Carbonyl Compounds Research Articles

Influence of Configurational Isomerism of Pyridine π Bridge in Donor-π Bridge-Acceptor Type Covalent Triazine Frameworks on The Photocatalytic Performance.

Covalent triazine frameworks (CTFs) involving a donor-π bridge-acceptor (D-π-A) structure are considered one of the most promising photocatalytic materials, in which the π bridge is known to play an important role in influencing the photocatalytic performance. So far, much effort has been directed at the designing of the different π bridge structure to facilitate the photo-induced charge separation. However, the orientation of the π bridge units (configurational isomerism) has not been considered. In this paper, a pair of pyridine-bridged D-π-A type CTFs, named TFA-P1-CTF and TFA-P2-CTF, were designed to investigate how the orientation of the π bridge would influence their performance in the photocatalytic oxidation of olefins into carbonyl compounds. Interestingly, due to the superior charge separation capability, TFA-P2-CTF was found to be able to catalyze the reaction more efficiently than TFA-P1-CTF. Our study eventually provided a guide for the design of D-π-A type CTFs as high-performance photocatalytic materials via tuning the configurational isomerism of the π bridge unit for use in chemical transformations.

Synthesis of Functionalized 2‐Hydrazono‐3‐thiazolines from 2‐Substituted Oxazoles through a One‐Pot Multicomponent/Rearrangement Process

The serendipitous rearrangement of an oxazole nucleus to a thiazoline ring under mild conditions is described. This transformation was achieved by a multicomponent reaction (MCR) featuring 2‐(bromomethyl)oxazoles, thiosemicarbazide, and a carbonyl compound to provide oxazole‐derived isothiosemicarbazones, which undergo oxazole ring‐opening and recyclization to 2‐hydrazono‐3‐thiazolines in a one‐pot procedure. This straightforward route produced highly functionalized thiazolines (34‐98% yield) in a chemo‐ and stereoselective manner.

Assessment of Crude Oil Extract from Citrullus lanatus (Water Melon) for Pharmaceutical Application

Purpose To examine crude extract from Citrullus lanatus (water melon) seed oil for pharmaceutical application. In addition determine the functional groups in the seed oil using infrared spectroscopy.  Methods The seeds of C. Lanatus was collected, dried at room temperature, seed, coat removed, pulverized, and extracted exhaustively using n-hexene in soxhlet extractor. Extract was concentrated using rotory evaporator. The oil stored in amber container physicochemical parameters were evaluated using titrimetric methods and the functional groups of chemical constituents were identified using IR.  Results The physicochemical analysis showed good iodine value, perioxide value and saponification value that falls within the acceptable range as recommended by FAO and WHO. The FTIR spectrum showed the presence of hydroxyl groups, carbonyl compounds, saturated compounds which includes CH2CH3 at specific range of absorption brands.  Conclusion The oil from C. Lanatus is excellent for human consumption and contains high amount of unsaturated fatty acids which gives it a better potential for pharmaceutical use.

Improvement of bifunctional organocatalysts performance by water as an additive in the Michael addition of carbonyl compounds to maleimides

The diastereoselective Michael addition of ketones to maleimides using bifunctional organocatalysts presents a significat challenge. We developed a protocol in which the addition of 5 equivalents of water boosted the diastereoselectivity of six-membered ring ketones. However, the results were influenced by steric effects and varied outcomes were observed with different ring sizes of ketones and acyclic carbonyl compounds. The improvement in the asymmetric synthesis of succinimides due to water appears to be more related to hydrogen bonds at the interface rather than a water molecule embedded in the transition state. Additionally, we explored 3-substituted maleimides and found that only those with phenyl and phenylethynyl groups underwent the reaction. Finally, the desymmetrization of N-(2-tert-butylphenyl)maleimide generated the atropoisomer with good selectivity.

