proton exchange membrane fuel cell (PEMFC). These results are useful for optimizing gas diffusion layer (GDL) fabrication processes and the operating conditions of the PEMFC. A traditional GDL with a micro porous layer (MPL) can enhance the water management ability. For the case of the one‐stage GDL manufacturing process, carbon paper with an FEP content of 10 wt% has the best fuel cell performance and limiting current density. Besides, in the two‐stage GDL fabrication process, when the cathode fuel is air, carbon paper with the same 10 wt% FEP content can delay the occurrence of limiting current density. The types of carbon black have remarkable influences on water management capabilities. It is noted that the XC‐72R carbon powder has a relatively appropriate pore volume to have enough water to keep the membrane moist and avoid water flooding. The higher the gas humidification temperature, the faster the electrochemical reaction rate. But when the operating current density is high, it will generate too much water, resulting in water flooding and a decrease in the PEMFC performance. Therefore, when the cathode fuel is air and the inlet humidification temperature is 80°C for the anode and 50°C for the cathode, the limiting current density can be effectively extended to maintain the cell performance. [ABSTRACT FROM AUTHOR]

Hydrogenating CO2 to produce light olefins is a highly promising route for olefin synthesis. However, the premise of achieving a high yield is to develop a catalyst with a high conversion rate, selectivity, and stability. This paper reports a Ca2−xKxFe2O5 catalyst with an CO2 conversion of up to 46%, a light olefin selectivity of 34.59%, and an olefin-alkane molar ratio of 8.31. Ca addition increased the oxygen vacancy concentration and strong basic sites of the catalyst, resulting in improved HCOO* intermediate formation, better CO selectivity, and higher CO2 conversion rates. Meanwhile, the addition of K further enhanced the rate of CO2 conversion while also improving the selectivity of light olefins by promoting C–C coupling. Furthermore, the Ca1.0K1.0Fe2O5 catalyst demonstrated no notable deactivation over a period of 72 h, indicating the strong industrial potential of this catalyst. [ABSTRACT FROM AUTHOR]

[Display omitted] • NiO-Al 2 O 3 based structured catalysts were tested in the ODH of ethane. • Three ceramic structures were used as substrates: a monolith, a foam and a paper. • Different NiO physicochemical properties were obtained within the substrates. • The systems with the stronger NiO-Al 2 O 3 interactions were the most selective. • The addition of Ce generated a marked productivity increment. Structured catalysts have important advantages compared to powder formulations and they are required for processes intensification. In this work, three different ceramic structures: a cordierite monolith, an alumina foam and an alumina-silica paper were used as substrates for the deposition of a NiO-Al 2 O 3 coating and tested in the oxidative dehydrogenation of ethane to produce ethylene. For comparison, a NiO-Al 2 O 3 powder catalyst was also prepared. Nickel oxide species with different physicochemical features were obtained over each structure, evidenced by morphological (SEM-EDX) and physicochemical characterization (XRD, LRS and XPS). The best distributions of the catalytic coatings and NiO physicochemical properties were obtained when the monolith and the foam were used as substrates. These led to higher NiO-Al 2 O 3 interactions and consequently to high ethylene selectivity values, 70–90 %, corresponding to the former an ethane conversion of 22 % and to the latter a 5 %. The distribution of the active phase on the ceramic paper was heterogeneous, with NiO agglomerations and poor NiO-support interaction thus achieving low olefin selectivity (∼ 30 %). The addition of a second element such as cerium was also studied in those structured catalysts with high selectivity, resulting in both cases in an increment of ethane conversion but a decrease in ethylene selectivity. This behavior was attributed to the generation of electrophilic oxygen species. [ABSTRACT FROM AUTHOR]

The DIBAL-H reduction of the Baylis-Hillman sugar adduct, obtained from 3-O-benzyl-1,2-isopropylidene-α-D-xylo-pentodialdo-1,4-furanose yielded trisubstituted alkenes by eliminating the β-hydroxyl group. Subsequently, the hydrolysis of the isopropylidene acetal to the corresponding hemiacetal was reacted with N-benzyl hydroxylamine hydrochloride to generate the nitrone, which underwent diastereoselective intramolecular 1,3-dipolar nitrone olefin cycloaddition (INOC) to give an isoxazolidine skeleton. The concomitant reductive cleavage of the N-O bond and benzyl group of the fused isoxazolidines afforded new functionalized aminocyclopentitols in good yields., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Rajendra Rohokale reports administrative support and equipment, or supplies were provided by the University of Florida. Rajendra Rohokale reports a relationship with the University of Florida that includes: employment (Research Scientist). I have no conflicts of interest to disclose. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The effect of halide substitution in Grubbs-Hoveyda II catalysts (GHII catalysts) embedded in the engineered β-barrel protein nitrobindin (NB4exp) on metathesis activity in aqueous media was studied. Maleimide tagged dibromido and diiodido derivates of the GHII catalyst were synthesized and covalently conjugated to NB4exp. The biohybrid catalysts were characterized spectroscopically confirming the structural integrity. When the two chloride substituents at ruthenium center were exchanged against bromide and iodide, the diiodo derivative was found to show significantly higher catalytic activity in ring-closing metathesis of α,ω-diolefins, whereas the dibromido derivative was less efficient when compared with the parent dichlorido catalyst. Using the diiodido catalyst, high turnover numbers of up to 75 were observed for ring-closing metathesis (RCM) yielding unsaturated six- and seven-membered N-heterocycles., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jun Okuda reports financial support was provided by BMBF Bundesministerium für Bildung und Forschung. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Inc.)

