-
The Journal of Physical Chemistry... Aug 2022Bicyclo[1.1.0]butane (BCB) derivatives are versatile coupling partners, and various reaction modes for their activation and transformation have been proposed. In this...
Bicyclo[1.1.0]butane (BCB) derivatives are versatile coupling partners, and various reaction modes for their activation and transformation have been proposed. In this work, three BCB-activation modes in Rh-catalyzed BCB transformations that construct diastereoselective α-quaternary β-lactones were investigated by density functional theory calculations. Our results show that, compared with C1-C3 insertion and C-C3 oxidative addition, C2-C3 oxidative addition is more favorable. The whole catalytic cycle involves five main steps: C-H activation, oxidative addition, β-C elimination/reductive elimination, Rh walking, and aldehyde insertion/protonation. Independent gradient model, intrinsic reaction coordinate, distortion-interaction energy, and Laplacian electron-density analyses were carried out to investigate the mode of BCB activation. Our calculation also showed that aldehyde-insertion is the diastereoselectivity determining step, which is controlled by the steric effect between the ligand, methyl group, and aldehyde.
Topics: Aldehydes; Butanes; Catalysis; Oxidation-Reduction; Rhodium
PubMed: 35960186
DOI: 10.1021/acs.jpclett.2c01528 -
ACS Nano Jul 2022The development of natural hydrogels with sufficient strength and self-healing capacity to accelerate skin wound healing is still challenging. Herein, a hyaluronic acid...
The development of natural hydrogels with sufficient strength and self-healing capacity to accelerate skin wound healing is still challenging. Herein, a hyaluronic acid nanocomposite hydrogel was developed based on aldehyde-modified sodium hyaluronate (AHA), hydrazide-modified sodium hyaluronate (ADA), and aldehyde-modified cellulose nanocrystals (oxi-CNC). This hydrogel was formed using dynamic acylhydrazone bonds a double-barreled syringe. This hydrogel exhibited improved strength and excellent self-healing ability. Furthermore, platelet-rich plasma (PRP) can be loaded in the hyaluronic acid nanocomposite hydrogels (ADAC) imine bonds formed between amino groups on PRP (.., fibrinogen) and aldehyde groups on AHA or oxi-CNC to promote skin wound healing synergistically. As expected, ADAC hydrogel could protect and release PRP sustainably. In animal experiments, ADAC@PRP hydrogel significantly promoted full-thickness skin wound healing through enhancing the formation of granulation tissue, facilitating collagen deposition, and accelerating re-epithelialization and neovascularization. This self-healing nanocomposite hydrogel with PRP loading appears to be a promising candidate for wound therapy.
Topics: Animals; Hyaluronic Acid; Nanogels; Platelet-Rich Plasma; Wound Healing; Hydrogels; Aldehydes
PubMed: 35848721
DOI: 10.1021/acsnano.2c05069 -
Current Opinion in Chemical Biology Dec 2020Biofuels and biochemicals derived from renewable resources are sconsidered as potential solutions for the energy crisis and associated environmental problems that human... (Review)
Review
Biofuels and biochemicals derived from renewable resources are sconsidered as potential solutions for the energy crisis and associated environmental problems that human beings are facing today. However, so far the available types of bioderived chemicals are rather limited, and production efficiency is generally low. Expanding the realm of bioderived chemicals and relevant derivatives can help motivate the development of bioenergy and the general bioeconomy. Aldehydes, possessing unique reactivity, hold great promise as platform chemicals for producing a large portfolio of bioproducts. In this review, we focus on production of aldehydes from renewable bioresources and derivatization of aldehydes through chemocatalysis, biocatalysis, or de novo biosynthesis. Perspectives on combining protein engineering and cascade reactions for advanced aldehyde derivatization are also provided.
