Production Of Aldehydes Research Articles

Alkaline hydrolysis of spent aromatic biomass for production of phenolic aldehydes, lignin, and cellulose

In order to combat the environmental issues associated with the burning of spent aromatic biomass (SAB), a method for alkaline hydrolysis of SAB has been developed to afford phenolic acids, predominantly the p-coumaric acid, lignin, and cellulose. Lignin (∼15 wt%) from alkaline hydrolysate was separated by precipitation while a mixture of phenolic acids obtained was directly reacted with a green reagent, PhI(OAc)2, under one-pot condition to afford a mixture of p-hydroxybenzaldehyde (>90 wt%) and vanillin (<10 wt%). Unreacted biomass obtained in the process was successfully used as a substrate for the production of cellulose (∼40 wt%). The developed method exhibits potential for application on an industrial scale.

Plastic waste recycling is gaining momentum.

Production of detergents and aldehydes could help tackle plastic pollution.

Enhanced Catalytic Aryl Alkene Oxidation by Constructing Hierarchical Polyoxometalate‐Based Metal‐Organic Framework

AbstractAchieving highly selective oxidation of aryl alkenes to aldehydes is of great significance in chemical industry. Herein, the performance of catalytic aryl alkene oxidation is enhanced via constructing a hierarchical fractal polyoxometalate‐based metal–organic framework (POM@MOF) containing hierarchical pores and layered surface structure, which improve the mass transfer efficiency of substrates and increase the accessibility to active POMs clusters. Accordingly, the activity of fractal POM@MOF is increased by 4.8 times compared with microporous counterpart in 4‐tert‐butylstyrene oxidation to aldehyde product. This work paves a way for designing efficient catalysts for selective oxidation of aryl alkenes via increasing the accessibility of active sites and broadening the diffusion channels by hierarchical construction.

Quantitative ligand effect and mechanism insight of Rh-biphosphine complexes in hydroformylation of formaldehyde

Hydroformylation is one of the most important homogenous reactions with more than 10 million tons of aldehydes production each year. Due to monodentate ligands instable coordination under hydroformylation of formaldehyde, here, we introduced a range of chelating biphosphine ligands onto rhodium catalysts. Ligands, such as BINAP (TOFGA = 106.4 h−1), present higher activity relative to common monodentate ligand PPh3 (TOFGA = 73.4 h−1) with lower ligand to metal ratio. Density functional theory calculation revealed that Rh-biphosphine complexes follow the anion mechanism, with H2 oxidation addition being the rate-determining step. Activation strain analysis further demonstrated that lower H2 distortion energy resulting higher TOF of glycolaldehyde formation. Besides, the predictable quantitative structure–activity relationship model was established and suggested that both electronic and steric properties synergistically controlled formaldehyde hydroformylation activity. This combination of mathematical modeling and theoretical calculation will provide a reliable approach to activity prediction and catalyst design for important industrial hydroformylation reaction.

Abstract P3173: Exposure Of Mitochondria Isolated From Left Ventricular Myocardium Of Dogs With Moderate Heart Failure To 4-hydroxy-2-nonenal (4-hne) Worsens Existing Mitochondrial Dysfunction

