Single-crystal X-ray Diffraction Research Articles

Supramolecular Binding of Phosphonate Dianions by Nanojars and Nanojar Clamshells.

Despite the widespread use of phosphonates (RPO32-) in various agricultural, industrial, and household applications and the ensuing eutrophication of polluted water bodies, the capture of phosphonate ions by molecular receptors has been scarcely studied. Herein, we describe a novel approach to phosphonate binding using chemically and thermally robust supramolecular coordination assemblies of the formula [RPO3⊂{cis-CuII(μ-OH)(μ-pz)}n]2- (Cun; n = 27-31; pz = pyrazolate ion, C3H3N2-; R = aliphatic or aromatic group). The neutral receptors, termed nanojars, strongly bind phosphonate anions by a multitude of hydrogen bonds within their highly hydrophilic cavities. These nanojars can be synthesized either directly from their constituents or by depolymerization of [trans-CuII(μ-OH)(μ-pz)]∞ induced by phosphonate anions. Electrospray-ionization mass spectrometry, UV-vis and variable-temperature, paramagnetic 1H and 31P NMR spectroscopy, single-crystal X-ray diffraction, along with chemical stability studies toward NH3 and Ba2+ ions, and thermal stability studies in solution are employed to explore the binding of various phosphonate ions by nanojars. Crystallographic studies of 12 different nanojars offer unprecedented structural characterization of host-guest complexes with doubly charged RPO32- ions and reveal a new motif in nanojar chemistry, nanojar clamshells, which consist of phosphonate anion-bridged pairs of nanojars and double the phosphonate-binding capacity of nanojars.

N-Confused strapped calix[4]pyrrole: the missing member of calix[4]pyrrole chemistry.

The first example of N-confused strapped calix[4]pyrrole 5 is presented. The structural integrity of 5 and its regular isomer 4 was unambiguously confirmed by single crystal X-ray diffraction analysis. Anion binding studies using 1H NMR titration carried out in CDCl3 revealed a small but detectable tendency of 5 to interact with an anion. Conversely, the isomeric regular strapped calix[4]pyrrole 4 displayed high selectivity for fluoride anions under similar experimental conditions. The high fluoride selectivity of 4 and unexpectedly low anion affinity of 5 were ascribed to the presence of intramolecular hydrogen bonds within strapping subunits.

The role of stereochemistry in the anticancer activity of Re(I) tricarbonyl complexes.

Cancer is a leading cause of death worldwide, accounting for about one among six deaths, so the quest for new and improved therapies is of crucial importance. The discovery of cisplatin as an anticancer agent has paved the way for the development of other metal-based therapeutic agents and Re(I)-based candidates have been recently found to show promising results. It is known as well that chirality plays a central role in the interactions of metal-based drugs with intrinsically chiral biomolecules such as membrane transport proteins or DNA. To further exploit this property, we have developed a series of diastereomeric dinuclear Re(I) complexes with chiral ligands containing pinene-bipyridine units. These complexes offer unique insights into the relation between stereochemistry and biological activity. Single-crystal X-ray diffraction studies, spectroscopic analysis, including UV-Vis and circular dichroism (CD), confirmed the chiral structures of these complexes. Biological activity assessments were carried out against various cancer cell lines, with a particular focus on breast and colon cancer. The diastereomers exhibited distinct anticancer activities, with some displaying promising results. Notably, one diastereomer showed exceptional cytotoxicity against HCT116 and MCF-7 cancer cells. This research underscores the significance of chirality in the design of novel anticancer agents, providing insights into the potential of dinuclear Re(I) complexes as effective candidates for cancer treatment.

Eurochevalierines A-I, Sesquiterpene Alkaloid Hybrids with Anti-Triple Negative Breast Cancer Activity from Penicillium sp. HZ-5.

Nine new sesquiterpene alkaloids, eurochevalierines A-I (1-9), were separated from the rice cultures of the endophytic fungus Penicillium sp. HZ-5 originated from the fresh leaf of Hypericum wilsonii N. Robson. The structures' illumination was conducted by single-crystal X-ray diffraction, extensive spectroscopic analysis, alkaline hydrolysis reaction, and Snatzke's method. Importantly, the antitumor activities screen of these isolates indicated that 1 could suppress triple negative breast cancer (TNBC) cell proliferation and induce apoptosis, with an IC50 value of 5.4 μM, which is comparable to the positive control docetaxel (DXT). Flow cytometry experiments mentioned that compound 1 significantly reduced mitochondrial membrane potential (MMP) of TNBC cells. In addition, 1 could activate caspase-3 and elevated the levels of reactive oxygen species (ROS) and expressions of suppressive cytokines and chemokines. Further Western blot analysis showed that 1 could selectively induce mitochondria-dependent apoptosis in TNBC cells via the BAX/BCL-2 pathway. Remarkably, these finding provide a new natural product skeleton for the treatment of TNBC.