Topics: Aldehydes; Animals; Bacteria; Biocatalysis; Biofuels; Biomass; Biosynthetic Pathways; Fungi; Lignin
PubMed: 32454426
DOI: 10.1016/j.cbpa.2020.04.007 -
Journal of Immunology Research 2022Oxidative stress plays an important role in the development of aging-related diseases by accelerating the lipid peroxidation of polyunsaturated fatty acids in the cell... (Review)
Review
Oxidative stress plays an important role in the development of aging-related diseases by accelerating the lipid peroxidation of polyunsaturated fatty acids in the cell membrane, resulting in the production of aldehydes, such as malondialdehyde and 4-hydroxy-2-nonenal (4-HNE) and other toxic substances. The compound 4-HNE forms adducts with DNA or proteins, disrupting many cell signaling pathways including the regulation of apoptosis signal transduction pathways. The binding of proteins to 4-HNE (4-HNE-protein) acts as an important marker of lipid peroxidation, and its increasing concentration in brain tissues and fluids because of aging, ultimately gives rise to some hallmark disorders, such as neurodegenerative diseases (Alzheimer's and Parkinson's diseases), ophthalmic diseases (dry eye, macular degeneration), hearing loss, and cancer. This review aims to describe the physiological origin of 4-HNE, elucidate its toxicity in aging-related diseases, and discuss the detoxifying effect of aldehyde dehydrogenase and glutathione in 4-HNE-driven aging-related diseases.
Topics: Aldehydes; Lipid Peroxidation; Oxidative Stress
PubMed: 35411309
DOI: 10.1155/2022/2233906 -
Journal of Agricultural and Food... May 2023Odor-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...
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(9)] were characterized and have shown highly interesting odor profiles, including citrus-like, soapy, herbaceous, and savory notes. In particular, ()-8-hexadecenal and ()-7-pentadecenal exhibited notable meaty odor characteristics. Submerged cultivation of revealed the accumulation of the above-mentioned, naturally uncommon fatty acid 17:1(9). 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 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.
Topics: Odorants; Aldehydes; Fatty Acids; Chromatography, Gas; Dioxygenases
PubMed: 37196237
DOI: 10.1021/acs.jafc.3c01972 -
Comprehensive Reviews in Food Science... Mar 2020Reactive carbonyl compounds are a large group of highly reactive electrophilic compounds containing one or more carbonyl groups, which can be created by lipid oxidation... (Review)
Review
Reactive carbonyl compounds are a large group of highly reactive electrophilic compounds containing one or more carbonyl groups, which can be created by lipid oxidation both in vivo and in food. Malondialdehyde (MDA) and 4-hydroxy-2-nonenel (HNE) are the two most important reactive carbonyl compounds in food. They can react with proteins and nucleic acids and cause biological damage to cells and lead to carbonyl stress. Therefore, they are regarded as representative products of lipid oxidation, toxic molecules, and biomarkers of oxidative stress. Apart from biological toxicity, they can also react with myoglobin and myofibrillar protein and further affect color, gel properties, hydrophobicity, or other properties of food. However, the effects of MDA and HNE on food qualities have not received as much attentions and it is noteworthy that the existing analytical methods for detecting MDA and HNE have a variety of limitations due to the complexity of food samples. To provide a comprehensive understanding of HNE and MDA, the formation mechanism, occurrence, and analytical methods for MDA and HNE in food matrix were summarized in this article. Emphasis is focused on formation mechanism including non-enzymatic pathway and enzymatic pathway, and detection methods including the extraction methods, the new development of sample pre-treatment technology and the selection of derivative reagents. Impressively, the reaction mechanism of MDA and HNE with myoglobin or myofibrillar protein is also described to explain how MDA and HNE affect food quality.
Topics: Aldehydes; Biomarkers; Food Quality; Lipid Peroxidation; Malondialdehyde; Muscle Proteins; Myoglobin; Oxidative Stress
PubMed: 33325172
DOI: 10.1111/1541-4337.12535 -
The Journal of Organic Chemistry Mar 2022The bicyclo[1.1.1]pentane (BCP) motif is an emerging scaffold in medicinal chemistry because of its bioisosterism to 1,4-phenylene and 1,2-alkynyl functions. The current...
The bicyclo[1.1.1]pentane (BCP) motif is an emerging scaffold in medicinal chemistry because of its bioisosterism to 1,4-phenylene and 1,2-alkynyl functions. The current drawback of its use is the lack of stable versatile synthetic building blocks. Aldehydes are among the most useful functionalities in organic chemistry. In this paper, a simple one-pot procedure from aryl-halides and [1.1.1]propellane is described. Preparation of various BCP molecules is conducted to showcase the versatility of these stable intermediates.
Topics: Aldehydes; Chemistry, Organic; Chemistry, Pharmaceutical
PubMed: 35050600
DOI: 10.1021/acs.joc.1c02267 -
An antibacterial and self-healing hydrogel from aldehyde-carrageenan for wound healing applications.Carbohydrate Polymers Feb 2023This study aimed to develop and characterize a novel antibacterial, self-healing hydrogel made from aldehyde-carrageenan. Thus, carrageenan (CA) was first oxidized using...
