Glutaraldehyde-crosslinked Rhizopus oryzae whole cells show improved catalytic performance in alkene epoxidation.

BACKGROUND: Existing methods for alkene epoxidation are based on lipase-catalysed perhydrolysis. However, the inactivation of the expensive lipase enzyme is problematic for enzymatic epoxidation at large scales due to the use of hydrogen peroxide and peracids at high concentrations in the reaction. The immobilisation of whole cells appears to be a promising approach to alleviate this problem. RESULTS: A green oxidation system containing hydrogen peroxide, Na3C6H5O7, an acyl donor, and glutaraldehyde (GA)-crosslinked cells of Rhizopus oryzae was developed for the epoxidation of alkenes. GA-crosslinked cells of Rhizopus oryzae were adopted as a biocatalyst into the epoxidation system. A variety of alkenes were oxidised with this system, with a 56-95% analytical yield of the corresponding epoxides. The catalytic performance of the crosslinked treated cells was substantially improved compared to that of the untreated cells and the initial reaction rate increased from 126.71 to 234.72 mmol/L/h, retaining 83% yields even after four batches of reactions. The addition of 3.5 mmol Na3C6H5O7 not only acts as an acid-trapping reagent to eliminate the negative effect of the carboxylic acid on the alkene oxide but also forms a saturated salt solution with the aqueous phase, affecting the concentration of H2O2 in the three phases and thus the epoxidation reaction. Organic solvents with a logP value > 0.68 were good at producing hydroxy peracids; however, this method is only suitable for oxidation in a two-liquid phase. CONCLUSIONS: Compared with other lipase biocatalysts, the GA-crosslinked whole-cell biocatalyst is inexpensive, readily available, and highly stable. Therefore, it can be considered promising for industrial applications.

Organogermanium Analogues of Alkenes, Alkynes, 1,3-Dienes, Allenes, and Vinylidenes.

In this review, the latest achievements in the field of multiply bonded organogermanium derivatives, mostly reported within the last two decades, are presented. The isolable Ge-containing analogues of alkenes, alkynes, 1,3-dienes, allenes, and vinylidenes are discussed, and for each class of unsaturated organogermanium compounds, the most representative examples are given. The synthetic approaches toward homonuclear multiply bonded combinations solely consisting of germanium atoms, and their heteronuclear variants containing germanium and other group 14 elements, both acyclic and cyclic, are discussed. The peculiar structural features and nonclassical bonding nature of the abovementioned compounds are discussed based on their spectroscopic and structural characteristics, in particular their crystallographic parameters (double bond length, trans-bending at the doubly bonded centers, and twisting about the double bond). The prospects for the practical use of the title compounds in synthetic and catalytic fields are also briefly discussed.

Application of Olefin Metathesis in the Synthesis of Carbo- and Heteroaromatic Compounds-Recent Advances.

The olefin metathesis reaction has found numerous applications in organic synthesis. This is due to a number of advantages, such as the tolerance of most functional groups and sterically demanding olefins. This article reviews recent advances in the application of the metathesis reaction, particularly the metathetic cyclization of dienes and enynes, in synthesis protocols leading to (hetero)aromatic compounds.

Kinetic Resolution of ß-Alkyl Phenylethylamine Derivatives through Palladium-Catalyzed, Nosylamide-Directed C-H Olefination.

Palladium-catalyzed C-H activation reactions have attracted the attention of organic researchers due to their unique high selectivity, broad functional group tolerance, and high efficiency, and they are widely used in natural products and asymmetric synthesis. Here, we report an example of enantioselective C-H alkenylation between ß-alkyl phenylethylamine compounds and styrenes with Boc-L-lle-OH as the ligand and nosylamide as the directing group. This reaction is applicable to styrene containing various electron-deficient and electron-donating substitutions and may be utilized for the synthesis of benzoazepine compounds.

Wittig and Wittig-Horner Reactions under Sonication Conditions.

