Synthesis, structure and photoluminescence properties of heterometallic-based coordination polymers of trimesic acid.

Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110 °C under hydrothermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetraaquazinc(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetraaquacobalt(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2- ligand to create a one-dimensional (1D) zigzag chain. Poly[[decaaquabis(µ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a temperature of 140 °C. It forms crystals in the orthorhombic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer composed of [Zn(TMA)] chains that are interconnected by CaII ions. The presence of aromatic carboxylic acid ligands and water molecules, which can form numerous hydrogen bonds and π-π interactions, increases the stability of the three-dimensional (3D) supramolecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420 °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low molecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone molecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.

Smart and UV-Resistant Edible Coating and Films Based on Alginate, Whey Protein, and Curcumin.

In this work, smart edible coating and films with excellent UV barrier properties were prepared from alginate, whey protein isolate, and curcumin. The primary focus of this investigation centered on assessing the impact of whey protein and curcumin on the physical and functional properties of the alginate films. Whey protein reduced the film transparency while simultaneously enhancing the hydrophobicity and antioxidant properties of the alginate film. Curcumin imparted a yellow hue to the film, consequently decreasing the transparency of the film. It also substantially improved hydrophobicity, antioxidant activity, and UV-blocking efficiency within the films. Remarkably, curcumin demonstrated a significant reduction in the water vapor transmission rate of the film. For the preservation of apples, a higher concentration of curcumin was required, which effectively suppressed the respiration rate and moisture loss post-harvest, resulting in an extended shelf-life for the apples. As a result, the coated apples exhibited significantly reduced enzymatic browning and weight loss in comparison to their uncoated counterparts. Furthermore, these curcumin-containing films underwent a reversible color change from orange to red when exposed to ammonia vapor. This attribute highlights the potential of the developed coating and film as a smart, active food packaging solution, particularly for light-sensitive food products.

Kaemtakols A-D, highly oxidized pimarane diterpenoids with potent anti-inflammatory activity from Kaempferia takensis.

Four highly oxidized pimarane diterpenoids were isolated from Kaempferia takensis rhizomes. Kaemtakols A-C possess a tetracyclic ring with either a fused tetrahydropyran or tetrahydrofuran motif. Kaemtakol D has an unusual rearranged A/B ring spiro-bridged pimarane framework with a C-10 spirocyclic junction and an adjacent 1-methyltricyclo[3.2.1.02,7]octene ring. Structural characterization was achieved using spectroscopic analysis, DP4 + and ECD calculations, as well as X-ray crystallography, and their putative biosynthetic pathways have been proposed. Kaemtakol B showed significant potency in inhibiting nitric oxide production with an IC50 value of 0.69 µM. Molecular docking provided some perspectives on the action of kaemtakol B on iNOS protein.

Base-Mediated and Silver-Catalyzed Divergent Synthesis of Hydroxynaphthalenamides and Phosphorylated Dihydronaphthylamides from Enone-Oxazolones.

An efficient divergent approach to functionalized naphthalene derivatives, the naphthalenamides, via base-mediated and silver-catalyzed cyclization has been developed using enone-oxazolones as the precursors. This protocol utilized base in methanol with heating to construct the corresponding hydroxynaphthalenamides 2 by a C-C bond formation, oxazolone ring-opening, and aromatization in good yields. On the other hand, phosphorylated dihydronaphthylamides 3 were generated by using H-phosphonate as the phosphonating reagent in a silver-catalyzed cyclization involving the phospha-1,4-addition/intramolecular ring closure with concomitant C-P/C-C bond formation in good yields.

Selective electrophilic cyclization of ortho-carbonylarylacetylenols for the synthesis of cyclopenta[a]naphthalenol and 2-phenylnaphthalen-1-ol analogs.

This work demonstrates a new method for the synthesis of cyclopenta[a]naphthalenol and 2-phenylnaphthalen-1-ol analogs via selective cyclization. ortho-Alkynylarylkenones were employed as the common substrates that could be prepared by Sonogashira coupling between 2-haloarylacetophenone and pent-4-yn-1-ol derivatives. These precursors were used without purification to construct 2-phenylnaphthalen-1-ol intermediates by treating with (+)-CSA under heating conditions. Selective cyclization occurred when the reaction was conducted in methyl trimethylacetate solvent which predominantly produced the 2-phenylnaphthalen-1-ol product through 6-endo-dig cyclization without elimination or the formation of cyclopenta[a]naphthalenol via shutting down the 5-exo-dig mode of cyclization. Switching the acid from a Brønsted acid to Bi(OTf)3 led to smooth reactions, providing the cyclopenta[a]naphthalenol products in moderate to good yields. Moreover, we also demonstrated the utilization of 2-phenylnaphthalen-1-ol to prepare naphthoquinone, which is an important core structure of bioactive and natural product compounds.

Nanotubule inclusion in the channels formed by a six-fold interpenetrated, triperiodic framework.

When reacted together with uranyl ions under solvo-hydrothermal conditions, a bis(pyridiniumcarboxylate) zwitterion (L) and tricarballylic acid (H3tca) give the complex [NH4]2[UO2(L)2][UO2(tca)]4·2H2O (1). The two ligands are segregated into different units, an anionic nanotubule for tca3- and a six-fold interpenetrated cationic framework with lvt topology for L. The entangled framework defines large channels which contain the square-profile nanotubules. Complex 1 has a photoluminescence quantum yield of 19% and its emission spectrum shows the superposition of the signals due to the two independent species.

