Search Results (402)

AAA+ ATPases are ring-shaped hexameric protein complexes that operate as elaborate macromolecular motors, driving a variety of ATP-dependent cellular processes. AAA+ ATPases undergo large-scale conformational changes that lead to the conversion of chemical energy from ATP into mechanical work to perform a wide range of functions, such as unfolding and translocation of the protein substrate inside a proteolysis chamber of an AAA+-associated protease. Despite extensive biochemical studies on these macromolecular assemblies, the mechanism of substrate unfolding and degradation has long remained elusive. Indeed, until recently, structural characterization of AAA+ protease complexes remained hampered by the size and complexity of the machinery, harboring multiple protein subunits acting together to process proteins to be degraded. Additionally, the major structural rearrangements involved in the mechanism of this complex represent a crucial challenge for structural biology. Here, we report the main advances in deciphering molecular details of the proteolytic reaction performed by AAA+ proteases, based on the remarkable progress in structural biology techniques. Particular emphasis is placed on the latest findings from high-resolution structural analysis of the ClpXP proteolytic complex, using crystallographic and cryo-EM investigations. In addition, this review presents some additional dynamic information obtained using solution-state NMR. This information provides molecular details that help to explain the protein degradation process by such molecular machines. Full article

Our work introduces a facile and efficient metal-free [3+3] annulation approach for the synthesis of polysubstituted pyridines via the reaction between β-enaminonitriles and β,β-dichloromethyl peroxides. This strategy operates under mild conditions, demonstrating broad substrate scope and excellent functional group tolerance. Mechanistic investigations suggest that the reaction proceeds through a Kornblum–De La Mare rearrangement followed by S_NV-type C-Cl bond cleavage and intramolecular cyclization/condensation. By circumventing the need for transition metal catalysts or radical initiators, our method offers practical utility in organic synthesis and provides a new avenue for the rapid construction of complex pyridine scaffolds. Full article

Furfural is a fascinating bio-based platform molecule that can be converted into useful cyclic compounds, among others. In this work, the hydrogenative rearrangement-dehydration of furfural towards cyclopentanone using a commercially available Pt/C catalyst was investigated in terms of its reaction performance to assess its feasibility as an industrial process. However, acquiring an acceptable cyclopentanone yield proved very difficult, and the reaction was constrained by unforeseen parameters, such as the relative liquid volume in the reactor and the substrate concentration. Most strikingly, the sacrificial formation of furanoic oligomers that precipitated onto the catalyst’s surface was a troublesome key factor that mediated the product’s selectivity versus the carbon mass balance. By applying a biphasic water–toluene solvent system, the yield of cyclopentanone was somewhat improved to a middling 59%, while tentatively positive distributions of reaction components over these solvent phases were observed, which could be advantageous for anticipated down-stream processing. Overall, the sheer difficulty of controlling this one-pot cascade transformation towards a satisfactory product output under rather unfavorable reaction parameters renders it unsuitable for industrial process development, and a multi-step procedure for this chemical transformation might be considered instead. Full article

This study investigates the potential for the microbial transformation of camelliagenin B, a saponin derived from Camellia oleifera seed cake meal, to develop novel metabolites. We employed three microbial strains, specifically Bacillus subtilis ATCC 6633, Bacillus megaterium CGMCC 1.1741, and Streptomyces griseus ATCC 13273, to biotransform camelliagenin B into its derivatives. The compounds were purified and separated using chromatographic techniques, such as high-performance liquid chromatography (HPLC). Structural identification was carried out using spectroscopic methods, including nuclear magnetic resonance (NMR) and mass spectrometry (MS). Ten bioactive compounds were obtained (1a-1j), of which nine were novel with multiple tailoring reactions, such as allyl oxidation, C-C double-bond rearrangement, hydroxylation, dehydrogenation, and glycosylation, observed in camelliagenin B analogs. The structures of these compounds were determined by 1D/2D NMR and HR-ESI-MS analysis. Therefore, this study showcases the capacity of microbial transformation as a sustainable and environmentally friendly method for generating bioactive compounds from C. oleifera seed cake meals. The individual chemicals can potentially facilitate the design of novel medicinal agents, functional foods, and natural preservatives. Full article