Stimulator of Interferon Genes (STING) is essential for the inflammatory response to cytosolic DNA. Despite that aberrant activation of STING is linked to an increasing number of inflammatory diseases, the development of inhibitors has been challenging, with no compounds in the pipeline beyond the preclinical stage. We previously identified endogenous nitrated fatty acids as novel reversible STING inhibitors. With the aim of improving the specificity and efficacy of these compounds, we developed and tested a library of nitroalkene-based compounds for in vitro and in vivo STING inhibition. The structure-activity relationship study revealed a robustly improved electrophilicity and reduced degrees of freedom of nitroalkenes by conjugation with an aromatic moiety. The lead compounds CP-36 and CP-45, featuring a β-nitrostyrene moiety, potently inhibited STING activity in vitro and relieved STING-dependent inflammation in vivo. This validates the potential for nitroalkene compounds as drug candidates for STING modulation to treat STING-driven inflammatory diseases, providing new robust leads for preclinical development., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Francisco J Schopfer reports a relationship with Creegh Pharmaceuticals Inc that includes: board membership and equity or stocks. Francisco J Schopfer & Fei Chang reports a relationship with Furanica Inc that includes: board membership and equity or stocks. Christian K Holm reports a relationship with UV Medico that includes: consulting or advisory and employment. Francisco J Schopfer, Fei Chang, Christian K Holm, Anne Louise Hansen, Sonia R Salvatore, Luis Villacorta are the inventors of a patent application related to the subject matter of this manuscript. The University of Pittsburgh is the lead institution for this patent application, with joint ownership also held by Aarhus University and Morehouse School of Medicine. Other authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Ethnopharmacological Relevance: Tripterygium wilfordii polyglycosides (TWP) tablet is the most widely used traditional Chinese medicine preparation for the treatment of rheumatoid arthritis (RA), but the hepatotoxicity often limits its widespread application. In traditional use, Salvia miltiorrhiza has cardioprotective and hepatoprotective effects. Salvianolic acid extract (SA) is a hydrophilic component of Salvia miltiorrhiza and has significant antioxidant and hepatoprotective effects., Aim of the Study: To investigate the protective effects of SA on the TWP-induced acute liver injury in rats and to explore the related mechanisms by integration of metabolomics and transcriptomics., Materials and Methods: SA and TWP extracts were identified by UPLC-Q/TOF-MS. SA (200 mg/kg) was administered for consecutive 7 days. On day 7, TWP (360 mg/kg) was administered by gavage to induce the acute liver injury in rats. Serum biochemical assay and H&E staining were used to evaluate liver damage. Liver metabolomics and transcriptomics were used to explore the potential mechanisms, and further molecular biological experiments such as qPCR and IHC were utilized to validate the relevant signaling pathways., Results: SA can prevent liver injury symptoms caused by TWP, such as elevated liver index, elevated ALT and AST, and pathological changes in liver tissue. Liver metabolomics studies showed that TWP can significantly alter the content of individual bile acid in the liver and SA had the most significant impact on the biosynthetic pathway of bile acids. The transcriptomics results of the liver indicated that the genes changed in the SA + TWP group were mainly involved in sterol metabolism, lipid regulation and bile acid homeostasis pathways. The gene expression of Nr1h4, which encodes farnesoid X receptor (FXR), an important regulator of bile acid homeostasis, was significantly changed. Further studies confirmed that SA can prevent the downregulation of FXR and its downstream signaling induced by TWP, thereby regulating bile acid metabolism, ultimately preventing acute liver injury caused by TWP., Conclusion: Our results demonstrated that SA could protect the liver from TWP-induced hepatic injury by modulation of the bile acid metabolic pathway. SA may provide a new strategy for the protection against TWP-induced acute liver injury., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microbial cell factories are an attractive alternative to produce high-value natural products using sustainable processes. However, product recovery is one of the main challenges to reduce production cost and make these technologies economically interesting. In this work, new resins were formulated to 3D print hydrophobic adsorbents for the recovery of biologics from microbial cultivations. Benzyl methacrylate (BEMA) and butyl methacrylate (BUMA) were selected as functional monomers suitable for the adsorption of hydrophobic compounds. Pore morphology was tailored through the inclusion of pore forming agents (porogens) in the resin. Different porogens and porogen concentrations were evaluated resulting in materials with different porous networks. Sudan 1 and the anticancer