Background: Reactive oxygen species (ROS) generated by dysfunction of mitochondria (MITO) of the failing heart plays an important role in lipid peroxidation of polyunsaturated fatty acids in cell and MITO membranes resulting in the production of aldehydes, such as malondialdehyde and 4-hydroxy-2-nonenal (4-HNE). MITO aldehyde dehydrogenase-2 (mALDH2) is a key enzyme for the detoxification of endogenous aldehyde substrates through NAD dependent oxidation. We previously showed that mALDH2 expression and activity are markedly reduced in MITO of failing LV cardiomyocytes, a maladaptation that can lead to considerable accumulation of 4-HNE in MITO. It is unclear whether such an accumulation of 4-HNE can further exacerbate MITO dysfunction resulting in further limitation to ATP formation via oxidative phosphorylation. Hypothesis: This study tested the hypothesis that exposure of MITO isolated from failing hearts to exogenous 4-HNE can result in further deterioration of MITO function. Methods: Freshly isolated MITO from LV myocardium of dogs with moderate heart failure (HF, LV ejection fraction ~40%) were incubated for 1 hour in absence (baseline) and presence of 4-HNE at concentrations of 3 and 30 μM. MITO energetic parameters namely ADP-stimulated respiration (ADPresp), maximal respiratory capacity (MRC) and ATP-linked respiration (ATPresp) were evaluated using an XFe96 analyzer (Seahorse Biosciences). Results: Compared to baseline, exposure of MITO to 3 μM 4-HNE has no significant effects on any of the MITO energetic measures. However, exposure of MITO to 30 μM 4-HNE resulted in significant reduction of ADPresp (490 ± 37 vs. 179 ± 7 OCR pmols/O 2 /min, p&lt;0.05), significant reduction of MRC (334 ± 56 vs. 124 ± 18 OCR pmols/O 2 /min, p&lt;0.05), and significant reduction of ATPresp (48 ± 10 vs. 20 ± 12 OCR pmols/O 2 /min, p&lt;0.05). Conclusions: Exposure of MITO from failing myocardium to elevated levels of 4-HNE can lead to marked deterioration of MITO function that can result in a further reduction of ATP leading to progression of LV dysfunction. Limiting the accumulation of 4-HNE through pharmacologic normalization of ALDH2 activity can potentially represent a therapeutic target for retarding the progression of LV dysfunction toward intractable HF.

Exploring the Interplay between Polyphenols and Lysyl Oxidase Enzymes for Maintaining Extracellular Matrix Homeostasis.

Collagen, the most abundant structural protein found in mammals, plays a vital role as a constituent of the extracellular matrix (ECM) that surrounds cells. Collagen fibrils are strengthened through the formation of covalent cross-links, which involve complex enzymatic and non-enzymatic reactions. Lysyl oxidase (LOX) is responsible for catalyzing the oxidative deamination of lysine and hydroxylysine residues, resulting in the production of aldehydes, allysine, and hydroxyallysine. These intermediates undergo spontaneous condensation reactions, leading to the formation of immature cross-links, which are the initial step in the development of mature covalent cross-links. Additionally, non-enzymatic glycation contributes to the formation of abnormal cross-linking in collagen fibrils. During glycation, specific lysine and arginine residues in collagen are modified by reducing sugars, leading to the creation of Advanced Glycation End-products (AGEs). These AGEs have been associated with changes in the mechanical properties of collagen fibers. Interestingly, various studies have reported that plant polyphenols possess amine oxidase-like activity and can act as potent inhibitors of protein glycation. This review article focuses on compiling the literature describing polyphenols with amine oxidase-like activity and antiglycation properties. Specifically, we explore the molecular mechanisms by which specific flavonoids impact or protect the normal collagen cross-linking process. Furthermore, we discuss how these dual activities can be harnessed to generate properly cross-linked collagen molecules, thereby promoting the stabilization of highly organized collagen fibrils.

Synthesized and hypothesized schiff base ligand and its metal(II) complexes DNA binding mode

ABSTRACT. Metal complexes play an important role in agriculture, pharmacology, medicine, and industrial chemistry. Schiff base metal compounds are the fusion products of propene and aldehydes, require a metal surrounded by an ion or cluster of molecules to form. Metal complexes of Co(II), Ni(II), Cu(II), and Zn(II) have also been created. Elemental analysis is used to analyses the structure and related compounds of the produced Schiff base ligand. According to deoxyribose nucleic acid (DNA) binding tests, Schiff base metal(II) complexes attach to DNA in an intercalative form with weak covalent connections. The predicted DNA binding mode supports an increase in the complexes' binding activity in the presence of newly generated ligand. The cleavage activities of the DNA were recorded using gel-electrophoresis in the presence and absence of the complexes. The findings of the cleavage experiment show that all of the produced chelates can successfully cut DNA.&#x0D; &#x0D; KEY WORDS: Schiff base ligand, DNA, Metal(II) complex, Hetero-ligand cobalt(II), Aldehydes&#x0D; Bull. Chem. Soc. Ethiop. 2023, 37(5), 1133-1139. &#x0D; DOI: https://dx.doi.org/10.4314/bcse.v37i5.6