Spirocyclic architectures, which feature two rings sharing a single atom, are common in natural products and exhibit beneficial biological and material properties. Due to the significance of these architectures, biocatalytic dearomative spirocyclization has recently emerged as a powerful approach for constructing three-dimensional spirocyclic frameworks under mild, sustainable conditions and with exquisite stereocontrol. This review surveys the latest advances in biocatalyzed spirocyclization of all-carbon arenes (phenols and benzenes), aza-aromatics (indoles and pyrroles), and oxa-aromatics (furans). We highlight cytochrome P450s, flavin-dependent monooxygenases, multicopper oxidases, and novel metalloenzyme platforms that effect regio- and stereoselective oxidative coupling, epoxidation/semi-pinacol rearrangement, and radical-mediated cyclization to produce diverse spirocycles. Mechanistic insights gleaned from structural, computational, and isotope-labeling studies are discussed where necessary to help the readers further understand the reported reactions. Collectively, these examples demonstrate the transformative potential of biocatalysis to streamline access to spirocyclic scaffolds that are challenging to prepare through traditional methods, underscoring biocatalysis as a transformative tool for synthesizing pharmaceutically relevant spiroscaffolds while adhering to green chemistry paradigms to ultimately contribute to a cleaner and more sustainable future. Full article

Complexes formed by sulfuric acid (H₂SO₄) with HX (X = OH, Cl, Br) are critical in various chemical processes. In this work, we theoretically investigated the isomerization pathways of these complexes, analyzing their structures, energies, and reaction mechanisms. We identified eight, eight, and nine isomers for the H₂SO₄ + HX systems with X = OH, Cl, and Br, respectively, including mirror-symmetrized structures. The most stable complexes in each system are cyclic, stabilized by double hydrogen bonds forming six-membered rings. We discovered 7, 10, and 10 new transition states for the reaction involving X = OH, Cl, and Br, respectively. Isomer rearrangements primarily involve the hydrogen bond dynamics, hydrogen atom exchange, and cis–trans isomerization of H₂SO₄ due to wagging of its non-interacting O–H bond. Our findings underscore the dominance of hydrogen bonding in these intermolecular interactions and provide fresh insights into the nature and reactivity of these complexes. Full article

1,2,4-Cyclohexatrienes are strained, reactive intermediates often formed by the tetradehydro-Diels–Alder (TDDA) reaction of a conjugated enyne bearing a tethered alkyne as the enynophile. The ene component is commonly the π-bond of an aromatic group. In this focused study, we investigated the reactivity of a symmetrical substrate in which the pair of terminal ene moieties were simple 2-propenyl groups. The intermediate 1,2,4-cyclohexatriene, now bearing a 5-isopropenyl group, underwent competitive aromatization (the most usual outcome of the strain-relieving event of the cyclohexatriene), along with an intramolecular [1,5]-hydrogen atom migration, ultimately producing a non-benzenoid, pyrrole derivative. This represents a previously unknown process for a 1,2,4-cyclohexatriene derivative. Mechanistic aspects of the competitive processes were revealed by experiments performed in the presence of various protic additives (MeOD and BHT). Full article

The [PdCl₂(cod)] complex was encapsulated inside a self-assembled hexameric capsule obtained via a reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was deduced from a combination of spectral measurements (UV-visible, ¹H NMR and DOSY spectroscopies). The latter proved effective in the dimerization of styrene derivatives under mild conditions, with a catalyst loading of 0.5 mol% at 60 °C. Electronically enriched vinyl arenes underwent cyclization of the catalytic products, leading to the quasi-quantitative formation of indanes from 4-tert-butylstyrene and 9-vinylanthracene. In the instance of 9-vinylanthracene, the rearrangement product is tribenzo–pentaphene, which is formed in 50% of conversions. Full article