Carbonyl olefinations are among the most important organic syntheses that form C=C bonds, as they usually have high yields and in addition offer excellent stereoselectivity. Due to these advantages, carbonyl olefinations have important pharmaceutical and industrial applications. These reactions contain an additional step of an α-functionalized carbanion to an aldehyde or ketone to produce alkenes, but syntheses performed using metal carbene complexes are also known. The Wittig reaction is an example of carbonyl olefination, one of the best ways to synthesize alkenes. This involves the chemical reaction between an aldehyde or ketone with a so-called Wittig reagent, for instance phosphonium ylide. Triphenylphosphine-derived ylides and trialkylphosphine-derived ylides are the most common phosphorous compounds used as Wittig reagents. The Wittig reaction is commonly involved in the synthesis of novel anti-cancer and anti-viral compounds. In recent decades, the use of ultrasound on the Wittig reaction (and on different modified Wittig syntheses, such as the Wittig-Horner reaction or the aza-Wittig method) has been studied as a green synthesis. In addition to the advantage of green synthesis, the use of ultrasounds in general also improved the yield and reduced the reaction time. All of these chemical syntheses conducted under ultrasound will be described further in the present review.

Synthesis and Application Dichalcogenides as Radical Reagents with Photochemical Technology.

Dichalcogenides (disulfides and diselenides), as reactants for organic transformations, are important and widely used because of their potential to react with nucleophiles, electrophilic reagents, and radical precursors. In recent years, in combination with photochemical technology, the application of dichalcogenides as stable radical reagents has opened up a new route to the synthesis of various sulfur- and selenium-containing compounds. In this paper, synthetic strategies for disulfides and diselenides and their applications with photochemical technology are reviewed: (i) Cyclization of dichalcogenides with alkenes and alkynes; (ii) direct selenylation/sulfuration of C-H/C-C/C-N bonds; (iii) visible-light-enabled seleno- and sulfur-bifunctionalization of alkenes/alkynes; and (iv) Direct construction of the C(sp)-S bond. In addition, the scopes, limitations, and mechanisms of some reactions are also described.

Catalytic Cross-Metathesis Reactions That Afford E- and Z-Trisubstituted Alkenyl Bromides: Scope, Applications, and Mechanistic Insights.

Stereochemically defined trisubstituted alkenes with a bromide and a methyl group at a terminus can be readily and stereoretentively derivatized through catalytic cross-coupling, affording unsaturated fragments found in many bioactive natural products. A direct method for generating such entities would be by stereocontrolled catalytic cross-metathesis (CM). Such methods are scarce however. Here, we present a stereoretentive strategy for CM between tri-, Z- or E-di, or monosubstituted olefins and Z- or E-2-bromo-2-butene, affording an assortment of E- or Z-trisubstituted alkenyl bromides. The majority of the transformations were catalyzed by two Mo monoaryloxide pyrrolide (MAP) complexes, one purchasable and the other accessible by well-established protocols. Substrates, such as feedstock trisubstituted olefins, can be purchased; the alkenyl bromide reagents are commercially available or can be prepared in two steps in a multigram scale. The catalytic process can be used to generate products that contain polar moieties, such as an amine or an alcohol, or sterically hindered alkenes that are α- or ß-branched. The utility of the approach is highlighted by a brief and stereocontrolled synthesis of an unsaturated fragment of phomactin A and a concise total synthesis of ambrein. An unexpected outcome of these investigations was the discovery of a new role for the presence of a small-molecule alkene in an olefin metathesis reaction. DFT studies indicate that this additive swiftly reacts with a short-lived Mo alkylidene and probably helps circumvent the formation of catalytically inactive square pyramidal metallacyclobutanes, enhancing the efficiency of a transformation.

Surfactant-enhanced bioremediation of petroleum-contaminated soil and microbial community response: A field study.