Rh nanoparticles supported on porous hexagonal boron nitride nanorods with hierarchical structure for highly efficient hydroformylation of olefins

Hydroformylation would be a promising alternative for partial technological process in petrochemical industry because it is a 100% atom-economical route for large-scale production of aldehydes and alcohols from olefins and synthesis gas (H2 and CO). However, there are still a few problems such as cost-intensive recycling and harsh operating conditions etc. encountering in the ligand-modified cobalt and rhodium as homogeneous catalysts in practical applications. Responding to the challenges, to exploit heterogeneous catalysts especially supported catalysts is desired and needs to make more efforts. Here, porous boron nitride (p-BN) with hierarchical structure is designed through a facile thermal polymerization procedure for catalyst support. The p-BN possesses nanorod morphology assembled by numerous highly crystallized hexagonal boron nitride (h-BN) nanoparticles with the diameter of about 20 nm as building blocks, thereby forming abundant interparticle pores. The Rh nanoparticles are then supported on p-BN by an impregnation-borohydride reduction method using RhCl3 as metal precursor, and the obtained catalyst of Rh nanoparticle supported on p-BN (Rh/p-BN) is applied in hydroformylation of styrene. The high porosity and accessible boron acid sites arising from hierarchical structure of p-BN nanorods make Rh nanoparticles homogeneously disperse on the surface of p-BN nanorods and also keep the diameter about 5 nm without further aggregations. Just for this reason, Rh/p-BN exhibits excellent activity of styrene hydroformylation with the highest turnover frequency of styrene as high as 12000 h−1, in comparison with other supported catalysts using different catalyst supports. Besides the detailed investigation of the catalytic properties of Rh/p-BN under different reaction conditions, the recycle of Rh/p-BN is also conducted for five times during which there is no significant decrease in catalytic activity. The present findings indicates that the combination of catalyst support of p-BN and metal nanoparticle catalysts could be an attractive strategy for designing heterogeneous hydroformylation catalysts.

Effect of ultrasound and Staphylococcus xylosus on the bioconversion of cooked chicken meat by-products

The chicken meat industry generates by-products containing lipids and proteins, requiring high treatment costs. Staphylococcus xylosus is used in fermented meat products to promote proteolysis and differentiated volatile compounds. Ultrasound (US) is an effective tool to accelerate the process in the meat industry. This study evaluated whether the US potentiates the action of S. xylosus in the bioconversion of cooked chicken meat by-products. By-product was sterilized and inoculated with S. xylosus. After, it was sonicated at 130 kHz and 35 kHz for 30 min at 37 °C and incubated for 24 h at 37 °C. The US stimulated the proteolytic activity of S. xylosus, forming compounds of 25 kDa and producing volatile compounds. At 130 kHz showed the production of alcohols and aldehydes, while at 35 kHz, carboxylic acids. US and S. xylosus promoted good bioconversion of the cooked by-products.

Liquid-Phase Oxidation of Butene–Butane Mixtures with N2O to Ketones and Aldehydes

Conventional methods for the production of ketones and aldehydes are usually quite complicated and require the use of specific catalysts. Thus, methyl ethyl ketone (MEK) is currently manufactured through a two-step catalytic process involving the hydration of n-butenes and dehydration of the formed alcohol. The non-catalytic oxidation of olefins with nitrous oxide (N2O) via the 1,3-dipolar cycloaddition mechanism opens a potential route for the direct synthesis of carbonyl compounds. In this work, the oxidation of the commercial butene–butane mixture (BBM) with N2O in the liquid phase at 220–260 °C and elevated pressure was studied using the gas chromatography, gas chromatography–mass spectrometry, and nuclear magnetic resonance analytical methods. It was shown that only butene isomers in BBM are selectively oxidized by N2O to yield ketones and aldehydes with a total selectivity of up to 86.6%, including MEK as the major product. During oxidation, alkyl-substituted cyclopropanes are also formed from butenes with a selectivity of up to 15%.

