Carbonyl Molecules Research Articles

The use of constrained methods to analyze the molecular reactivity and to define a new type of pseudo atoms

ContextConstrained methods in electronic structure methodologies add terms to the variational equations and generate solutions that represent distorted electronic distributions. In some cases, the new solutions can be used to study the chemical reactivity of parts of the molecule. Additionally, this contribution presents the use of population constraints to define pseudo atoms in a molecule. The effects of the pseudo atom on the molecular properties are analyzed. The pseudo atoms are used to simulate the inductive effect of the substituent in a group of carbonyl molecules and their effect on the stability of the complexes between these organic species and one molecule of water. A discussion on the assumptions involved in the present definition of pseudo atoms is also included.MethodThe constrained RHF computations are done in a modified Hartree-Fock code for Gaussian basis sets. The selected basis set is STO-6 G.

Carbene-Catalyzed Enantioselective Addition of Sulfinate to Ketones.

A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities and chirality. Sulfone, as an important class of sulfur-containing functional groups, represents highly valuable motifs in medicines and natural products. It remains undeveloped for the catalytic asymmetric addition of sulfinate to carbonyls. Herein we disclosed the first catalytic enantioselective addition of sulfinate to ketones for the synthesis of sulfones via N-heterocyclic carbene (NHC) catalysis. The sulfonyl chloride behaves both as an oxidant and as a nucleophilic substrate in this carbene-catalyzed process. Experimental studies suggested that the Breslow intermediate can be SET oxidized by sulfonyl chloride to generate the sulfonyl radical. This novel synthetic approach for the asymmetric addition of sulfinate to carbonyls can also be used to modify the commercially available functional molecules.

High throughput identification of carbonyl compounds in natural organic matter by directional derivatization combined with ultra-high resolution mass spectrometry

Carbonyl compounds are important components of natural organic matter (NOM) with high reactivity, so that play a pivotal role in the dynamic transformation of NOM. However, due to the lack of effective analytical methods, our understanding on the molecular composition of these carbonyl compounds is still limited. Here, we developed a high-throughput screening method to detect carbonyl molecules in complex NOM samples by combining chemical derivatization with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). In six different types of dissolved organic matter (DOM) samples tested in this study, 20–30 % of detected molecules contained at least one carbonyl group, with relative abundance accounted for 45–70 %. These carbonyl molecules displayed lower unsaturation level, lower molecular weight, and higher oxidation degree compared to non-carbonyl molecules. More importantly, the measured abundances of carbonyl molecules were consistent with the results of 13C nuclear magnetic resonance (NMR) analysis. Based on this method, we found that carbonyl molecules can be produced at DOM-ferrihydrite interface, thus playing a role in shaping the molecular diversity of DOM. This method has broad application prospects in screening carbonyl compounds from complex mixtures, and the same strategy can be used to directional identification of molecules with other functional groups as well.

Recent developments in catalytic and antimicrobial applications of benzimidazole Schiff base: A review

An amino acid and a carbonyl molecule are combined to generate Schiff bases complexes, which are useful compounds. Catalytic activity is high in many metals Schiff base complexes, especially chiral ones. Examples of processes include epoxidation, aldol condensation, hydroxylation, and oxidation. In several activities and in the presence of moisture, complexes display considerable catalytic activity. They have antibacterial, antifungal, antiviral, antimalarial, anticancer, and anti-HIV properties, among other biological activities. Research into these compounds’ coordination behavior has exploded because of specific metals on them, their biological activity and their intrinsic chemical interest as multidentate ligands. This article provides an overview of the numerous syntheses and uses for Schiff bases and their metal complexes.