drug paclitaxel were employed as model compounds to test the adsorption performance of hydrophobic and terpene molecules onto the developed 3D printed materials. The material with greatest adsorption capacity was obtained using BEMA monomer with 40 % (v/v) porogen (BEMA40). The performance of BEMA40 to recover taxadiene from small-scale (5 mL) Saccharomyces cerevisiae cultivations was tested and compared with commercial Diaion HP-20 beads. Taxadiene titres on BEMA40 (46 ± 2 mg/L) and Diaion HP-20 (54 ± 4 mg/L) were comparable, with no taxadiene detected in the cells and cell-free media, suggesting near 100 % taxadiene partition on the adsorbents. Compared to commercial beads, 3D printed adsorbents can be customized with adjustments in the resin formulation, are well adaptable to diverse bioreactor types, do not clog sampling ports and columns and are easier to handle during post processing. The results of this work demonstrate the potential of 3D printing to fabricate hydrophobic interaction adsorbent materials and their application in the recovery of biological products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Microbial biodegradation of commercially available poly(butylene adipate-co-terephthalate)-polylactic acid-thermoplastic starch based bio-plastic has been pursued at high temperatures exceeding 55 °C. Herein, we first reported three newly isolated fungal strains from farmland soil samples of Republic of Korea namely, Pyrenochaetopsis sp. strain K2, Staphylotrichum sp. S2-1, and Humicola sp. strain S2-3 were capable of degrading a commercial bio-plastic film with degradation rates of 9.5, 8.6, and 12.2%, respectively after 3 months incubation at ambient conditions. Scanning electron microscopy (SEM) analyses showed that bio-plastic film was extensively fragmented with severe cracking on the surface structure after incubation with isolated fungal strains. X-ray diffraction (XRD) analysis also revealed that high crystallinity of the commercial bio-plastic film was significantly decreased after degradation by fungal strains. Liquid chromatography-mass spectrometry (LC-MS) analyses of the fungal culture supernatants containing the bio-plastic film showed the peaks for adipic acid, terephthalic acid (TPA), and terephthalate-butylene (TB) as major metabolites, suggesting cleavage of ester bonds and accumulation of TPA. Furthermore, a consortium of fungal strain K2 with TPA degrading bacterium Pigmentiphaga sp. strain P3-2 isolated from the same sampling site exhibited faster degradation rate of the bio-plastic film within 1 month of incubation with achieving complete biodegradation of accumulated TPA. We assume that the extracellular lipase activity presented in the fungal cultures could hydrolyze the ester bonds of PBAT component of bio-plastic film. Taken together, the fungal and bacterial consortium investigated herein could be beneficial for efficient biodegradation of the commercial bio-plastic film at ambient conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Green polymeric foams are an important research topic for sustainable development. In this study, a natural multifunctional flame-retardant additive based on food waste was developed and evaluated for its ability to replace the commercial additives tricresyl phosphate (TCP) and trioctyl phosphate (TOP) in a polylactide/poly(butylene adipate-co-terephthalate) (PLA/PBAT) foam. A series of blend foams with additives were prepared by melt extrusion. According to the results, the blend foam with 20 phr of TCP showed the best combination of impact toughness and flame retardancy. TCP, however, poses health and environmental risks. Therefore, natural flame retardants (NFRs) were used to partially replace the commercial flame retardant (CFR). A combination of TCP and soybean residue (SB) produced an impact toughened and flame-retardant blend foam. When compared to the neat PLA/PBAT foam, the impact toughness of the best sample was increased by about 256 %. The optimal foam showed excellent flame resistance with a V-0 UL-94 rating and a high LOI value (31.8 %). SB has the potential to partially replace TCP as flame retardant and could be used in a broad range of PLA/PBAT foam applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Blending poly (butylene adipate-co-terephthalate) (PBAT) and polylactic acid (PLA) is a cost-effective strategy to obtain biodegradable plastic with complementary properties. However, the incompatibility between PBAT and PLA is a great challenge for fabricating high-performance composite films. Herein, the ethyl acetate fractionated lignin with the small glass transition temperature and low molecular weight was achieved and incorporated into the PBAT/PLA composite as a compatibilizer. The fractionated lignin can be uniformly dispersed within the PBAT/PLA matrix through a melt blending process and interact with the molecular chain of PBAT and PLA as a bonding bridge, which enhances the intermolecular interactions and reduces the interfacial tension of PBAT/PLA. By adding fractionated lignin, the tensile strength of the PBAT/PLA composite increased by 35.4 % and the yield strength