Position of substituents directs the electron transfer properties of entatic state complexes: new insights from guanidine-quinoline copper complexes.

In a previous study, we showed that the properties and the ability as an entatic state model of copper guanidine quinoline complexes are significantly influenced by a methyl or methyl ester substituent in the 2-position. To prove the importance of the 2-position of the substituent, two novel guanidine quinoline ligands with a methyl or methyl ester substituent in the 4-position and the corresponding copper complexes were synthesized and characterized in this study. The influence of the substituent position on the copper complexes was investigated with various experimental and theoretical methods. The molecular structures of the copper complexes were examined in the solid state by single-crystal X-ray diffraction (SCXRD) and by density functional theory (DFT) calculations indicating a strong dependency on the substituent position compared to the systems substituted in the 2-position from the previous study. Further, the significantly different influence on the donor properties in dependency on the substituent position was analyzed with natural bond orbital (NBO) calculations. By the determination of the redox potentials, the impact on the electrochemical stabilization was examined. With regard to further previously analyzed guanidine quinoline copper complexes, the electrochemical stabilization was correlated with the charge-transfer energies calculated by NBO analysis and ground state energies, revealing the substituent influence and enabling a comparatively easy and accurate possibility for the theoretical calculation of the relative redox potential. Finally, the electron transfer properties were quantified by determining the electron self-exchange rates via the Marcus theory and by theoretical calculation of the reorganization energies via Nelsen's four-point method. The results gave important insights into the dependency between the ability of the copper complexes as entatic state model and the type and position of the substituent.

Fluorinated high-valent Sn(IV) porphyrins show remarkable photodynamic activity in cancer cells.

In recent years, Sn(IV) porphyrins have proven to be excellent choice as photosensitizers for photodynamic therapy. This work reports the synthesis, characterization and photodynamic activity of four high-valent fluorinated Sn(IV) porphyrins having different numbers of F-atoms in the peripheral of meso-phenyl groups viz. (Dichloro)meso-tetrakis(4-fluorophenylporphyrinato)stannic(IV), [Sn(IV)FTPP(Cl)2] or Sn1; (Dichloro)meso-tetrakis(2,4-difluorophenylporphyrinato)stannic(IV), [Sn(IV)2,4-FTPP(Cl)2] or Sn2; (Dichloro)meso-tetrakis(2,6-difluorophenylporphyrinato)stannic(IV), [Sn(IV)2,6-FTPP(Cl)2] or Sn3 and (Dichloro)meso-tetrakis(4-trifluoromethylphenylporphyrinato)stannic(IV), [Sn(IV)CF3TPP(Cl)2] or Sn4. The solid-state structure of Sn1 has been determined by single crystal X-ray diffraction analysis. The increasing number of F-atoms attached to the meso-phenyl positions of the porphyrin framework results in increase of their lipophilicity, singlet oxygen quantum yield (ΦΔ) and photocytotoxicity in A549 (human lung adenocarcinoma cells), MCF-7 and MDA-MB-231 (human breast adenocarcinoma) cells. Sn4 predominantly localize in the mitochondria of A549 cells. The light-induced cell death by the Sn(IV) porphyrins in A549 cells occur primarily via apoptosis.

Synthesis of Cytotoxic Benzofurans and Ethers Derivatives of Paeonol.

Paeonol is a broadly studied natural product due to its many biological activities. Using a methodology previously employed by our research group, 11 derivatives of paeonol were synthesized (seven of them are unpublished compounds), including four ethers and seven benzofurans. Additionally, we determined the crystal structure of one of these ether derivatives (1a) and of five benzofuran derivatives (2a, 2b, 2c, 2f and 2g) by single crystal X-Ray diffraction. To continue studying the cytotoxicity of this natural product and its derivatives, all compounds were tested against two cancer cell lines, HCT116 and MCF-7. Compounds 2b, 2e, and 2g were considered active against the colorectal adenocarcinoma cells HCT116 (Growth inhibition > 60%). Compound 2e showed an IC50 of 0.2 µM and was selected for further analysis, results reinforce its anticancer potential.