Switchable transformation of biomass-derived furfural to furfuryl alcohol and isopropyl furfuryl ether over a zirconium-based bifunctional catalyst

Selectively converting biomass-derived furfural (FF) to furfuryl alcohol (FFA) and isopropyl furfuryl ether (IPFE) via the same catalytic system is an important strategy for the production of high-value chemicals and fuels. However, this strategy still faces a great challenge because the formation of FFA and IPFE requires different catalyst types and reaction conditions. Hence, developing a compatible catalytic system is extremely necessary. In this work, we designed a high-efficiency zirconium-based bifunctional catalyst (Zr-HC-SO3H), simultaneously containing Lewis acid-base sites (Zr4+–O2−) and Brønsted acid sites (–SO3H), which were mainly responsible for the Meerwein-Ponndorf-Verley reduction reaction of FF and further etherification reaction of FFA, respectively. By controlling reaction conditions, the action orders and catalytic activities of Zr4+–O2− and –SO3H could be accurately regulated. Thus, Zr-HC-SO3H showed excellent catalytic performance for the switchable transformation of FF, leading to 98.9 % FFA yield at 120 °C for 4 h and 95.1 % IPFE yield at 170 °C for 12 h in isopropanol (iPrOH). Additionally, the analysis results of reaction pathways indicated that the etherification of FFA was much more difficult than the reduction of FF over Zr-HC-SO3H in iPrOH, so IPFE was only formed under the harsher reaction conditions. More significantly, Zr-HC-SO3H also catalyzed the switchable transformation of many other carbonyl compounds and demonstrated satisfactory catalytic universality in iPrOH. In conclusion, this work offered some momentous clues for the development of multipurpose catalytic systems and the controllable synthesis of valuable products in the biorefinery process.

C–H/C–H Aromative carbonylation of diarylalkynes enabled palladium-catalyzed by 6-endo-dig carbocyclization

Transition metal-catalyzed cycloaromatization reactions of diarylalkynes offer a swift and versatile approach to synthesizing a wide array of polycyclic aromatic compounds. However, the specific mechanism of Pd-catalyzed C–H/C–H aromative carbonylation of diarylalkynes, particularly those bearing adjacent functional groups, remains a relatively unexplored area. Herein, we present a palladium-catalyzed C–H/C–H aromative carbonylation of diarylalkynes, which proceeds through an exclusive 6-endo-dig carbocyclization pathway, followed by the incorporation of CO to yield carbonyl compounds. This methodology provides a novel and efficient route for generating complex aromatic structures, thus expanding the potential applications in organic synthesis.

Anion Relay Chemistry Enables Stereoselective Carbonyl-Alkyne Metathesis Reactions.

Dithiane chemistry is increasingly advantageous in the development of novel anion relay chemistry (ARC) modes that harness their umpolung properties to address new chemical challenges. Herein, we report the use of an ARC strategy to promote the regioselective carbonyl alkyne metathesis (CAM) of various carbonyl compounds with alkynyl 1,3-dithianes. Notably, this ARC transformation provides a platform for obtaining stereodefined polysubstituted 1,3-dienes.

Development of Organocatalytic Darzens Reactions Exploiting the Cyclopropenimine Superbase.

A truly organocatalytic approach to the Darzens reaction affording α,β-epoxy carbonyl compounds in good yields was developed taking advantage of the high basic strength and low nucleophilicity of cyclopropenimine superbases. The catalytic active free base can easily be generated in situ from its hydrochloride salt and maintained in the active deprotonated form by performing the reactions in a heterogeneous reaction system in the presence of excess potassium carbonate as a sacrificial base.

Isotope-Labeled Chemoselective Probes for Labeling, Separation, and Comprehensive Quantitative Analysis of Sub-Metabolome.

The significance of small molecule metabolites as biomarkers for disease diagnosis and prognosis is growing increasingly evident, necessitating the development of highly sensitive qualitative and quantitative methods. Herein, multi-chemoselective probes are synthesized and applied for profiling metabolites, including carboxyl, phosphate, hydroxyl, amino, thiol, and carbonyl compounds. This approach seamlessly integrates magnetic solid-phase materials, orthogonal cleavage sites, isotopic tags, and selective coupling sites, minimizes matrix interference, and enhances quantitative accuracy. Meanwhile, a homemade program, High-Resolution Isotope-Assisted Identification and Quantitative (HRIAIQuant) is developed to process the data, which adeptly filters through 33,874 ion pairs present in human serum, leading to the identification of 701 known metabolites and a remarkable 1,062 potential novel ones. This method is successfully applied to analyze metabolites in multiple brain regions of SAMP8 and SAMR1 models, offering a novel tool for Alzheimer's disease research.