increased by 37.7 %. Owing to lignin, the composite films possessed the ultraviolet shielding function and exhibited better water vapor barrier properties (1.73 ± 0.08 × 10 -13  g·cm/cm 2 ·s·Pa). This work conclusively demonstrated that fractionated lignin can be used as a green compatibilizer and a low-cost functional filler for PBAT/PLA materials, and provides guidance for the application of lignin in biodegradable plastics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Marine microorganisms have been reported to degrade microplastics. However, the degradation mechanisms are still poorly understood. In this study, a bacterium Roseibium aggregatum ZY-1 was isolated from seawater, which can degrade poly(butylene adipate-co-terephthalate) (PBAT). The PBAT-PLA(polylactic acid, PLA) films, before and after degradation, were characterized by scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FTIR), the weight loss rate and water contact angle were measured. The results indicate that ZY-1 colonized on PBAT-PLA film, changed the functional groups and decreased water contact angle of PBAT-PLA film. Moreover, liquid chromatography mass spectrometry (LC-MS) analysis reveales that PBAT was degraded into its oligomers (TB, BTB) and monomers (T, A) during 10 days, and adipic acid (A) could be used as a sole carbon source. The whole genome sequencing analyses illustrate the mechanisms and enzymes such as PETase, carboxylesterases, arylesterase (PpEst) and genes like pobA, pcaBCDFGHIJKT, dcaAEIJK, paaGHJ involved in PBAT degradation. Therefore, the R. aggregatum ZY-1 will be a promising candidate of PBAT degradation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Synthetic radicals have intrinsic power for cascading and multifunctional reactions to construct diverse molecular scaffolds. In the previous review series, we covered 1,2-difunctionalizations, remote 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalizations, addition followed by cyclization reactions, and cycloaddition-initiated difunctionalizations. Presented in this paper are radical addition-initiated trifunctionalization reactions of alkenes, alkynes, and their derivatives. After the initial radical addition, there are different pathways, such as group or hydrogen atom transfer, cyclization, and radical coupling, to complete the second and third functionalizations. [ABSTRACT FROM AUTHOR]

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 199 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOx), on the following-day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation, and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more fully chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOx, VOCs and chlorine-containing constituents. [ABSTRACT FROM AUTHOR]

Methyltrioxorhenium(VII) (MTO) is a widely employed catalyst for metathesis, olefination, and most importantly, oxidation reactions. It is often preferred to other oxometal complexes due to its stability in air and higher efficiency. The seminal papers of K. B. Sharpless showed that when pyridine derivatives are used as co-catalysts, MTO-catalyzed olefin epoxidation with H2O2 as oxidant, a particularly useful reaction, is accelerated, with pyridine speeding up catalytic turnover and increasing the lifetime of MTO under the reaction conditions. In this paper, combined experimental and theoretical results show that the occurrence of σ-hole interactions in catalytic systems extends to MTO. Four crystalline adducts between MTO and aliphatic and heteroaromatic bases are obtained, and their X-ray analyses display short Re⋯N/O contacts opposite to both O–Re and C–Re covalent bonds with geometries consistent with σ-hole interactions. Computational analyses support the attractive nature of these close contacts and confirm that their features are typical of σ-hole interactions. The understanding of the nature of Re⋯N/O interactions may help to optimize the ligand-acceleration effect of pyridine in the epoxidation of olefins under MTO catalysis. [ABSTRACT FROM AUTHOR]

As one of the traditional Chinese herbs, Danshen ( Salvia miltiorrhiza Bunge) has been widely studied and widely used in the treatment of cardiovascular, cerebrovascular, and other immune diseases. Tanshinones and salvianolic acids isolated from Danshen are considered to be the main components of its biological activity and pharmacology that play important roles in increasing the index of immune organs, regulating the number and function of immune cells, and releasing immunoreactive substances. Especially tanshinone IIA, cryptotanshinone, salvianolic acid B, and rosmarinic acid show good biological activity in treating rheumatoid arthritis, some immune-mediated inflammatory diseases, psoriasis, and inflammatory bowel disease. In order to understand their pharmacological effects and provide references for future research and clinical treatment, the regulation of immune response by tanshinones and salvianolic acids is summarized in detail in this paper. In addition, the challenges in their pharmacological development and the opportunities to exploit their clinical potential have been documented.