Green Synthesis of Cobalt Oxide Nanoparticles (Co<sub>3</sub>O<sub>4</sub> NPs) using <i>Bauhinia Racemosa</i> (Thiruvachi) Leaves Extract and Its antioxidant, anti-diabetic, and Anti-inflammatory Properties

This study aims to appraise the antioxidant, anti-diabetic, and anti-inflammatory accomplishments of green synthesized cobalt oxide nanoparticles (Co3O4 NPs) mediated by Bauhinia racemosa leaves. Bauhinia racemosa is commonly called ''Thiruvachi' leaf tree in Tamil. The green synthesized Co3O4 NPs are calcinated at 350 °C, then characterized by TG/DTA, UV, FTIR, FL, XRD, DLS, SEM with EDS analysis, TEM, and Supercapacitor performance studies with CV analysis. TGA/DTA result associated with weight loss and exothermic reaction due to desorption of chemisorbed water. FTIR was performed to identify the functional groups of carbonyl, hydroxyl, amine, and protein molecules, which form a layer covering Co3O4 NPs and stabilize the Co3O4 NPs in the medium. The XRD pattern peaks are associated with a poly cubic crystalline form of metallic cobalt oxide nanoparticles. The average grain size of Co3O4 NPs is 36.45 nm. This research focused on Biological studies like antioxidant, anti-diabetic, and anti-inflammatory, total antioxidant measured by phosphomolyptenium reagent with vitamin C as the standard, Anti-diabetics studies carried out by α-amylase inhibition method and anti-inflammatory bustle followed by BSA denaturation technique. The spectral and morphological data confirms the Co3O4 NPs formation. The anti-inflammatory activity showed good results than the antioxidant and anti-diabetic activity.

A near-infrared fluorescence-on fluorescent probe for formaldehyde imaging in Arabidopsis thaliana

As a reactive carbonyl molecule, formaldehyde (FA) plays an important part in plant physiological and pathological activities. It is necessary to probe FA in plant for the study of its functions. In this paper, we report DISE, a dicyanoisophorone-based turn-on near-infrared fluorescent probe, which exhibits a highly sensitive response to FA. In addition, confocal imaging experiments showed that DISE could image endogenous and exogenous FA in Arabidopsis root tissue. It demonstrates that the probe has the potential to be an imaging tool to research the FA's biological roles in plant.

A long-lifetime aqueous organic redox flow battery utilizing multi-redox anolyte

High-volumetric-capacity and long-lifetime aqueous organic redox flow batteries (AORFBs) have received considerable attention for electrochemical energy storage. Here, we report a six-electron transfer π-conjugated heteroaromatic hexaazatrinaphthalene tricarboxylic acid (HATNTA) as a promising anolyte for AORFBs. HATNTA, synthesized by a straightforward and scalable one-step condensation reaction of cyclic carbonyl molecules, can undergo a reversible three-step six-electron redox process of -0.69, -0.87, and -0.94 V (versus Ag/AgCl) at pH=14. The redox reactions of HATNTA are unveiled by combining ultraviolet-visible spectrophotometry and density functional theory calculations. When paired with ferrocyanide catholyte, HATNTA-based AORFB with 1.5 M electron concentration exhibits high open-circuit voltage of 1.24 V, impressive specific capacity of 37.2 Ah L−1, high output power density of 238 mW cm−2 and superior cycling stability with a capacity fade rate of 0.021% per cycle. The outstanding battery performance substantiates that multi-redox HATNTA breaks a novel pathway to develop advanced AORFBs for large-scale energy storage.

The Hydrogenation of Crotonaldehyde on PdCu Single Atom Alloy Catalysts.

Recyclable PdCu single atom alloys supported on Al2O3 were applied to the selective hydrogenation of crotonaldehyde to elucidate the minimum number of Pd atoms required to facilitate the sustainable transformation of an α,β-unsaturated carbonyl molecule. It was found that, by diluting the Pd content of the alloy, the reaction activity of Cu nanoparticles can be accelerated, enabling more time for the cascade conversion of butanal to butanol. In addition, a significant increase in the conversion rate was observed, compared to bulk Cu/Al2O3 and Pd/Al2O3 catalysts when normalising for Cu and Pd content, respectively. The reaction selectivity over the single atom alloy catalysts was found to be primarily controlled by the Cu host surface, mainly leading to the formation of butanal but at a significantly higher rate than the monometallic Cu catalyst. Low quantities of crotyl alcohol were observed over all Cu-based catalysts but not for the Pd monometallic catalyst, suggesting that it may be a transient species converted immediately to butanol and or isomerized to butanal. These results demonstrate that fine-tuning the dilution of PdCu single atom alloy catalysts can leverage the activity and selectivity enhancement, and lead to cost-effective, sustainable, and atom-efficient alternatives to monometallic catalysts.