Effects of Drying Treatments on Nutritional Compositions, Volatile Flavor Compounds, and Bioactive Substances of Broad Beans.

In this study, different drying methods, including hot air drying, sun drying, and freeze drying were employed to dry fresh broad beans. The nutritional composition, volatile organic components and bioactive substances of the dried broad beans were systematically compared. The results indicated significant differences (p < 0.05) in nutritional composition, such as protein and soluble sugar content. Among the 66 identified volatile organic compounds, freeze drying and hot air drying significantly promote the production of alcohols and aldehydes, while sun drying effectively preserves esters. In terms of bioactive substances, broad beans dried by freeze drying exhibit the highest total phenol content as well as the strongest antioxidant capacity and gallic acid, followed by sun drying. The chemometric analysis revealed that the bioactive compounds in broad beans dried by three different methods were primarily composed of flavonoids, organic acids, and amino acids with significant differentiation. Notably, freeze-dried and sun-dried broad beans exhibited a higher concentration of differential substances.

Biocatalytic Production of Odor-Active Fatty Aldehydes from Fungal Lipids.

Odor-active fatty aldehydes are important compounds for the flavor and fragrance industry. By a coupled enzymatic reaction using an α-dioxygenase (α-DOX) and an aldehyde dehydrogenase (FALDH), scarcely available aldehydes from the biotransformation of margaroleic acid [17:1(9Z)] were characterized and have shown highly interesting odor profiles, including citrus-like, soapy, herbaceous, and savory notes. In particular, (Z)-8-hexadecenal and (Z)-7-pentadecenal exhibited notable meaty odor characteristics. Submerged cultivation of Mortierella hyalina revealed the accumulation of the above-mentioned, naturally uncommon fatty acid 17:1(9Z). Its production was significantly increased by the modulation of culture conditions, whereas the highest accumulation was observed after 4 days at 24 °C and l-isoleucine supplementation. The lipase-, α-DOX-, and FALDH-mediated biotransformation of M. hyalina lipid extract resulted in a complex aldehyde mixture with a high aldehyde yield of ∼50%. The odor qualities of the formed aldehydes were assessed by means of gas chromatography-olfactometry, and several of the obtained fatty aldehydes have been sensorially described for the first time. To assess the aldehyde mixture's potential as a flavor ingredient, a sensory evaluation was conducted. The obtained product exhibited intense citrus-like, green, and soapy odor impressions.

Combinatorial gene inactivation of aldehyde dehydrogenases mitigates aldehyde oxidation catalyzed by E. coli resting cells

Aldehydes are attractive chemical targets both as end products in the flavors and fragrances industry and as synthetic intermediates due to their propensity for C–C bond formation. Here, we identify and address unexpected oxidation of a model collection of aromatic aldehydes, including many that originate from biomass degradation. When diverse aldehydes are supplemented to E. coli cells grown under aerobic conditions, as expected they are either reduced by the wild-type MG1655 strain or stabilized by a strain engineered for reduced aromatic aldehyde reduction (the E. coli RARE strain). Surprisingly, when these same aldehydes are supplemented to resting cell preparations of either E. coli strain, under many conditions we observe substantial oxidation. By performing combinatorial inactivation of six candidate aldehyde dehydrogenase genes in the E. coli genome using multiplexed automatable genome engineering (MAGE), we demonstrate that this oxidation can be substantially slowed, with greater than 50% retention of 6 out of 8 aldehydes when assayed 4 h after their addition. Given that our newly engineered strain exhibits reduced oxidation and reduction of aromatic aldehydes, we dubbed it the E. coli ROAR strain. We applied the new strain to resting cell biocatalysis for two kinds of reactions – the reduction of 2-furoic acid to furfural and the condensation of 3-hydroxybenzaldehyde and glycine to form a non-standard β-hydroxy-α-amino acid. In each case, we observed substantial improvements in product titer 20 h after reaction initiation (9-fold and 10-fold, respectively). Moving forward, the use of this strain to generate resting cells should allow aldehyde product isolation, further enzymatic conversion, or chemical reactivity under cellular contexts that better accommodate aldehyde toxicity.