How to effectively improve the poor interfacial adhesion between polylactic acid/poly(butylene adipate-co-terephthalate) (PLA/PBAT) matrix and thermoplastic starch (TPS) is still a challenge. Therefore, this work aims to introduce a convenient method to enhance the performance of PLA/PBAT/TPS blend by melt reactive extrusion. Here, using 4,4'-methylene-bis(N,N-diglycidyl-aniline) (MBDG) containing four epoxy groups as a reactive compatibilizer, and respectively using 1-methylimidazole (MI) or triethylenediamine (TD) as a catalyzer, serial PLA/PBAT/TPS ternary bio-composites are successfully prepared via melt reactive extrusion. The results showed that, under the catalysis of organic base, especially MI, the epoxy groups of MBDG can effectively react with hydroxyl and carboxyl groups of PLA/PBAT and hydroxyl groups in TPS to form chain-expanded and cross-linked structures. The tensile strength of the composites is increased by 20.0 % from 21.1 MPa, and the elongation at break is increased by 182.4 % from 17.6 % owing to the chain extension and the forming of cross-linked structures. The molecular weight, thermal stability, crystallinity, and surface hydrophobicity of the materials are gradually improved with the increase of MBDG content. The melt fluidity of the composites is also improved due to the enhancement of compatibility. The obtained PLA/PBAT/TPS materials have the potential to be green plastic products with good properties., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The preparation and characterization of lignin nanoparticles (LNPs) were described. LNPs were produced via the precipitation technique. Nanocomposites of LNPs with poly (butylene adipate-co-terephthalate) (PBAT) were prepared by melt mixing with various concentrations up to 6 wt% of LNPs. The assessment of the effects of LNP addition on the mechanical, thermal, morphological, cytotoxicity, antioxidant, antibacterial, and antiviral properties of nanocomposites was carefully performed. The addition of LNPs to PBAT enhances the thermal stability of the nanocomposites. The antioxidant effect of LNPs on PBAT increased with increasing filler content. LNPs showed higher efficiency as antioxidant agents than lignin particles (LP). The tensile modulus increased by 20 % for the nanocomposites with 6 % LNPs in comparison with neat PBAT. The crystallization peak temperature of PBAT was 80 °C, which increased to 104.6 °C with the addition of 6 wt% of LNPs, suggesting their strong nucleation activity. Antibacterial tests demonstrated the bacteriostatic activities of LNP, LP, and nanocomposites. Both LP and LNP showed considerable antiviral activity against herpes simplex virus type 1 and human coronavirus 229e. The antiviral activity of LNP was concentration-dependent. The findings suggest that LNP is a promising bio-additive for PBAT and can enhance its properties for various applications, including food packaging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The wide application of fully biodegradable polylactic acid/polybutylene terephthalate (PLA/PBAT) blends in environmentally friendly packaging were limited because of poor compatibility. Normal compatibilizers suffer from poor thermal stability and non-biodegradability. In this work, epoxy copolymer (MDOG) with different molecular structures were made of 2-methylene-1, 3-dioxoheptane, and glycidyl methacrylate as raw materials by free radical copolymerization. MDOG copolymers have good biodegradability and a high thermal decomposition temperature of 361 °C. The chemical reaction of the epoxy groups in MDOG with PLA and PBAT during the melting reaction improved the interfacial bonding by decreasing the particle size of PBAT. Compared to the PLA/PBAT blends, the tensile strength and fracture toughness of PLA/PBAT/MDOG blends were enhanced to 34.6 MPa and 115.8 MJ/m 3 , which are 25 % and 81 % higher, respectively. As a result, this work offers new methods for developing thermally stable and biodegradable compatibilizers, which will hopefully promote the development of packaging industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The olive fruit fly Bactrocera oleae, is the major key pest of olive groves worldwide. As an odor-driven species, its intraspecific communication has been thoroughly investigated, yielding a combination of spiroacetals, esters and hydrocarbons. However, its management with pheromone is still restricted to olean, the major pheromone component. Given the crucial role of circadian rhythm and pheromone blends in mediating flies reproductive behavior compared to single compounds, B. oleae headspace chemical profile was carefully examined, through the combination of Proton Transfer Reaction Time of Flight Mass Spectrometry (PTR-ToF) and Gas Chromatography coupled with Mass Spectrometry (GC-MS). This novel approach aimed at continuously investigating the temporal scale of volatilome profile of B. oleae individuals, as well as the determination of new candidate sex-borne compounds (particularly those emitted in traces or having low molecular weight), that may be relevant to the fly's chemical communication