ABa6Cu31Te22 (A = K, Rb, Cs) Featuring Polyanionic Copper-Telluride Frameworks with Ultralow Thermal Conductivity.

Three polyanionic tellurides, ABa6Cu31Te22 (A = K, Rb, Cs), were synthesized in salt flux. The isostructural tellurides crystallize in a new structure type, in the cubic Pa3 space group with a Wyckoff sequence of d10c2b1 and large unit cell volumes of over 5500 Å3. The structures feature a framework of [CuTe4] tetrahedra and [CuTe3] trigonal pyramids with disorder in the Cu sites. The polyanionic frameworks have large square antiprism and cuboctahedral voids where Ba and alkali metal cations are situated, forming [BaTe8] and [ATe12], respectively. The overall compositions are close to being charge balanced. The large [ATe12] cuboctahedra allowed for significant anisotropic displacement of the A cations, as observed from both single crystal X-ray diffraction and heat capacity studies. Alkali cations rattling together with Cu atom displacement and disorder leads to the dispersion of phonons, thus softening the lattice and subsequently reducing the thermal conductivity. Evaluations of the electronic band structure revealed the occurrence of a narrow bandgap together with the presence of a flat band near the valence band maximum, giving rise to the high thermopower. The Cs and Rb analogues show a slope change in the temperature dependence of electrical resistivity around room temperature, which is typical for semimetals or degenerate semiconductors. For the as-synthesized and unoptimized materials, high values of the thermoelectric figure-of-merit of ∼0.2 were observed at 623 K.

The Halogenation Effect Induces a Variety of Switchable Phase Transition and Second-Harmonic-Generation Materials.

Halogen engineering offers a means of enhancing the physical properties of materials by fine-tuning the rotational energy barrier and dipole moment, which proved to be effective in achieving switchable phase transitions and optical responses in materials. In this work, by substituting the methyl group in ligand N-ethyl-1,5-diazabicyclo[3.3.0]octane (CH3CH2-3.3.0-Dabco) with halogen atoms X (Cl or Br) and then contining to react it with FeBr3 in a HBr aqueous solution, we successfully synthesized three kinds of organic-inorganic hybrid switchable phase-change materials, [CH3CH2-3.3.0-Dabco]FeBr4 (1), [ClCH2-3.3.0-Dabco]FeBr4 (2), and [BrCH2-3.3.0-Dabco]FeBr4 (3), which were fully characterized by single-crystal X-ray diffraction and variable-temperature powder X-ray diffraction. Compared to compound 1, compounds 2 and 3 show two pairs of reversible phase transitions, dielectric anomalies, and a second-harmonic-generation effect, which are successfully induced due to the halogen substitution. This study offers an effective molecular design strategy for the exploration and construction of iron halide organic-inorganic hybrid materials with temperature-adjustable physical properties.

U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo-salt Framework.

Pentavalent uranium compounds are key components of uranium's redox chemistry and play important roles in environmental transport. Despite this, well-characterized U(V) compounds are scarce primarily because of their instability with respect to disproportionation to U(IV) and U(VI). In this work, we provide an alternate route to incorporation of U(V) into a crystalline lattice where different oxidation states of uranium can be stabilized through the incorporation of secondary cations with different sizes and charges. We show that iriginite-based crystalline layers allow for systematically replacing U(VI) with U(V) through aliovalent substitution of 2+ alkaline-earth or 3+ rare-earth cations as dopant ions under high-temperature conditions, specifically Ca(UVIO2)W4O14 and Ln(UVO2)W4O14 (Ln=Nd, Sm, Eu, Gd, Yb). Evidence for the existence of U(V) and U(VI) is supported by single-crystal X-ray diffraction, high energy resolution X-ray absorption near edge structure, X-ray photoelectron spectroscopy, and optical absorption spectroscopy. In contrast with other reported U(V) materials, the U(V) single crystals obtained using this route are relatively large (several centimeters) and easily reproducible, and thus provide a substantial improvement in the facile synthesis and stabilization of U(V).

A Four-Coordinate Pr4+ Imidophosphorane Complex.