3D Porous Gel from the Orthogonal-junction of Nanosheet Photosensitizers with Efficient and Selective Photosensitization

Photocatalysis waste decomposition is a promising candidate for efficient cleaning of volatile organic compounds (VOCs) with enhanced safety because of the self-degradation of toxic compounds by reactive oxygen species (ROS) under light irradiation. However, the complete removal of pollutants remains challenging due to the inert characteristics of their inactivity in the presence of electrophilic ROS. Herein, a new strategy for efficient degradation of inert VOCs such as benzaldehyde has been proposed, basing on the synergism of selective adsorption and chemical activation by the construction of 3D porous gel through an orthogonal-junction of nanosheet-shaped photosensitizers. The key to the success of the combination is the use of hierarchically assembled hydrogen bonded laminates (HBLs) as gelation scaffolds. The backbone could integrate organic photosensitizers (PSs) into robust gel skeleton with enhanced ROS generation, which promotes the photocatalytic degradation. Especially, the backbone is able to directionally recognize glue clusters by hydrogen bonding to result in orthogonal 3D gel, giving remarkable selective adsorption for inert aromatic aldehydes. The synergistic integration of chemical activation and selective entrapment gives rise to unusual rapid photo-degradation for carbonyl compounds, resulting in efficient removal of inert pollutants from the environment without any adverse effect.

Nitrogen-doped mesoporous carbon as metal-free catalysts for the aerobic oxidation of alcohols

The selective oxidation of alcohols to carbonyl compounds is a crucial reaction in organic chemistry. In this study, we report the synthesis of nitrogen-doped mesoporous carbon material by hard template method using biomass derivative sucrose and melamine as carbon and nitrogen sources and silica sol as template agent. Using molecular oxygen as the oxidant, the obtained NC-900 exhibits excellent selectivity in the oxidation of primary alcohols to the corresponding aldehydes without generating over-oxidized acid. For example, under optimal reaction conditions, 4-methoxybenzyl alcohol is almost quantitatively converted to 4-methoxybenzaldehyde. The catalytic system showed robust tolerance to sensitive functional groups and demonstrated favorable reaction effects in gram-scale experiments and multi-step, one-pot reaction sequences. The catalyst was reused for 5 times, and its catalytic activity did not decrease significantly. Hammett correlation studies indicated that the reaction favored substrates with electron-donating substituents. Characterization and experimental results indicate that the synergistic effect of graphitic N and mesoporous structure plays a pivotal role in enhancing the catalytic activity of NC-900 in this transformation. The mechanism study shows that the reaction involves free radical process.

Multimodal Molecular Imaging Reveals a Novel Membrane Component in Sporangia of the Rare Actinomycete Actinoplanes missouriensis.

The bacterium Actinoplanes missouriensis belongs to the genus Actinoplanes, a prolific source of useful natural products. This microbe forms globular structures called sporangia, which contain many dormant spores. Recent studies using transmission electron microscopy have shown that the A. missouriensis sporangium membrane has an unprecedented three-layer structure, but its molecular components remain unclear. Here, we present multimodal (spontaneous Raman scattering, coherent anti-Stokes Raman scattering, second harmonic generation, sum frequency generation, and third-order sum frequency generation) label-free molecular imaging of intact A. missouriensis sporangia. Spontaneous Raman imaging assisted with multivariate curve resolution-alternating least-squares analysis revealed a novel component in the sporangium membrane that exhibits unique Raman bands at 1550 and 1615 cm-1 in addition to those characteristic of lipids. A plausible candidate for this component is an unsaturated carbonyl compound with an aliphatic moiety derived from fatty acid. Furthermore, second harmonic generation imaging revealed that a layer(s) of the sporangium membrane containing this unknown component has an ordered, noncentrosymmetric structure like fibrillar proteins and amylopectin. Our results suggest that the sporangium membrane is a new type of biological membrane, not only in terms of architecture but also in terms of components. We demonstrate that multimodal molecular imaging with Raman scattering as the core technology will provide a promising platform for interrogating the chemical components, whether known or unknown, of diverse biological structures produced by microbes.