and were unreported due to limitations of frequently used analytical techniques. Our results describe the dynamics and diversity of B. oleae chemical profile, highlighting the emission of 90 compounds, with clear diel rhythm of release, of known pheromone components of B. oleae (e.g., olean, alpha-pinene and muscalure) and new candidates. In contrast to ammonia, acetaldehyde and muscalure, which were highly emitted during the afternoon by males and mixed groups, olean was mostly released by mature females and mixed groups, with a peak of emission during early-morning and afternoon. This emission of olean around dawn is reported for the first time, suggesting early-morning mating activity in B. oleae. Furthermore, esters, such as methyl tetradecanoate, which had been earlier identified as a pheromone for B. oleae, did not exhibit any discernible release patterns. These findings are the first to demonstrate the emission of chemicals, which are only produced when males and females are close to one another, with an emission peak during the afternoon (mating period), and that may have aphrodisiac properties for B. oleae males. These results emphasize the relevance of compounds with distinct diel rhythm and address their potential function as intraspecific messengers, according to their source and timing of release., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

China's growing demand for bulk chemicals and concerns regarding energy security are scaling up coal-to-olefins (CTO) production. Three generations of independent dimethyl ether/methanol-to-olefins technologies have been successively launched with greatly improved production efficiencies. However, to date, widespread concerns regarding the intensive environmental impacts and potential economic risks have not been addressed in the context of this industrialization. Here we show that, through the technological progress from the first to the third generation, life cycle energy consumption, water consumption, and carbon emissions can be reduced to 119.5 GJ/t, 27.6 t/t, and 9.1 t CO 2 -eq/t, respectively, and human health damage, ecosystem quality damage, and resource scarcity impacts can be decreased by 40.5 %, 50.1 %, and 16.4 %, respectively. This is accompanied by an excellent performance in terms of production cost, net present value, and internal return rate at 792.5 USD/t, 173.4 USD/t, and 19.4 %, respectively. Substantial environmental and economic benefits can be gained by coupling renewables in the form of using green hydrogen from solar and wind power to synthesize methanol. Particularly, life cycle carbon emissions and resource scarcity impacts are reduced by 23.4 % and 22.4 %, respectively, exceeding the reduction in technological progress. However, coupling renewables increases the life cycle energy consumption to 154.5 GJ/t, counteracting the benefits of technological progress. Our results highlight the importance of technological progress and coupled renewables for enhancing the sustainability of the CTO industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The effectiveness of biofertilizers as a cost-effective crop yield enhancer can be compromised by residual soil pollutants. However, the impact of accumulated polyadipate/butylene terephthalate microplastics (PBAT-MPs) from biodegradable mulch films on biofertilizer application and the consequent growth of crop plants remains unclear. Here, the effects of different levels of PBAT-MPs in soil treated with Bacillus amyloliquefaciens biofertilizer were assessed in a four-week potted experiment. PBAT-MPs significantly decreased the growth-promoting effect of the biofertilizer on Brassica chinensis L., resulting in a notable reduction in both above- and belowground biomass (up to 52.91% and 57.53%, respectively), as well as nitrate and crude fiber contents (up to 12.18% and 13.64%, respectively). In the rhizosphere microenvironment, PBAT-MPs increased soil organic carbon by 2.63-fold and organic matter by 2.68-fold, while enhancing sucrase (from 67.55% to 108.89%) and cellulase (from 31.26% to 49.10%) activities. PBAT-MPs also altered the rhizospheric bacterial community composition/diversity, resulting in more complex microbial networks. With regard to microbial function, PBAT-MPs impacted carbon metabolic function by inhibiting the 3-hydroxypropionate/4-hydroxybutyrate fixation pathway and influencing chitin and lignin degradation processes. Overall, the rhizospheric microbial profiles (composition, function, and network interactions) were the main contributors to plant growth inhibition. This study provides a practical case and theoretical basis for rational use of biodegradable mulch films and indicates that the residue of biodegradable films needs pay attention., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Ultrasonic-assisted activated carbon separation (UACS) was first employed to improve product quality by regulating adsorption rate and removing bacterial endotoxin from salvia miltiorrhizae injection. The adsorption rate was related to three variables: activated carbon dosage, ultrasonic power, and pH. With the increase