Surfactant-enhanced bioremediation (SEBR) is frequently employed to clean up soil polluted with petroleum hydrocarbons, but few studies have focused on how surfactants affect microbial communities and different fractions of petroleum hydrocarbons, particularly in the field. Here, the surfactants sodium dodecyl benzene sulfonate (SDBS), alpha olefin sulfonate (AOS), Triton X-100 (TX-100), Tween80, and rhamnolipid were combined with the oil-degrading bacterium Pseudomonas sp. SB to remediate oil-contaminated soil in the laboratory. AOS gave the highest removal efficiency (65.1%) of total petroleum hydrocarbons (TPHs). Therefore, AOS was used in a field experiment with Pseudomonas sp. SB and the removal efficiency of TPHs and long-chain hydrocarbons C21-C40 reached 57.4 and 53.0%, respectively, significantly higher than the other treatments. During bioremediation the addition of Pseudomonas sp. SB significantly stimulated the growth of bacterial genera such as Alcanivorax, Luteimonas, Parvibaculum, Stenotrophomonas, and Pseudomonas and AOS further stimulated the growth of Sphingobacterium, Pseudomonas and Alcanivorax. This study validates the feasibility of surfactant-enhanced bioremediation in the field and partly reveals the mechanism of surfactant-enhanced bioremediation from the perspective of changes in different fractions of petroleum and microbial community dynamics.

Seeing the cis-Dihydroxylating Intermediate: A Mononuclear Nonheme Iron-Peroxo Complex in cis-Dihydroxylation Reactions Modeling Rieske Dioxygenases.

The nature of reactive intermediates and the mechanism of the cis-dihydroxylation of arenes and olefins by Rieske dioxygenases and synthetic nonheme iron catalysts have been the topic of intense research over the past several decades. In this study, we report that a spectroscopically well characterized mononuclear nonheme iron(III)-peroxo complex reacts with olefins and naphthalene derivatives, yielding iron(III) cycloadducts that are isolated and characterized structurally and spectroscopically. Kinetics and product analysis reveal that the nonheme iron(III)-peroxo complex is a nucleophile that reacts with olefins and naphthalenes to yield cis-diol products. The present study reports the first example of the cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex that yields cis-diol products.

Chain Walking in the AlCl3 Catalyzed Cationic Polymerization of α-Olefins.

Continuing efforts aimed at performing the 1-decene polymerization to low viscosity polyalphaolefins (PAO)s using a less hazardous AlCl3 catalyst than boron-based analogs, the basic mechanisms of this system were revealed in this research. In this aspect, neat AlCl3 and AlCl3 /toluene were carried out to perform 1-decene polymerizations. Microstructure analyses of the as-synthesized oils revealed low molecular weight (708 vs. 1529 g/mol), kinematic viscosity (KV100 =6.4 vs. 22.2 cSt), and long chain branching (82.1 vs. 84.7) of PAO from the system containing toluene solvent. Furthermore, NMR analysis confirmed various types of short chain branch (SCB) with the inclusion of toluene ring in the structure of final PAO chains. Then, to shed light on the basic mechanisms of cationic polymerization of 1-decene including: i) chain initiation, ii) chain transfer to the monomer, iii) isomerization of the carbocation via a chain walking mechanism (causes different SCB length), and iv) binding of toluene ring to the propagating PAO chain (to yield aromatic containing oligomers), molecular modeling at the DFT level was employed. The energies obtained confirmed the ease of carbocation isomerization and chain transfer mechanisms in toluene medium, which well confirms the highly branched structure experimentally obtained for related PAO.

σ-Hole interactions in organometallic catalysts: the case of methyltrioxorhenium(VII).

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.

Phosphine Oxide-Promoted Rh(I)-Catalyzed C-H Cyclization of Benzimidazoles with Alkenes.