A cooperation of ceric ammonium nitrate and N-hydroxyphthalimide in the aerobic oxidation from ketones to lactones/esters: Catalytic characterization and mechanistic investigation

When molecular oxygen is employed as the oxidant in the Baeyer-Villiger reaction, the addition of an excess amount of sacrificial aldehyde/alcohol to generate peroxyacids or peroxides in situ is the most frequently adopted strategy. In this work, we report a sacrifice-free approach to lactone/esters from ketones using molecular oxygen as the oxidant, in which cerium ammonium nitrate and N-hydroxyphthalimide were utilized as the catalysts with a good tolerance to cyclic and aromatic ketones. Experiments have shown that the presence of α-hydrogens in ketone compounds is a critical condition for the reaction, and the 2H labeling experiments demonstrated that the oxidation is initiated via the deprivation of the α-hydrogen of ketone by phthalimide N-oxy radical (PINO), which is significantly different from the Criegee-Intermediate mechanism of traditional BV reaction. And the 18O labeling experiment suggested that NO3− participates in the oxidation of the carbonyl compounds and NO3− could be regenerated by molecular oxygen. The redox process of cerium and the structure of the catalytic complex were also illustrated by the EPR and XRD characterization. Meanwhile, cerium ammonium nitrate was proved to be capable recycle although its reactivity was decreased after two cycles. The unprecedented mechanism for the synthesis of lactone/ester was hoped to provide a new prospect in the academic study and industrial manufacture.

Huang-Lian-Jie-Du Decoction alleviates diabetic encephalopathy by regulating inflammation and pyroptosis via suppression of AGEs/RAGE/NF-κB pathways

Ethnopharmacological relevanceCognitive dysfunction associated with diabetes, known as diabetic encephalopathy (DE), is a grave neurodegenerative condition triggered by diabetes, and persistent inflammation plays a vital role in its development. The renowned traditional Chinese medicine Huang-Lian-Jie-Du Decoction (HLJDD) is clinically proven to manage diabetes mellitus and Alzheimer's disease and is famous for its heat-clearing and detoxifying effects. However, the underlying mechanisms through which HLJDD affects DE remain to be elucidated. Aim of the studyTo explore the beneficial effects of HLJDD on improving cognitive dysfunction in DE mice. Study design and methodsA diabetic mouse was established through a high-fat diet and subsequent administration of streptozotocin over five consecutive days. After the animals were confirmed to have diabetes, they were treated with HLJDD. After oral administration of HLJDD or metformin for 14 weeks, behavioral tests were used to assess their cognitive capacity. Biochemical analyses were then performed to detect levels of glucose metabolism, followed by histological analyses to assess pathological damage. Furthermore, AGEs/RAGE/NF-κB axis related proteins were detected by Western blot or immunofluorescence techniques. An advanced UPLC-Q-Orbitrap HRMS/MS analytical technique utilizing a chemical derivatization strategy was employed for comprehensive metabolic profiling of carbonyl compounds in the plasma of DE mice. ResultsPharmacological assessment revealed that HLJDD effectively mitigated cognitive dysfunction, normalized glucose metabolic imbalances, and repaired neuronal damage in DE mice. It reduced neuroinflammation by attenuating carbonyl stress, deactivating astrocytes and microglia, and preserving dopaminergic neurons. Additionally, metabolomics analysis revealed 18 carbonyl compounds with marked disparities between DE and control mice, with 12 metabolites approaching normal levels post-HLJDD intervention. Further investigations showed that HLJDD regulated inflammation and pyroptosis through suppressing AGEs/RAGE/NF-κB pathways. ConclusionOur study indicated that HLJDD could ameliorate carbonyl stress via the regulation of carbonyl compound metabolism profiling, and inhibiting the AGEs/RAGE/NF-κB pathway, thereby alleviating inflammation and pyroptosis to exert beneficial effects on DE.