The imidophosphorane ligand, [NPtBu3]- (tBu = tert-butyl), enables isolation of a pseudo-tetrahedral, tetravalent praseodymium complex, [Pr4+(NPtBu3)4] (1-Pr), which is characterized by a suite of physical characterization methods including single-crystal X-ray diffraction, electron paramagnetic resonance, and L3-edge X-ray near-edge spectroscopies. Variable-temperature direct-current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce3+ analogue, driven by increased crystal field. The four-coordinate environment around Pr4+ in 1-Pr, which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin-orbit coupling in a molecular tetravalent lanthanide within a pseudo-tetrahedral coordination geometry.

Unravelling the kinetics of electro- and photochemical S → O linkage isomerization in Ru(II)-NHC-DMSO complexes utilised for photoinduced substitution reactions.

Our recently reported Ru(III)-NHC complexes 1a and 1b were utilized as suitable precursors to prepare new Ru(II)-NHC-(DMSO)2 complexes 2a and 2b. Complexes 2a and 2b reacted with 2,2'-bipyridine to give complexes 3a and 3b, respectively, with substitution of only one of the DMSO ligands. All new complexes were characterized using various spectroscopic techniques and the molecular structures of 2a and 3a were determined using single-crystal X-ray diffraction technique. Complexes 2a, 2b, 3a, and 3b showed the S → O linkage isomerization of the DMSO ligand upon oxidation of the Ru centre from +II to +III, as confirmed by the thermodynamic and kinetic data obtained from cyclic voltammetry experiments. It was observed that in the bisdimethylsulfoxide complexes 2a and 2b, only one DMSO ligand isomerized, which was further corroborated by the computational studies performed to optimize the geometry of the possible linkage isomers of complexes 2a and 3a in +2 and +3 oxidation states, whereas complexes 3a and 3b showed a high preference for the O-bound isomer in the Ru(III) redox state. The role of NHC in stabilizing the mixed isomer in complexes 2a and 2b and preventing the isomerization of both DMSO ligands coordinated to the Ru centre was studied; moreover, NHC provided good solvent compatibility for photochemical S → O isomerization in all the complexes. Taking advantages of the photoinduced linkage isomerization in 2a and 2b, the synthesis of 3a and 3b was revisited and performed using 2a and 2b, respectively, following a photoinduced substitution reaction in the presence of 2,2'-bipyridine. The kinetics of the reversion from the O-bound to S-bound isomer was found to follow the DMSO-assisted intermolecular S → O isomerization pathway.

1,2,4-Triazolo-quinazolinones as Effective Antifoulants: Molecular Design, Synthesis, and Biological Evaluation.

A series of 1,2,4-triazolo-quinazolinones and 1,2-benzisothiazolone derivatives (S1-S12) were successfully synthesized as environmentally friendly alternatives to copper-based antifouling paints using N-alkylation, cyclocondensation, and one-pot three-component and amide coupling reactions. The monoclinic structure of single-crystal 1,2,4-triazolo-quinazolin-acetic acid (S8) was confirmed by single-crystal X-ray diffraction analysis. All the synthesized molecules were studied for their in silico molecular docking interactions with three target proteins, namely, RbmA, ToxR, and Bap. Following that, the antialgal activity was assessed against two types of marine algae: Chlorella sp. and Chaetoceros curvisetus. The minimal inhibitory concentration and zone of inhibition have been used to evaluate the antibacterial activities of S1-S12 against both marine Gram-positive (Staphylococcus aureus) and Gram-negative (Vibrio parahemolyticus and Vibrio vulnificus) bacteria. Additionally, antifouling studies have been done on all the compounds, and among them, 1,2,4-triazolo-quinazolinyl-acetate (S7), 1,2,4-triazolo-quinazolinyl-acetic acid (S8), 1,2,4-triazolo-quinazolinyl-oxobutanoate (S9), benzo[d]isothiazolyl butanoate (S10), benzo[d]isothiazolyl-acetic acid (S11), and 1,2,4-triazolo-quinazolinyl-acetyl-benzo[d]isothiazolone (S12) exhibited good antialgal, antibacterial, and antifouling activities.

Crystal Growth of Quaternary AkRE2Si2S8 (Ak = Ca and Sr; RE = La-Tb) Thiosilicates Using Flux-Assisted Boron Chalcogen Mixture Method: Exploring X-ray Scintillation, Luminescence, and Magnetic Properties.