The development of alternative energies has become a concern for all countries to ensure domestic energy supply and provide environmental friendliness. One of the providential alternative energies is biodiesel. Biodiesel, commonly stated as fatty acid alkyl ester (FAAE), is a liquid fuel intended to substitute petroleum diesel. Nevertheless, implementation of pure biodiesel is not recommended for conventional diesel engines. It holds poor values of cold flow properties, as the effect of high saturated FAAE content contributes to this constraint. Several processes have been proposed to enhance cold flow properties of biodiesel, but this work focuses on the skeletal isomerization process. This process rearranges the skeletal carbon chain of straight-chain FAAE into branched isomeric products to lower the melting point, related to the good cold flow behavior. This method specifically requires an acid catalyst to elevate the isomerization reaction rate. And then, sulfated tin(IV) oxide emerged as a solid superacid catalyst due to its superiority in acidity. The results of biodiesel isomerization over this catalyst and its modification with iron had not satisfied the expectation of high isomerization yield and significant CFP improvement. However, they emphasized that the skeletal isomers demonstrated minimum impact on biodiesel oxidation stability. They also affirmed the role of an acid catalyst in the reaction mechanism in terms of protonation, isomerization, and deprotonation. Furthermore, the metal promotion was theoretically necessary to boost the catalytic activity of this material. It initiated the dehydrogenation of linear hydrocarbon before protonation and terminated the isomerization by hydrogenating the branched carbon chain after deprotonation. Finally, the overall findings indicated promising prospects for further enhancement of catalyst performance and reusability. Full article

This paper presents novel soluble (co)poly(hydroxyimide)s ((co)PIOH) based on 4,4′-oxydiphthalic anhydride (ODPA), 3,3′-dihydroxybenzidine (HAB), and 3,6-diaminodurene (D) with the 3/1, 1/1, and 1/3 HAB/D ratios. This chemical structure of the compounds provides the possibility of their future modification through the thermal rearrangement (polybenzoxazoles) or functionalization via Mitsunobu reaction (azo side-chain polyimides), i.e., obtaining new materials with interesting properties and therefore with expanded applications. Copolymers were characterized via FTIR, NMR, XRD, and GPC methods to confirm their structure, composition, and molar masses. The effect of copolymer composition on the thermal, mechanical, optical, and permeation properties studied for He, O₂, N₂, and CO₂, as well as hydrophobicity, was investigated. They exhibited a large interval between the glass transition temperature and the decomposition temperature, making them promising for the thermoforming technique. Transmittance above 90% was noted in the visible range for all (co)PIOH films deposited on a glass substrate. Young’s modulus of fabricated membranes was in the range of 2.37 to 3.38 GPa. The highest permeability coefficients were recorded for (co)PIOH with a 1:3 HAB-to D-ratio. Full article

The rearrangement of a total of 56 members of 22 series of orthogonally protected N-alkyl arylsulphonamides of general structure 4-XC₆H₄SO₂NR¹CO₂R² [X = H, CH₃, F, Cl, Br, CH₃O, CN, CF₃ or C(CH₃)₃; R¹ = CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂ or CH₂CH(CH₃)₂; R² = CH₃, C₂H₅ or C(CH₃)₃] when treated with lithium di-isopropylamide in tetrahydrofuran at −78 °C has been studied. The competition between directed ortho metalated rearrangement, to form 4-X-2-(R²O₂C)C₆H₃SO₂NHR¹ and the production of a substituted saccharin, is strongly influenced by the size of R¹ and R², especially in the series with X = CH₃. When R¹ = CH₃ or to a lesser degree, C₂H₅, formation of the saccharin competes to a significant extent, especially when the migrating group is CO₂CH₃ or CO₂C₂H₅. In contrast, when R¹ is a larger alkyl group, particularly if it is branched at either the α- or β-carbon atom [CH(CH₃)₂ or CH₂CH(CH₃)₂], the increased steric hindrance essentially prevents cyclisation, thus facilitating rearrangement to 4-X-2-(R²O₂C)C₆H₃SO₂NHR¹ in high yield. The size of the migrating CO₂R² group also exerts an effect on the competition between the reactions: when R² = C(CH₃)₃, clean rearrangement is possible even when R¹ = CH₃ in each series of X. These results have implications for further elaboration and rearrangement of 4-X-2-(R²O₂C)C₆H₃SO₂NHR¹ in order to prepare substituted saccharins containing a 6-CO₂R³ group. Full article