Selective Oxidation of Alkylarene in H2O Catalyzed by the Polyoxometalate Supported Chromium Catalyst

AbstractThe selective oxidation of alkylarene is a quite straightforward and appealing way for production of aromatic aldehydes, ketones and aromatic acid derivatives. We synthesized Cr(III) catalyst, (NH4)3[CrMo6O18(OH)6], with reasonable activity towards selective oxidation of alkylarenes under mild conditions. The catalyst is supported by a central chromium mononucleus and a cyclic inorganic ligand composed of six MoVIO6 octahedra, avoiding the disadvantages of expensive and non‐recyclable organic ligand. It is efficient, green and can be recycled at least six times with high activity. At the same time, a wide range of substituted alkylarenes were found to be compatible, providing the corresponding carbonyl compounds in moderate‐to‐high yield.

Structural Variations in Biobased Polyfurfuryl Alcohol Induced by Polymerization in Water.

Poly(furfuryl alcohol) is a thermostable biobased thermoset. The polymerization of furfuryl alcohol (FA) is sensitive to a number of side reactions, mainly the opening of the furan ring into carbonyl species. Such carbonyls can be used to introduce new properties into the PFA materials through derivatization. Hence, better understanding of the furan ring opening is required to develop new applications for PFA. This article studies the structural discrepancies between a PFA prepared in neat conditions versus a PFA prepared in aqueous conditions, i.e., with more carbonyls, through NMR and MALDI ToF. Overall, the PFA prepared in water exhibited a structure more heterogeneous than the PFA prepared in neat conditions. The presence of ketonic derivatives such as enols and ketals were highlighted in the case of the aqueous PFA. In this line, the addition of water at the beginning of the polymerization stimulated the production of aldehydes by a factor two. Finally, the PFA prepared in neat conditions showed terminal lactones instead of aldehydes.

Importance of Mitochondria in Cardiac Pathologies: Focus on Uncoupling Proteins and Monoamine Oxidases.

On the one hand, reactive oxygen species (ROS) are involved in the onset and progression of a wide array of diseases. On the other hand, these are a part of signaling pathways related to cell metabolism, growth and survival. While ROS are produced at various cellular sites, in cardiomyocytes the largest amount of ROS is generated by mitochondria. Apart from the electron transport chain and various other proteins, uncoupling protein (UCP) and monoamine oxidases (MAO) have been proposed to modify mitochondrial ROS formation. Here, we review the recent information on UCP and MAO in cardiac injuries induced by ischemia-reperfusion (I/R) as well as protection from I/R and heart failure secondary to I/R injury or pressure overload. The current data in the literature suggest that I/R will preferentially upregulate UCP2 in cardiac tissue but not UCP3. Studies addressing the consequences of such induction are currently inconclusive because the precise function of UCP2 in cardiac tissue is not well understood, and tissue- and species-specific aspects complicate the situation. In general, UCP2 may reduce oxidative stress by mild uncoupling and both UCP2 and UCP3 affect substrate utilization in cardiac tissue, thereby modifying post-ischemic remodeling. MAOs are important for the physiological regulation of substrate concentrations. Upon increased expression and or activity of MAOs, however, the increased production of ROS and reactive aldehydes contribute to cardiac alterations such as hypertrophy, inflammation, irreversible cardiomyocyte injury, and failure.

Low-Field Benchtop NMR Spectroscopy for Quantification of Aldehydic Lipid Oxidation Products in Culinary Oils during Shallow Frying Episodes.