Anti-cancer activity of Hypnea valentiae seaweed loaded gold nanoparticles through EMT signaling pathway in A549 cells

The biological synthesis of gold nanoparticles (AuNPs) offers enormous promise for the formulation of a new generation anti-carcinogenic drugs. In this study, AuNPs were eco-friendly synthesized using the marine red algae species, Hypnea valentiae. Multiple spectroscopic methods were used to confirm and characterized the synthesized Hv-AuNPs. UV spectroscopy revealed 540 nm is where Hv-AuNPs' Surface Plasmon Resonance (SPR) peak. Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) showed that Hv-AuNPs were 7–45 nm size ranges with round shapes. With the help of an X-ray Diffraction (XRD) spectrum, the crystalline nature of Hv-AuNPs was found, and FTIR analytical tools were used to find the organic compounds, like phenols and carbonyl molecules, that were involved in the reduction of Hv-AuNPs. The biosynthesized Hv-AuNPs' potential to scavenge free radicals was measured using the DPPH test (84.5 ± 1.45%), the hydrogen peroxide assay (70.6 ± 0.8%) and the FRAP assay (90.54 ± 2.3%). Lung cancer (A549) cells were used to test the anti-cancer effects of Hv-AuNPs through EMT signaling pathway (E-cadherin, Vimentin and SNAIL). The Hv-AuNPs showed strong cytotoxic activity against lung cancer cells (IC50 = 23.68 μg/mL) and the nanoparticles effectively control the cell migration and colony formation at 50 μg/mL. The RT-PCR gene expression analysis confirmed the Hv-AuNPs potentially downregulated the Vimentin expression at 50 μg/mL and demonstrated high anti-cancer activity. Therefore, this investigation found that H. valentiae synthesized AuNPs have high therapeutic potential for lung cancer and suggests their use in drug development.

Why does thionating a carbonyl molecule make it a better electron acceptor?

The past decade has witnessed a surge of biomedical and materials applications of thiocarbonyl molecules (R2CS), such as in photodynamic therapy, organic field-effect transistors, and rechargeable batteries. The success of these applications originates from thiocarbonyl's small optical gap in the visible region and the enhanced electron affinity compared to the carbonyl analogues (R2CO). Although these observations seem to be contrary to the implication based on a simple electronegativity consideration (2.58 for sulfur and 3.44 for oxygen), a natural bond orbital (NBO) analysis gives a straightforward explanation for the LUMO-lowering effect of CO → CS substitution. In comparison to the valence (2p)C/(2p)O interactions in CO, the higher 3p orbital of sulfur and its weaker overlap with the 2p level of carbon result in a weaker antibonding interaction in NBO, a prominent contributor to the LUMO. Such an analysis also provides a semi-quantitative understanding of the electronic effect of substituents on or in π-conjugation with a (thio)carbonyl functionality. The intuitive concepts uncovered here offer a simple rule to predict the electronic properties of π-conjugated molecules that incorporate heavy heteroelements and would facilitate materials development.