Bi(III)-Catalyzed Michael Addition of Tautomerizable Heterocycles with α,β-Unsaturated Carbonyl Compounds: Regioselective Construction of C-N Bonds.

A Bi(III)-catalyzed synthetic strategy for regioselective construction of C-N bonds via a simple Michael addition reaction is reported. A wide range of tautomerizable heterocycles such as benzoxazolones, benzothiazolones, benzimidazolinones, indolinones, and 2-pyridones along with α,β-unsaturated carbonyls (ketones and esters) are employed to create a library of corresponding N-alkylated derivatives exclusively. High regioselectivity, high atom economy, and the participation of a range of tautomerizable heterocycles highlight the uniqueness and generality of the developed methodology.

Current Status of Amine Dehydrogenases: From Active Site Architecture to Diverse Applications Across a Broad Substrate Spectrum

AbstractAmine dehydrogenases (AmDHs) are NAD(P)H‐dependent oxidoreductases that catalyze the reductive amination between carbonyl compounds and ammonia as the amine donor yielding valuable amines, typically with excellent enantioselectivity. While nature has provided enzymes with inherent AmDH activities, protein engineering techniques allowed researchers to expand the toolbox of available AmDHs, extend their substrate scope, improve their catalytic activities and stability under synthetically relevant conditions and even enable new reactivity concepts. The biocatalytic synthesis of amines using AmDHs has matured to a point where hundreds of aldehydes or ketones, of varying steric demands and bearing diverse functional groups, can be efficiently transformed. This review offers an overview of the available AmDHs and their substrate spectrum, covering from structural and evolutionary analyses to diverse methods employing these enzymes. Depending on the catalytic activities of other enzymes as reaction partners, AmDHs were applied in kinetic resolution (KR) and deracemization processes, cascade reactions for the amination of alcohols and alkenes or for the synthesis of amines and amino alcohols featuring multiple stereogenic centers. Moreover, the synthetic potential of AmDHs in novel pathways, such as the synthesis of secondary amines or alcohols, presents exciting opportunities for expanding their catalytic repertoire.

Utilization of the mixture of ethylene tar and different petrochemical by-products as collectors for coal flotation

ABSTRACT The ethylene tar and mixtures of ethylene tar with other petrochemical by-products were used as collectors for coal flotation. The results showed that the 1# compound collector was better than kerosene in terms of selectivity and collectibility for coal flotation. When the collector dosage was 1500 g/t, the yield of clean coal using the 1# compound collector increased by 4.05%, and the reduction in ash content was 0.36% lower compared to using kerosene. The mechanism of action of 1# compound collector on the coal surface was analyzed in combination with GC-MS tests and FTIR tests. The 1# compound collector contains more aromatics, olefins and heteropolar substances than kerosene. When the aromatics in the 1# compound collector interact with the nonpolar sites on the coal surface via π–π stacking interactions, some of the polar sites sandwiched between the aromatic compound molecules are covered. The olefins contained therein engage with the nonpolar sites on the surface experiences interactions attributable to van der Waals forces. The oxygenated functional groups of alcohols, acids, esters and carbonyl compounds engage with the polar sites on the surface of the particles through hydrogen bonding.