Lanthanide biosorption is important for recycling value-added materials. Previously, we analyzed dysprosium (Dy) absorption in screening strains of the unpopular yeast species Schizoblastosporion sp. However, it would be more desirable to use the well-known yeast Saccharomyces cerevisiae to make an easy-to-breed and efficient Dy-absorbing strain. Thus, we analyzed the physiological response and gene regulation of S. cerevisiae under Dy-absorbing conditions. The Dy content was measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES). Transcriptional regulation was compared under Dy-absorbing and non-absorbing conditions through mRNA analysis and quantitative real-time polymerase chain reaction (qRT-PCR). In the yeast cells, approximately 40% of the Dy was located in the cell wall fraction, and the remaining 60% was located in the intracellular fraction. qRT-PCR analysis showed that the expression of four genes, NCW2, PIR1, CRH1, and OLE1, was upregulated, and that of ATP14 was downregulated. These results suggest that NCW2, PIR1, and CRH1 were responsible for cell wall rearrangement; OLE1 initiated repair of the oxidative damage to the membrane lipids; and intracellular oxidation was caused by an imperfect ATP14 product. Full article

The oxidation of imines may give several products, such as oxaziridines, nitrones, amides, and other rearranged compounds. Therefore, its selectivity is a challenge that various methods have to face. The controversial selectivity of the oxidation of imines using urea hydrogen peroxide (UHP) catalyzed by methyltrioxorhenium (MTO) is addressed by varying the solvent, temperature, reaction time, amount of oxidant, and catalyst used. The reactivity and selectivity of the oxidation of imines proved to be particularly sensitive to the type of solvent. The use of methanol furnished the corresponding nitrones as the exclusive products, except for very hindered N-tert-alkyl substituted substrates. Using the ionic liquid [bmim]BF₄ as a solvent resulted in a complete switch in reactivity and selectivity. N-methyl substituted imines gave the corresponding amides, while imines with bulkier substituents at nitrogen did not show any reactivity. An exception was the C-phenyl,N-tert-butyl imine—the only substrate that was oxidized to the corresponding oxaziridine, albeit with low conversion. The results reported herein reaffirm the oxidation of imines with UHP/MTO in MeOH as the method of choice for their interconversion to nitrones. Full article

The [1,2]-phospha-Brook rearrangement serves as a powerful synthetic strategy that enables efficient carbonyl umpolung through phosphoryl group migration, providing direct access to α-hydroxyphosphoryl compounds—a privileged class of synthons with broad applications in organophosphorus chemistry, medicinal chemistry, and materials science. This review provides a comprehensive overview of recent progress in synthetic methodologies, possible mechanisms, and asymmetric transformations, highlighting key breakthroughs and future directions in this rapidly evolving field. Full article

Structural rearrangements in metal–organic supramolecules constructed from the coordination of Cu(II) with m-xpt (m-xylylenebis(pyridyltriazole)) are investigated upon their interaction with 1,4-diazabicyclo[2.2.2]octane (dabco) and carbon dioxide-enriched air. The binuclear [Cu₂(m-xpt)₂]⁴⁺ complexes react with dabco to produce a carbonate-bridged trinuclear complex, [Cu₃(m-xpt)₃(µ-CO₃)]⁴⁺, and an oxalate-bridged binuclear complex, [Cu₂(m-xpt)₂(µ-C₂O₄)]²⁺, where carbonate and oxalate likely originate from CO₂ and dabco, respectively. The trinuclear complex reassembles the original dimer upon the removal of the carbonate ion. Similarly, polymeric [Cu(o-xpt)(PF₆)]_n, formed from Cu(I) and o-xpt (o-xylylenebis(pyridyltriazole)) coordination, undergoes oxidation in CO₂-enriched air to yield a tetranuclear Cu(II) complex, Cu₄(o-xpt)₃(μ₄-CO₃)(μ₂-OH)(μ₂-OCOCH₃)⁴⁺. The reaction progress is monitored by UV-Vis spectroscopy, and the major products are characterized by single-crystal X-ray diffraction. Full article