Toxic aldehydic lipid oxidation products (LOPs) arise from the thermo-oxidative deterioration of unsaturated fatty acids present in heated culinary oils when exposed to high-temperature frying episodes, and currently these effects represent a major public health concern. In this study, we investigated the applications of low-field (LF), benchtop NMR analysis to detect and quantify toxic aldehyde species in culinary oils following their exposure to laboratory-simulated shallow frying episodes (LSSFEs) at 180 °C. Four culinary oils of variable fatty acid (FA) composition were investigated to determine the analytical capabilities of the LF NMR instrument. Oil samples were also analysed using a medium-field (400 MHz) NMR facility for comparative purposes. Aldehydes were quantified as total saturated and total α,β-unsaturated classes. The time-dependent production of α,β-unsaturated aldehydes decreased in the order chia > rapeseed ≈ soybean > olive oils, as might be expected from their polyunsaturated and monounsaturated FA (PUFA and MUFA, respectively) contents. A similar but inequivalent trend was found for saturated aldehyde concentrations. These data strongly correlated with medium-field 1H NMR data obtained, although LF-determined levels were significantly lower in view of its inability to detect or quantify the more minor oxygenated aldehydic LOPs present. Lower limit of detection (LLOD) values for this spectrometer were 0.19 and 0.18 mmol/mol FA for n-hexanal and trans-2-octenal, respectively. Aldehydic lipid hydroperoxide precursors of aldehydic LOPs were also detectable in LF spectra. We therefore conclude that there is scope for application of these smaller, near-portable NMR facilities for commercial or 'on-site' quality control determination of toxic aldehydic LOPs in thermally stressed frying oils.

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds.

Introduction of Brønsted acids into biomimetic nonheme reactions promotes the oxidative ability of metal-oxygen complexes significantly. However, the molecular machinery of the promoted effects is missing. Herein, a comprehensive investigation of styrene oxidation by a cobalt(III)-iodosylbenzene complex, [(TQA)CoIII(OIPh)(OH)]2+ (1, TQA = tris(2-quinolylmethyl)amine), in the presence and absence of triflic acid (HOTf) was performed using density functional theory calculations. Results revealed for the first time that there is a low-barrier hydrogen bond (LBHB) between HOTf and the hydroxyl ligand of 1, which forms two valence-resonance structures [(TQA)CoIII(OIPh)(HO---HOTf)]2+ (1LBHB) and [(TQA)CoIII(OIPh)(H2O--OTf-)]2+ (1'LBHB). Due to the oxo-wall, these complexes (1LBHB and 1'LBHB) cannot convert to high-valent cobalt-oxyl species. Instead, styrene oxidation by these oxidants (1LBHB and 1'LBHB) shows novel spin-state selectivity, i.e., on the ground closed-shell singlet state, styrene is oxidized to an epoxide, whereas on the excited triplet and quintet states, an aldehyde product, phenylacetaldehyde, is formed. The preferred pathway is styrene oxidation by 1'LBHB, which is initiated by a rate-limiting bond-formation-coupled electron transfer process with an energy barrier of 12.2 kcal mol-1. The nascent PhIO-styrene-radical-cation intermediate undergoes an intramolecular rearrangement to produce an aldehyde. The halogen bond between the OH-/H2O ligand and the iodine of PhIO modulates the activity of the cobalt-iodosylarene complexes 1LBHB and 1'LBHB. These new mechanistic findings enrich our knowledge of nonheme chemistry and hypervalent iodine chemistry and will play a positive role in the rational design of new catalysts.

A Catalytic Method for the Enantioselective Synthesis of α‐Quaternary Ketones, α‐Ketoesters and Aldehydes

AbstractA practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α‐quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl‐substituted ketone and aldehyde products in 25–94 % yield and 90 : 10 to &gt;99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.

A Catalytic Method for the Enantioselective Synthesis of α-Quaternary Ketones, α-Ketoesters and Aldehydes.

A practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α-quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl-substituted ketone and aldehyde products in 25-94 % yield and 90 : 10 to >99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.