Enhanced morphological and thermal properties of epoxy composites reinforced with Palm and Prosopis Juliflora fibers

Abstract This study investigates the fabrication and characterization of a hybrid epoxy matrix composite reinforced with Palm and Prosopis Juliflora fibers fabricated using the hand layup technique. Three composite samples were prepared with varying weight percentages of palm and Prosopis Juliflora fiber reinforcements: 5% (Sample A), 10% (Sample B), and 15% (Sample C). Sample B having 10 weight percentage each of Palm fiber and Prosopis Juliflora fiber and 80 weight percentage of Epoxy matrix, exhibited superior performance with a tensile strength of 45.5 MPa and a hardness of 86.5 Shore D. Thermal analysis revealed Sample B’s exceptional thermal stability, with distinct decomposition stages observed through Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA). Void content analysis indicated Sample C had the lowest void content at 4.5%. Energy Dispersive x-ray (EDX) Analysis confirmed homogeneous fiber distribution and strong fiber-matrix adhesion, supported by carbon and oxygen peaks. Fourier-transform infrared spectroscopy (FTIR) spectra showed interactions between functional groups, including alcohols, carboxylic acids, and carbonyl compounds. These findings underscore the composite’s potential for high strength, toughness, and thermal stability applications.

Synthesis and structural characterization of 2,2′:6,2″-Terpyridine zinc Formate: Hydroboration and hydrosilylation of CO2 and carbonyl compounds

The zinc formate compound (terpy)Zn(O2CH)2 is obtained via the reaction of Zn(O2CH)2 with 2,2′:6′,2″-terpyridine (terpy) and has been structurally characterized by X-ray diffraction as possessing formate ligands that coordinate via a κ1-monodentate coordination mode, which is in accord with IR spectroscopic studies. In terms of reactivity, (terpy)Zn(O2CH)2 participates in catalytic transformations involving CO2 and carbonyl compounds via hydrosilylation and hydroboration reactions. For example, (terpy)Zn(O2CH)2 achieves hydroboration of Me2CO and Ph2CO by HBpin to afford R2C(H)OBpin, and triple insertion of Ph2CO, PhC(O)Me, Me2CO and PhCHO into the Si–H bonds of PhSiH3 to afford PhSi[OCH(R)R’]3. In addition, CO2 also undergoes hydroboration and hydrosilylation by HBpin and (MeO)3SiH in the presence of (terpy)Zn(O2CH)2 to afford HCO2Bpin and HCO2Si(OMe)3, respectively.

Microcystin-RR is a biliary toxin selective for neonatal extrahepatic cholangiocytes

BACKGROUND AND AIMSBiliary atresia is a fibrosing cholangiopathy affecting neonates that is thought to result from a prenatal environmental insult to the bile duct. Biliatresone, a plant toxin with an α-methylene ketone group, was previously implicated in biliary atresia in Australian livestock, but is found in a limited location and is highly unlikely to be a significant human toxin. We hypothesized that other unsaturated carbonyl compounds, some with the potential for significant human exposure, might also be biliary toxins. METHODSWe focused on the family of microcystins, cyclic peptide toxins from blue-green algae that are found worldwide, particularly during harmful algal blooms. We used primary extrahepatic cholangiocyte spheroids and extrahepatic bile duct explants from both neonatal (a total of 86 P2 mouse pups and 18 P2 rat pups (n=8-10 per condition for both species)) and adult rodents (a total of 31 P15-18 mice (n=10-11 per condition)) to study the biliary toxicity of microcystins and potential mechanisms RESULTSWe found that 400 nM microcystin-RR, but not six other microcystins or the related algal toxin nodularin, caused greater than 80% lumen closure in cell spheroids made from extrahepatic cholangiocytes isolated from 2-3-day-old mice (p<0.0001). In contrast, it resulted in less than an average of 5% lumen closure in spheroids derived from neonatal intrahepatic cholangiocytes or cells from adult mice (p=0.4366). We also found that microcystin-RR caused occlusion of extrahepatic bile duct explants from 2-day-old mice (p<0.0001), but not 18-day-old mice. Microcystin-RR caused a 2.3 times increase in reactive oxygen species in neonatal cholangiocytes (p<0.0001), and treatment with N-acetyl cysteine partially prevented microcystin-RR-induced lumen closure (p=0.0004), suggesting a role for redox homeostasis in its mechanism of action. CONCLUSIONSWe identify microcystin-RR as a selective neonatal extrahepatic cholangiocyte toxin and suggest that it acts by increasing redox stress.