of activated carbon dosage from 0.05 % to 1.0 %, the adsorption rates of salvianolic acids and bacterial endotoxin increased simultaneously. The adsorption rates at which bacteria endotoxins increased from 52.52 % to 97.16 % were much higher than salvianolic acids. As the ultrasonic power increased from 0 to 700 W, the adsorption rates of salvianolic acids on activated carbon declined to less than 10 %, but bacterial endotoxin increased to more than 87 %. As the pH increased from 2.00 to 8.00, the adsorption rate of salvianolic acid dropped whereas bacterial endotoxin remained relatively stable. On the basis of response surface methodology (RSM), the optimal separation conditions were established to be activated carbon dose of 0.70 %, ultrasonic power of 600 W, and pH of 7.90. The experimental adsorption rates of bacterial endotoxin were 94.15 %, which satisfied the salvia miltiorrhizae injection quality criterion. Meanwhile, salvianolic acids' adsorption rates were 1.92 % for tanshinol, 4.05 % for protocatechualdehyde, 2.21 % for rosmarinic acid, and 3.77 % for salvianolic acid B, all of which were much lower than conventional activated carbon adsorption (CACA). Salvianolic acids' adsorption mechanism on activated carbon is dependent on the component's molecular state. Under ideal separation conditions, the molecular states of the four salvianolic acids fall between 1.13 % and 6.60 %. The quality of salvia miltiorrhizae injection can be improved while maintaining injection safety by reducing the adsorption rates of salvianolic acids to less than 5 % by the use of ultrasound to accelerate the desorption mass transfer rate on the activated carbon surface. When activated carbon adsorption was used in the process of producing salvia miltiorrhizae injection, the pH of the solution was around 5.00, and the proportion of each component's molecular state was tanshinol 7.05 %, protocatechualdehyde 48.93 %, rosmarinic acid 13.79 %, and salvianolic acid B 10.28 %, respectively. The loss of useful components was evident, and the corresponding activated carbon adsorption rate ranged from 20.74 % to 41.05 %. The average variation rate in plasma His and IgE was significant (P < 0.05) following injection of 0.01 % activated carbon, however the average variation rate of salvia miltiorrhizae injection was dramatically decreased with the use of UACS and CACA (P > 0.05). The ultrasonic at a power intensity of 60 W/L and the power density of 1.20 W/cm 2 may resolve the separation contradiction between salvianolic acids and bacterial endotoxin, according to experiments conducted with UACS at different power intensities. According to this study, UACS has a lot of potential applications in the pharmaceutical manufacturing industry and may represent a breakthrough in the field of ultrasonic separation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

The thermocatalytic conversion of carbon dioxide (CO 2 ) into high value-added chemicals provides a strategy to address the environmental problems caused by excessive carbon emissions and the sustainable production of chemicals. Significant progress has been made in the CO 2 hydrogenation to long chain α-olefins, but controlling C-O activation and C-C coupling remains a great challenge. This review focuses on the recent advances in catalyst design concepts for the synthesis of long chain α-olefins from CO 2 hydrogenation. We have systematically summarized and analyzed the ingenious design of catalysts, reaction mechanisms, the interaction between active sites and supports, structure-activity relationship, influence of reaction process parameters on catalyst performance, and catalyst stability, as well as the regeneration methods. Meanwhile, the challenges in the development of the long chain α-olefins synthesis from CO 2 hydrogenation are proposed, and the future development opportunities are prospected. The aim of this review is to provide a comprehensive perspective on long chain α-olefins synthesis from CO 2 hydrogenation to inspire the invention of novel catalysts and accelerate the development of this process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

In steam cracking, upstream pyrolysis oil hydroprocessing, and in many downstream processes, olefinic content is key to assess process performance and process safety risk associated with highly exothermic reactions. When looking to plastic pyrolysis oils as a potential feedstock, as well as downstream products such as pyrolysis gasoline (pygas), these materials contain unsaturated hydrocarbons which are not present in fossil feedstocks. Pygas is a product of pyrolysis and exhibits a large number of chemical structural similarities with plastic pyrolysis oils, especially in terms of olefins structure. Quantification of the unsaturation content (olefins and di-olefins) is extremely important in industry, hence the focus of this manuscript. Detailed hydrocarbon analysis with flame ionization detection is inadequate to fully characterize the hydrocarbon composition of such samples, especially when peaks are closely eluting, or even co-eluting. In this study, the gas