Ligands play a critical role in promoting transition-metal-catalyzed C-H activation reactions. However, owing to high sensitivity of the reactivity of C-H activation to metal catalysts, the development of effective ligands has been a formidable challenge in the field. Rh(I)-catalyzed C-H cyclization of benzimidazoles with alkenes has been faced with low reactivity, often requiring very harsh conditions. To address this challenge, a phosphine oxide-enabled Rh(I)-Al bimetallic catalyst was developed for the reaction, significantly promoting the reactivity and allowing the reaction to run at 120 °C with up to 97% yield.

Rapid effective treatment of waxy oily sludge using a method of dispersion combined with biodegradation in a semi-fluid state.

Waxy oily sludge (WOS) from petrochemical enterprises has complex components and difficult treatment. Long-term large-scale stacking has seriously threatened human health and the ecological environment. In this paper, a new rapid and effective treatment method combining dispersion and biodegradation in a semi-fluid state was developed for the WOS. The degradation mechanism of the WOS in the bioreactor was preliminarily discussed. The component analysis results showed that the compounds with large molecular weight (M ≥ 282) in the WOS accounted for more than 50%. Among all microbial consortiums, the treatment effect of the consortium FF: NY3 = 9: 1 was the best for treating the crude oil in WOS, which was significantly different from that of a single strain (p < 0.05). Under the optimal nitrogen source NH4NO3 and the concentration of rhamnolipid, the developed high-efficiency microbial consortium (FF: NY3 = 9:1) could remove 85% of the total hydrocarbon pollutants in the 20 L semi-fluid bioreactor within 9 days. The degradation characteristics of WOS components in the bioreactor showed that the developed consortium has good degradation ability for n-alkanes (about 90%), middle- (77.35%)/long-chain (72.66%) isomeric alkanes, alkenes (79.12%), alicyclic hydrocarbons (78.9%) and aromatic hydrocarbons (62.78%). The kinetic analysis results indicated that, in comparison, the middle-chain n-alkanes, middle-chain isomeric saturated alkanes, alkenes, and alicyclic hydrocarbons were most easily removed. The removal rates of long-chain n-alkanes, long-chain isomeric saturated alkanes, and aromatic hydrocarbons were relatively low. The biological toxicity test showed that the germination rate of wheat seeds in treated waxy sludge was Significantly higher than that in untreated waxy sludge (p < 0.01). These results suggest that the new method developed in this paper can treat refractory WOS quickly and effectively. This method lays the foundation for the pilot-scale treatment of the semi-fluid bioreactor.

Effect of silver(I) ion reduction on the selectivity of olefins, paraffins, and aromatic compounds by gas chromatographic stationary phases consisting of silver(I) salts in ionic liquids.

The olefin/paraffin selectivity offered by ionic liquid (IL) stationary phases can be enhanced through the addition of silver(I) ion, which is well-known to undergo selective complexation with unsaturated compounds. However, such stationary phases often suffer from the loss of chromatographic selectivity as silver(I) ion can be reduced to elemental silver. To maintain the separation performance of silver(I) ion/IL stationary phases, an understanding of factors and conditions that promote the reduction of silver(I) ion is needed. In this study, capillary gas chromatography columns featuring a stationary phase consisting of the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C10MIM+][NTf2-]) IL impregnated with [Ag+][NTf2-] were examined to investigate the effects of temperature, hydrogen content in exposure gas stream, and time of heating/exposure events on olefin selectivity. Retention factors of representative analytes, such as C6 olefins and paraffins as well as aromatic compounds, were measured after subjecting the columns to the aforementioned conditions, followed by an evaluation of selectivity factors over time. Selectivity factors of olefins and aromatic compounds were observed to decrease significantly when the stationary phases were heated to temperatures higher than 110°C as well as being subjected to mixed gas streams containing greater than 50 mol% of hydrogen. As constant column heating temperatures were applied under exposure gas mixtures containing hydrogen and nitrogen, a gradual decrease in analyte selectivity factors was observed under prolonged periods of time. However, application of a ternary gas mixture comprised of 25/50/25 mol% hydrogen/nitrogen/methane resulted in an increase in the 3-hexyne/cis-2-hexene selectivity when measured at 120°C for 60 h, due to a smaller decrease in the retention factor of 3-hexyne compared to cis-2-hexene.