Tailoring the size and magnetic property of biogenic silver nanoparticles

By exploring biological sources, the area of nanotechnology is currently thriving and offers a fresh method. Plant extract-mediated green nanomaterial synthesis has gained appeal as a result of its cost-effectiveness and environmentally beneficial characteristics. In this study, Ag NPs were successfully synthesized from reducing Ag+ ions using Mangifera indica leaf extracts as a source of reducing and capping agents. Several different microscopic and spectroscopic approaches were used in order to characterize the produced Ag NPs. Analyses using XRD and SEM have been carried out to look into the morphology of the generated Ag NPs. The (XRD) pattern peaks are associated with the metallic silver in the (FCC) shape. Silver nanoparticles average grain size is in the 10–100 nm range for all concentrations of AgNO3. The shape of the produced silver nanoparticles was determined to be round and spherical by (SEM), and their total size was determined to be between 50 and 100 nm. Analysis using EDX spectroscopy also demonstrated the production of silver and the presence of components that performed the function of a capping agent. (FT-IR) spectra were performed in order to determine the organic groups like carbonyl, hydroxyl, amine, and protein molecules. Analysis using (FT-IR) spectroscopy publicized the presence of flavonoids, polyphenols, and amide groups, all of which are candidates for being responsible for the environmentally friendly creation of silver nanoparticles. From (VSM) analysis, the biosynthesized Ag NPs were weak ferromagnetic in nature, which would be a potential research arena, especially for device application and medical equipment construction using these magnetic crystalline AgNPs. Keywords: Ag NPs, synthesized, X-ray Diffraction, TGA, magnetization

Oxidative Cleavage of Alkenes by Photosensitized Nitroarenes

This article highlights the recent seminal findings on the possibility to use photoexcited nitroarenes as modular and easily dosable reagents which can mimic the reactivity of ozonolysis for the oxidative conversion of alkenyl bonds into carbonyl groups in a highly selective fashion.

Oxidative Cleavage of Alkenes by Photosensitized Nitroarenes

AbstractOxidative cleavage of alkenes into carbonyl molecules mainly relies on either ozonolysis or Lemieux‐Johnson oxidation involving high valent transition metal oxides. Safety, technical concerns and highly oxidizing conditions of both these procedures limited their adoption in streamlined synthesis. Like ozone, photosensitized nitroarenes can deliver similar types of [3+2] cycloaddition products with alkenes through biradical formation and the resulting “N‐doped” ozonides can safely be converted to the corresponding carbonyl compounds through hydrolysis. The high prevalence of nitroarenes with diverse electronic and steric profiles combined with the mild oxidizing power allow to modulate site‐selectivity and tolerate highly sensitive functional groups ideal for application in complex molecular setup.

Valorization of discarded face mask for bioactive compound synthesis and photodegradation of dye

To keep COVID-19 at bay, most countries have mandated the use of face masks in public places and imposed heavy penalties for those who fail to do so. This has inadvertently created a huge demand for disposable face masks and worsened the problem of littering, where a large number of used masks are constantly discarded into the environment. As such, an efficient and innovative waste management strategy for the discarded face mask is urgently needed. This study presents the transformation of discarded face mask into catalyst termed ‘mask waste ash catalyst (MWAC)’ to synthesise bisindolylmethanes (BIMs), alkaloids that possess antibacterial, antioxidant and antiviral properties. Using commercially available aldehydes and indole, an excellent yield of reaction (62–94%) was achieved using the MWAC in the presence of water as the sole solvent. On the other hand, the FT-IR spectrum of MWAC showed the absorption bands at 2337 cm−1, 1415 cm−1 and 871 cm−1, which correspond to the signals of calcium oxide. It is then proposed that the calcium oxides mainly present in MWAC can protonate oxygen atoms in the carbonyl molecule of the aldehyde group, thus facilitating the nucleophile attack by indole which consequently improved the product yield. Moreover, the MWAC is also observed to facilitate the photodegradation of methylene blue with an efficiency of up to 94.55%. Our results showed the potential applications of the MWAC derived from discarded face masks as a sustainable catalyst for bioactive compound synthesis and photodegradation of dye compounds.

A Mini-Review on the Insight into the Effect of Natural and Synthetic α,β-Unsaturated Carbonyl-Containing Compounds on PI3K/AKT/mTOR Signaling Pathways to Treat Breast Cancer

Breast cancer, which has been one of the most frequently diagnosed cancers worldwide for decades, continues to defy treatment. While researching a remedy to this problem, it was discovered that mTOR has a strong association with breast cancer. Uncontrolled activation of mTOR is shown in a variety of different cancer, making it a critical target for cancer treatment. Inhibition of the mTOR protein kinase can cause autophagic cell death. It is known that covalent inhibitors have become a prominent issue in drug discovery, with covalent inhibitors focusing on [Formula: see text]-unsaturated carbonyl molecules. Structural modifications to [Formula: see text]-unsaturated carbonyl may be one of the finest avenues for developing the best breast cancer medication. This review article discusses recent research on natural and synthetic [Formula: see text]-unsaturated carbonyls and their anti-cancer properties targeting on mTOR, with SAR to showcase the efficacy of synthetic natural products compared to parental compounds using both biological assays and in silico studies.