This study aimed to develop and characterize a novel antibacterial, self-healing hydrogel made from aldehyde-carrageenan. Thus, carrageenan (CA) was first oxidized using different amounts of sodium periodate (NaIO), and the highest concentration of aldehyde was obtained when the ratio of NaIO to CA was 1.5:1. Using dopamine (PDA) and zinc ions (Zn), various hydrogels were synthesized from oxidized carrageenan (O-CA). The effects of dopamine and zinc ions on the properties of O-CA hydrogel were examined. According to Fourier Transform Infrared Spectroscopy (FTIR) studies, the hydrogel's components are linked by Schiff bases, hydrogen bonds, and ion complexes. The rheological tests confirmed that hydrogels were elastic gels, not viscous sol, and were able to recover rapidly. Adding zinc to the hydrogel reduced weight loss (38 %) and provided extra antibacterial properties, particularly against E. coli. In addition, collagen secretion and cell attachment to Zn-containing hydrogels were significantly increased, and fibroblast viability reached 118 %. Overall, a hybrid O-CA/PDA/Zn hydrogel has excellent potential for wound healing applications.
Topics: Hydrogels; Carrageenan; Escherichia coli; Aldehydes; Dopamine; Anti-Bacterial Agents; Wound Healing; Zinc
PubMed: 36604050
DOI: 10.1016/j.carbpol.2022.120371 -
Archiv Der Pharmazie Jun 2023The Biginelli reaction has received significant consideration in recent years due to its easily accessible aldehyde, urea/thiourea, and active methylene compounds. When... (Review)
Review
The Biginelli reaction has received significant consideration in recent years due to its easily accessible aldehyde, urea/thiourea, and active methylene compounds. When it comes to pharmacological applications, the Biginelli reaction end-products, the 2-oxo-1,2,3,4-tetrahydropyrimidines, are vital in pharmacological applications. Due to the ease of carrying out the Biginelli reaction, it offers a number of exciting prospects in various fields. Catalysts, however, play an essential role in Biginelli's reaction. In the absence of a catalyst, it is difficult to form products with a good yield. Many catalysts have been used in search of efficientmethodologies, including biocatalysts, Brønsted/Lewis acids, heterogeneous catalysts, organocatalysts, and so on. Nanocatalysts are currently being applied in the Biginelli reaction to improve the environmental profile as well as speed up the reaction process. This review describes the catalytic role in the Biginelli reaction and pharmacological application of 2-oxo/thioxo-1,2,3,4-tetrahydropyrimidines. This study provides information that will facilitate the development of newer catalytic methods for the Biginelli reaction, by academics as well as industrialists. It also offers a broad scope for drug design strategies, which may enable the development of novel and highly effective bioactive molecules.
Topics: Molecular Structure; Structure-Activity Relationship; Catalysis; Aldehydes; Urea
PubMed: 36899497
DOI: 10.1002/ardp.202300008 -
Angewandte Chemie (International Ed. in... Aug 2022Protein-protein coupling reactions under physiological conditions that do not impact the three-dimensional structures of the proteins are in high demand. Owing to the...
Protein-protein coupling reactions under physiological conditions that do not impact the three-dimensional structures of the proteins are in high demand. Owing to the combination of phenylsulfonyl and aldehyde groups in 5-fluoro-4-(phenylsulfonyl)picolinaldehyde (FPPA), the fluorine substituent shows high reactivity toward free thiols. In FPPA, the fluorine is more reactive than phenylsulfonyl for free thiols. Thus the first quantitative nucleophilic substitution can be followed by selective substitution of phenylsulfonyl by an additional thiol or cyclization of aldehyde with a 1,2-aminothiol molecule. The FPPA mediated protein-protein coupling proceeds efficiently under mild conditions, resulting in stable protein conjugates. This coupling method has negligible 3D structural perturbations on the target proteins, and it produces overall intact, nearly traceless, and native structural folds of proteins. It is highly suitable for reconstruction of proteins that are difficult to make and segmental isotopic labeling of multidomain proteins.
Topics: Aldehydes; Fluorine; Isotope Labeling; Proteins; Sulfhydryl Compounds
PubMed: 35691826
DOI: 10.1002/anie.202205597