[Vertical Distribution Characteristics of Boundary Layer Volatile Organic Compounds in Autumn in the Mixed Industrial and Rural Areas over the Northern Suburb of Nanjing].

Based on the sounding data of VOCs in the lower troposphere (0-1000 m) in the northern suburb of Nanjing in the autumn of 2020, the vertical profile distribution, diurnal variation, and photochemical reactivity of VOCs in this area were analyzed. The results showed that the volume fraction of VOCs decreased with the increase in height (72.1×10-9±28.1×10-9-56.4×10-9±24.8×10-9). Alkanes at all heights accounted for the largest proportion (68%-75%), followed by aromatics (10%-12%), halohydrocarbons (10%-11%), alkenes (3%-7%), and acetylene (2%). The diurnal variation of the boundary layer had a great influence on the VOCs profile. The lower boundary layer in the morning and evening caused the volume fraction of VOCs to accumulate near the ground and lower in the upper layer. The vertical distribution of VOCs was more uniform in the afternoon. In the morning, the volume fraction proportion of alkenes (alkanes) with strong (weak) photochemical reactivity decreased (increased) with the increase in height, indicating that the photochemical aging of VOCs in the upper layer was significant. In the afternoon, the vertical distribution of VOCs volume fraction and OFP in the lower troposphere were more uniform. Affected by the surrounding air masses with different sources, the volume fraction and component proportion of VOCs at each height were significantly different. The alkanes in rural air masses were vertically evenly distributed, and the proportion increased gradually with the height. The vertical negative gradient of VOCs volume fraction in the urban air mass was the largest, the volume fraction of VOCs near the ground was high, and it was rich in aromatics. The proportion of aromatics increased with the increase in VOCs volume fraction between 200-400 m height of industrial air mass. The near-surface VOCs volume fraction of the highway traffic air mass was high, and alkanes accounted for the largest proportion.

Mechanism and Origin of Site Selectivity and Regioselectivity of Scandium-Catalyzed Benzylic C-H Alkylation of Tertiary Anilines with Alkenes.

Benzylic C(sp3)-H alkylation of tertiary anilines with alkenes by an anilido-oxazoline-ligated scandium alkyl catalyst was recently reported with C-H site selectivity and alkene-dependent regioselectivity. Revealing the mechanism and origin of selectivity is undoubtedly of great importance for understanding experimental observations and developing new reactions. Herein, density functional theory (DFT) calculations have been carried out on the model reaction of Sc-catalyzed benzylic C(sp3)-H alkylation of N,N-dimethyl-o-toluidine with allylbenzene. The reaction generally undergoes the generation of active species, alkene insertion, and protonation steps. The difference of the distortion energy of the aniline moiety in transition states, which is related to the ring size of the forming metallacycles, accounts for the site selectivity of C-H activation. Benzylic C(sp3)-H activation possessing less strained five-membered metallacycle compared to the ortho-C(sp2)-H and α-methyl C(sp3)-H activation results in benzylic C(sp3)-H alkylation observed experimentally. Both steric and electronic factors are responsible for the 1,2-insertion regioselectivity for alkyl-substituted alkenes, while electronic factors control the 2,1-insertion manner for vinylsilanes. The analysis of original alkene substrates further strengthens the understanding of the alkene-dependent regioselectivity. These results help us to obtain the mechanistic understanding and are expected to be conducive to the development of new C-H functionalization reactions.

Influence of 1-Butene Adsorption on the Dimerization Activity of Single Metal Cations on UiO-66 Nodes.