Towards an Understanding of Halide Interactions with the Carbonyl-Containing Molecule CH3 CHO.

The anion photoelectron spectra of Cl- ⋅⋅⋅CD3 CDO, Cl- ⋅⋅⋅(CD3 CDO)2 , Br- ⋅⋅⋅CH3 CHO, and I- ⋅⋅⋅CH3 CHO are presented with electron stabilisation energies of 0.55, 0.93, 0.48, and 0.40 eV, respectively. Optimised geometries of the singly solvated species featured the halide appended to the CH3 CHO molecule in-line with the electropositive portion of the C=O bond and having binding energies between 45 and 52 kJ mol-1 . The doubly solvated Cl- ⋅⋅⋅(CH3 CHO)2 species features asymmetric solvation upon the addition of a second CH3 CHO molecule. Theoretical detachment energies were found to be in excellent agreement with experiment, with comparisons drawn between other halide complexes with simple carbonyl molecules.

Research progress of flexible sodium-ion batteries derived from renewable polymer materials

Sodium-ion batteries have been developing rapidly in recent years due to abundant sodium resources. Organic polymers and their derived carbon materials are abundant in resources, with small environmental footprint and controllable structural design, and can be directly used in the positive and anode of sodium ion batteries, which is of great significance for green and sustainable development. Organic polymers also offer great advantages in flexible Sodium-ion batteries due to their inherent flexibility. The research progress of flexible organic polymer materials and flexible polymer derived carbon materials in sodium ion batteries are reviewed. Among them, flexible organic polymer materials will be divided into flexible organic polymer carbonyl molecules and their composites with graphene/carbon nanotubes. For polymer-derived carbon materials, we will introduce several different precursors and preparation methods. Perspectives are envisioned for the further development of flexible renewable polymer materials.

Fixed-Bed Reactor with Side Injection: A Promising Option for the Aldol Condensation of Acetaldehyde

The aldol condensation of acetaldehyde with other carbonyl molecules is a complex reaction wherein there is often formation of multiple undesirable side products. These side products include higher...

A single benzene fluorescent probe for efficient formaldehyde sensing in living cells using glutathione as an amplifier

Formaldehyde (FA), a simple reactive carbonyl molecule, is endogenously produced in the cell at various physiological condition. At elevated level, FA causes severe cell toxicity as well as damage in macromolecules such proteins and DNA. For detecting FA in living cell, we identify a small but effective fluorescent turn on probe comprising single benzene-based orothophenylenediamine compound. Further study reveals that carboxylic group in orothophenylenediamine plays the important role in enhancing fluorescent signal than another electron withdrawing group. It is even interesting to observe the occurrence of fluorescent enhancement in glutathione (GSH) environment which is generally abundant in every cell. Our probe enables to detect FA over other bio-analytes efficiently with limit of detection of 123 nM and 355-fold of enhancement in cellular mimicking conditions. Moreover, this probe could be useful in discriminating cell that has high concentration of FA as well as GSH.

Constructing chiral bicyclo[3.2.1]octanes via palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes

Transition-metal-catalyzed tandem Heck/carbonylation reaction has emerged as a powerful tool for the synthesis of structurally diverse carbonyl molecules, as well as natural products and pharmaceuticals. However, the asymmetric version was rarely reported, and remains a challenging topic. Herein, we describe a palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes. Alcohols, phenols and amines are employed as versatile coupling reagents for the construction of multifunctional chiral bicyclo[3.2.1]octanes with one all-carbon quaternary and two tertiary carbon stereogenic centers in high diastereo- and enantioselectivities. This study represents an important progress in both the asymmetric tandem Heck/carbonylation reactions and enantioselective difunctionalization of internal alkenes.