chromatography coupled to vacuum ultraviolet (GC-VUV) detection method previously described for the analysis of liquid hydrocarbon streams 1 and plastic pyrolysis oils 2 has been compared with comprehensive gas chromatography (GC × GC) and the industry standard for olefin quantification (i.e., bromine number titration). Although based on different methodologies, a correlation between the olefin content obtained from GC-VUV and the bromine number titration method is hereby presented., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Radical reactions are powerful in the synthesis of diverse molecular scaffolds bearing functional groups. In previous review articles, we have presented 1,2-difunctionalizations, remote 1,3-, 1,4-, 1,5-, 1,6- and 1,7-difunctionalizations, and addition followed by cyclization reactions. Presented in this paper is radical cyclization followed by the second functionalization reaction. The second functionalization could be realized by atom transfer reactions, radical or transition metal-assisted coupling reactions, and reactions with neutral molecules, cationic and anionic species. [ABSTRACT FROM AUTHOR]

The present paper reports a remote carbon‐to‐carbon boryl migration via an intramolecular 1,4‐B/Cu shift, which establishes an in situ stereospecific electrophilic trap on the alkene moiety. The synthetic application is developed to prepare functionalized cyclopentenes by means of a palladium‐catalyzed regioselective intramolecular coupling that completes a strategic cyclopropanation and generates valuable structural bicyclic systems. The mechanism is characterized by DFT (density functional theory) calculations which showed that the 1,4‐migration proceeds through an intramolecular, nucleophilic attack of the copper‐alkyl moiety on the boron atom bonded to the C(sp2), leading to a 5‐membered boracycle structure. The computation of the 1,3‐ and 1,4‐B/Cu shifts is also compared as is the impact of the endo‐ or exocyclic alkene on the reaction kinetics. [ABSTRACT FROM AUTHOR]

For regulating the olefin metathesis (OM) activity of the Hoveyda–Grubbs second-generation complex (HG-II), the structural modification of the benzylidene ligand is a useful strategy. This paper reports the effect of a chalcogen atom placed at the end of the benzylidene group on the catalytic properties of HG-II derivatives, using complexes with a thioether or ether component in the benzylidene ligand (ortho-Me-E-(CH2)2O-styrene; E = S, O). Nuclear magnetic resonance and X-ray crystallographic analyses of the complex with a thioether moiety (E = S) proved the (O,S)-bidentate and trans-dichlorido coordination for the complex. A stoichiometric ligand exchange between HG-II and the benzylidene ligand (E = S) produced the corresponding complex with an 86% yield, confirming higher stability of the complex (E = S) than that of HG-II. Despite the bidentate chelation, the complex (E = S) exhibited OM catalytic activity, indicating the exchangeability of the S-chelating ligand with an olefinic substrate. The green solution color, a characteristic of HG-II derivatives, was retained after the complex (E = S)-mediated OM reactions, indicating high catalyst durability. Conversely, the complex (E = O) rapidly initiated OM reactions; however, it showed low catalyst durability. In the OM reactions conducted in the presence of methanol, the complex (E = S) exhibited higher yields than the complex (E = O) and HG-II: the S-coordination increased the catalyst tolerance to methanol. A coordinative atom (such as sulfur) placed at the terminal of the benzylidene ligand can precisely regulate the reactivity of HG-II derivatives. [ABSTRACT FROM AUTHOR]

ZnZrOx has been used in large quantities for the preparation of light olefins from CO2, but the relationship between structure and performance remains unclear at present. In this paper, ZnZrOx were prepared by co-precipitation method, and a series of oxides with different sizes were prepared by varying the calcination temperatures. Subsequently, these oxides were combined with SAPO-34 to create a composite bifunctional catalyst for the synthesis of light olefins by CO2 hydrogenation, in which the impact of nanocrystal size effect was examined. The catalytic performance significantly increased as the nanocrystal size reduced from 18 to 12 nm. However, when the nanocrystal size was further decreased to 8 nm, the catalytic performance decline. Characterizations revealed a gradual increase in the number of oxygen vacancies with decreasing nanocrystal size. However, the oxide with the smallest nanocrystal size, prepared by varied calcination temperatures, did not yield the optimal catalytic performance due to sintering occurring during the reaction process. The results show that the assumption that smaller nanocrystal sizes inherently equate to improved catalytic performance is not universally valid, and stability must be considered when the nanocrystal size is decreased. The bifunctional catalysts used in this paper for the prepared light olefins from CO2 in yield as high as 13.8%, which is higher than most previous reports. [ABSTRACT FROM AUTHOR]