We report on the detailed structural analysis of a series of 11 new quaternary rare earths containing thiosilicates, AkRE2Si2S8 (Ak = Ca and Sr; RE = La, Ce, Pr, Nd, Sm, Gd, and Tb), synthesized using the flux-assisted boron chalcogen mixture method. High quality crystals were grown and used to determine their crystal structures by single crystal X-ray diffraction. All members of the AkRE2Si2S8 series crystallize in the trigonal crystal system with space group R3̅c (space group no. 167). Polycrystalline powders were used for physical property measurements, including magnetic susceptibility, diffuse reflectance in the UV-visible range, and scintillation. Magnetic measurements indicated that CaRE2Si2S8 (RE = Nd and Tb) exhibits paramagnetic behavior with a slightly negative Weiss constant. The band gaps of the materials were determined from diffuse reflectance data, and optical band gaps were estimated to be 2.5(1) and 2.9(1) eV for CaCe2Si2S8 and CaGd2Si2S8, respectively. CaCe2Si2S8, CaTb2Si2S8, and SrCe2Si2S8 exhibited intense green luminescence upon irradiation with 375 nm ultraviolet light and, furthermore, scintillated when exposed to X-rays. Radioluminescence measurements of CaCe2Si2S8 powder revealed green emission with an intensity approximately 14% of that emitted by bismuth germanium oxide powder.

Crystal Structure of Bis(1-butyl-1-methypyrrolidinium) Perthiodicarbonate Complex

Bis(1-butyl-1-methypyrrolidinium) perthiodicarbonate was obtained by the reaction of carbon disulfide with 1-butyl-1-methypyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. Structural characterization of this original complex was achieved by single-crystal X-ray diffraction (SCXRD) analysis. The asymmetric unit of the title compound, C2S6·2C9H20N, consisted of two crystallographically 1-methyl-1-butyl pyrrolidinium cations and one perthiodicarbonate anion. The complex C2S6·2C9H20N crystallized in the monoclinic space group, C 2/c, and possessed the following cell parameters: a = 16.0970(10) Å, b = 14.7140(9) Å, c = 12.3280(8) Å, α = 90°, β = 112.3730(12)°, γ = 90°, V = 2700.11 Å3, and Z = 8, Z’ = 0.5.

Structural chemistry of mixed-ligand fluoride complexes of uranyl

AbstractThe crystal structures of mixed-ligand sulfato-, selenato-, phosphato-, arsenato-, and chromato-fluoride complexes of uranyl and of mixed-ligand carboxylato-fluoride and mixed-ligand fluoride complexes with neutral donor ligands studied by the single-crystal X-ray diffraction method were systematized and discussed. The crystal chemical features of the structures of the mixed-ligand fluoride complexes of uranyl were determined: the coordination polyhedron of the hexavalent uranium atom in the structures of the mixed-ligand fluoride complexes of uranyl (except for three hexagonal-bipyramidal complexes) has a pentagonal-bipyramidal structure: the oxygen atoms of the uranyl group are located on the vertical axis of the pentagonal bipyramid, perpendicular to the equatorial plane in which five atoms are located. In dimeric and polymeric chains of mixed-ligand fluoride complexes of uranyl (with the exception of one compound in which the common bridge in the dimer complex is oxygen atoms), the uranyl units are linked via fluoride bridges. Inorganic and organic ligands, which contained O-donor atoms, combine dimers and polymer chains into layers and three-dimensional formation.

Solvent Free Potassium 3,5-dinitro-6-oxo-1,6-dihydropyrazin-2-olate 3D EMOF as Thermally Stable Energetic Material.

Heat-resistant explosives play a vital role in indispensable applications. For this, we have synthesized a novel, three-dimensional, solvent-free energetic metal-organic framework (EMOF) potassium 3,5-dinitro-6-oxo-1,6-dihydropyrazin-2-olate (KDNODP) straightforwardly. The synthesized EMOF was characterized through IR, NMR spectroscopy, elemental analysis, and differential scanning calorimetry studies. Furthermore, single-crystal X-ray diffraction provided a complete description of KDNODP. It exhibits a three-dimensional EMOF structure with remarkably balanced properties such as high density (2.11 g cm-3), excellent thermal stability (291 °C), good detonation performance (8127 m s-1 and 26.94 GPa) and low mechanical sensitivity (IS=35 J; FS=360 N) than the commonly used heat-resistant explosives HNS (density=1.74 g cm-3; VOD=7164 m s-1, DP=21.65 GPa, IS=5 J) as well as the similar reported energetic potassium MOFs. To gain insights into the packing and intermolecular interactions, the Hirshfeld surface and a 2D fingerprint analysis were examined. Additionally, scanning electron microscopy was used to investigate the particle size and morphological characteristics of KDNODP. These outcomes highlight a successful method for creating 3D EMOF based on a six-membered heterocycle as a potential heat-resistant energetic material.