Grafting metal cations to missing linker defect sites in zirconium-based metal-organic frameworks, such as UiO-66, produces a uniquely well-defined and homotopic catalytically active site. We present here the synthesis and characterization of a group of UiO-66-supported metal catalysts, M-UiO-66 (M = Ni, Co, Cu, and Cr), for the catalytic dimerization of alkenes. The hydrogen-deuterium exchange via deuterium oxide adsorption followed by infrared spectroscopy showed that the last molecular water ligand desorbs from the sites after evacuation at 300 °C leading to M(OH)-UiO-66 structures. Adsorption of 1-butene is studied using calorimetry and density functional theory techniques to characterize the interactions of the alkene with metal cation sites that are found active for alkene oligomerization. For the most active Ni-UiO-66, the removal of molecular water from the active site significantly increases the 1-butene adsorption enthalpy and almost doubles the catalytic activity for 1-butene dimerization in comparison to the presence of water ligands. Other M-UiO-66 (M = Co, Cu, and Cr) exhibit 1-3 orders of magnitude lower catalytic activities compared to Ni-UiO-66. The catalytic activities correlate linearly with the Gibbs free energy of 1-butene adsorption. Density functional theory calculations probing the Cossee-Arlman mechanism for all metals support the differences in activity, providing a molecular level understanding of the metal site as the active center for 1-butene dimerization.

Coupled Rotary and Oscillatory Motion in a Second-Generation Molecular Motor Pd Complex.

Molecular machines offer many opportunities for the development of responsive materials and introduce autonomous motion in molecular systems. While basic molecular switches and motors carry out one type of motion upon being exposed to an external stimulus, the development of molecular systems capable of performing coupled motions is essential for the development of more advanced molecular machinery. Overcrowded alkene-based rotary molecular motors are an ideal basis for the design of such systems as they undergo a controlled rotation initiated by light allowing for excellent spatio-temporal precision. Here, we present an example of a Pd complex of a second-generation rotary motor whose Pd center undergoes a coupled oscillatory motion relative to the motor core upon rotation of the motor. We have studied this phenomenon by UV-vis, NMR, and density functional theory calculations to support our conclusions. With this demonstration of a coupled rotation-oscillation motion powered by a light-driven molecular motor, we provide a solid basis for the development of more advanced molecular machines integrating different types of motion in their operation.

Intermolecular Organophotocatalytic Cyclopropanation of Unactivated Olefins.

Intermolecular cyclopropanation of mono-, di-, and trisubstituted olefins with α-bromo-ß-ketoesters and α-bromomalonates under organophotocatalysis is reported. The reaction displays broad functional group tolerance, including substrates bearing acids, alcohols, halides, ethers, ketones, nitriles, esters, amides, carbamates, silanes, stannanes, boronic esters, as well as arenes, and furnishes highly substituted cyclopropanes. The transformation may be performed in the presence of air and moisture with 0.5 mol % of a benzothiazinoquinoxaline as organophotocatalyst. Mechanistic investigations, involving Stern-Volmer quenching, quantum yield determination, and deuteration experiments, are carried out, and a catalytic cycle for the transformation is discussed.

Proximity-enhanced protein crosslinking through an alkene-tetrazine reaction.

The inverse electron demand Diels-Alder (iEDDA) reaction between a tetrazine and a strained alkene has been widely explored as useful bioorthogonal chemistry for selective labeling of biomolecules. In this work, we exploit the slow reaction between a non-conjugated terminal alkene and a tetrazine, and apply this reaction to achieving a proximity-enhanced protein crosslinking. In one protein subunit, a terminal alkene-containing amino acid was site-specifically incorporated in response to an amber nonsense codon. In another protein subunit, a tetrazine moiety was introduced through the attachment to a cysteine residue. Fast protein crosslinking was achieved due to a large increase in effective molarity of the two reactants that were brought to close proximity by the two interacting protein subunits. Such a proximity-enhanced protein crosslinking is useful for the study of protein-protein interactions.