Organo Chalcogenone-Triggered Luminescent Copper(I) Clusters for Light Emitting Applications.

A novel organo sulfur and selenium-controlled emission behavior in discrete copper(I) clusters has been demonstrated for the first time. The pentanuclear [Cu5Br5(L1)2] (1), trinuclear [Cu3Br3(L2)2] (2), dinuclear [Cu2I2(L1)2] (3), and tetranuclear [Cu4I4(L2)2CH3CN] (4) copper(I) discrete clusters have been synthesized from the reaction between L1 [L1 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] or L2 [L2 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] chelating ligands and corresponding copper(I) halide salts. These new clusters have been characterized by FT-IR, UV-visible, thermogravimetric analysis, and fluorescence spectroscopy techniques. Single-crystal X-ray diffraction studies reveal that 1-4 consists of abundant d10-d10 interactions. The structural and bonding features of clusters have been investigated using density functional theory calculations. Notably, the L2-ligated 2 and 4 are poorly emissive, while L1-ligated 1 and 3 showed strong emission in the orange and green regions, respectively. The time-dependent density functional theory natural transition orbital calculations of 1 and 3 reveal the nature of the transitions contributed by 3MLCT/3LLCT/3ILCT. Photoluminescence quantum yields of 1 and 3 are 19 and 11%, with average lifetimes of 21.55 and 6.57 μs, respectively. 1 and 3 were coated on prototype LED bulbs for light-emitting performance.

Synthesis of paeonol hydrazone derivatives and their anti-oomycete, anti-fungal, and nematicidal activities.

The natural product paeonol is a rich and sustainable natural bioresource, and its derivatives have various unique biological efficacy. As is well known, Schiff bases are a class of organic compounds with a wide range of biological activities, including anti-fungal, insecticidal, anti-viral, and nematicidal. To discover biorational natural product-based pesticides, nine intermediates (2-10), 12 sulfonylhydrazones (11a-11c, 12a-12c, 13a-13c, and 14a-14c) and 20 benzylidene hydrazones (18a-18r, 19a, and 20a) were synthesized by structural modification of paeonol, and their structures were characterized by proton nuclear magnetic resonance (1H NMR), carbon-13 (13C) NMR, and high-resolution mass spectrometry (HRMS). The stereochemical configurations of compounds 14a, 18d, and 18r were unambiguously confirmed by single-crystal X-ray diffraction. Furthermore, bioactivities of these compounds as anti-oomycete, anti-fungal, and nematicidal agents against three serious agricultural pests, Phytophthora capsici, Fusarium graminearum, and Heterodera glycines were evaluated. Among all tested compounds: (i) compound 7 exhibited promising anti-oomycete against Phytophthora capsici, with a half maximal effective concentration (EC50) value of 15.81 mg L-1; (ii) compounds 2, 7, 10, and 19a displayed promising anti-fungal against F. graminearum, with EC50 values of 12.22, 14.72, 23.39, and 33.10 mg L-1, respectively; (iii) ten compounds (12a-12c, 14c, 18g-18j, 18m, and 19a) showed significant nematicidal activity against H. glycines, with median lethal concentration (LC50) values all less than 30.00 mg L-1. Especially for compound 18g, its LC50 value is the smallest, at 12.65 mg L-1. The research results indicate that introducing nitro groups at the C5 position of paeonol, or introducing halogens at both C5 and C3 positions, can significantly enhance its biological activity against Phytophthora capsici, F. graminearum, and H. glycines. © 2024 Society of Chemical Industry.

Isoxerophilusins A and B, Two Novel Polycyclic Asymmetric Diterpene Dimers from Isodon xerophilus: Structural Elucidation, Modification, and Inhibitory Activities against α-Glucosidase.

Isoxerophilusins A (1) and B (2), two unprecedented diterpene heterodimers biogenetically from ent-atisanes and abietanes, were isolated from the rhizomes of Isodon xerophilus. Their structures were determined by extensive spectroscopic analysis and single-crystal X-ray diffraction. Selective esterification of 1 generated 11 new derivatives. All derivatives showed excellent α-glucosidase inhibitory activity in comparison to acarbose. Compounds 12 and 13 demonstrated significant inhibition against α-glucosidase with IC50 values of 4.92 and 3.83 μM, respectively.