Molecularly dispersed nickel complexes on N-doped graphene for electrochemical CO2 reduction.

In this work, new hybrid catalysts based on molecularly dispersed nickel complexes on N-doped graphene were developed for electrochemical CO2 reduction (ECR). Nickel(II) complexes (1-Ni, 2-Ni), and a new crystal structure ([2-Ni]Me), featuring N4-Schiff base macrocycles, were synthesized and investigated for their potential in ECR. Cyclic voltammetry (CV) in NBu4PF6/CH3CN solution demonstrated that the nickel complexes bearing N-H groups (1-Ni and 2-Ni) showed a substantial current enhancement in the presence of CO2, while the absence of N-H groups ([2-Ni]Me) resulted in an almost unchanged voltammogram. This indicated the necessity of the N-H functionality towards ECR in aprotic media. All three nickel complexes were successfully immobilized on nitrogen-doped graphene (NG) via non-covalent interactions. All three Ni@NG catalysts exhibited satisfactory CO2-to-CO reduction in aqueous NaHCO3 solution with the faradaic efficiency (FE) of 60-80% at the overpotential of 0.56 V vs. RHE. The ECR activity of [2-Ni]Me@NG also suggested that the N-H moiety from the ligand is less important in the heterogeneous aqueous system owing to viable hydrogen-bond formation and proton donors from water and bicarbonate ions. This finding could pave the way for understanding the effects of modifying the ligand framework at the N-H position toward fine tuning the reactivity of hybrid catalysts through molecular-level modulation.

Woven, Polycatenated, or Cage Structures: Effect of Modulation of Ligand Curvature in Heteroleptic Uranyl Ion Complexes.

Combining the flexible zwitterionic dicarboxylate 4,4'-bis(2-carboxylatoethyl)-4,4'-bipyridinium (L) and the anionic dicarboxylate ligands isophthalate (ipht2-) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda2-), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO2)2(L)(ipht)2] (1) and [(UO2)2(L)(1,2-pda)2]·2H2O (2) have the same stoichiometry, and both crystallize as monoperiodic coordination polymers containing two uranyl-(anionic carboxylate) strands united by L linkers into a wide ribbon, all ligands being in the divergent conformation. Complex 3, [(UO2)2(L)(1,3-pda)2]·0.5CH3CN, with the same stoichiometry but ligands in a convergent conformation, is a discrete, binuclear species which is the first example of a heteroleptic uranyl carboxylate coordination cage. With all ligands in a divergent conformation, [(UO2)2(L)(1,4-pda)(1,4-pdaH)2] (4) crystallizes as a sinuous and thread-like monoperiodic polymer; two families of chains run along different directions and are woven into diperiodic layers. Modification of the synthetic conditions leads to [(UO2)4(LH)2(1,4-pda)5]·H2O·2CH3CN (5), a monoperiodic polymer based on tetranuclear (UO2)4(1,4-pda)4 rings; intrachain hydrogen bonding of the terminal LH+ ligands results in diperiodic network formation through parallel polycatenation involving the tetranuclear rings and the LH+ rods. Complexes 1-3 and 5 are emissive, with complex 2 having the highest photoluminescence quantum yield (19%), and their spectra show the maxima positions usual for tris-κ2O,O'-chelated uranyl cations.

Study on the absolute configuration and biological activity of rotenoids from the leaves and twigs of Millettia pyrrhocarpa Mattapha, Forest & Hawkins, sp. Nov.

BACKGROUND: M. pyrrhocarpa is a new plant in the Fabaceae: Faboideae family that is found in Thailand. A literature search revealed that the Milletia genus is rich in bioactive compounds possessing a wide range of biological activities. In this study, we aimed to isolate novel bioactive compounds and to study their bioactivities. METHODS: The hexane, ethyl acetate, and methanol extracts from the leaves and twigs of M. pyrrhocarpa were isolated and purified using chromatography techniques. These extracts and pure compounds were tested in vitro for their inhibitory activities against nine strains of bacteria, as well as their anti-HIV-1 virus activity and cytotoxicity against eight cancer cell lines. RESULTS: Three rotenoids, named 6aS, 12aS, 12S-elliptinol (1), 6aS, 12aS, 12S-munduserol (2), dehydromunduserone (3), and crude extracts were evaluated for antibacterial, anti-HIV, and cytotoxic activities. It was found that compounds 1-3 inhibited the growth of nine strains of bacteria, and the best MIC/MBC values were obtained at 3/ > 3 mg/mL. The hexane extract showed anti-HIV-1 RT with the highest %inhibition at 81.27 at 200 mg/mL, while 6aS, 12aS, 12S-elliptinol (1) reduced syncytium formation in 1A2 cells with a maximum EC50 value of 4.48 µM. Furthermore, 6aS, 12aS, 12S-elliptinol (1) showed cytotoxicity against A549 and Hep G2 cells with maximum ED50 values of 2.27 and 3.94 µg/mL. CONCLUSION: This study led to the isolation of constituents with potential for medicinal application, providing compounds (1-3) as lead compounds against nine strains of bacteria. The hexane extract showed the highest %inhibition of HIV-1 virus, Compound 1 showed the best EC50 in reducing syncytium formation in 1A2 cells, and it also showed the best ED50 against human lung adenocarcinoma (A549) and human hepatocellular carcinoma (Hep G2). The isolated compounds from M. pyrrhocarpa offered significant potential for future medicinal application studies.

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 µmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Two new serratene triterpenes from club moss cultivars.

Two new serratene triterpenes, 14α,21ß-dihydroxyserrat-3ß-yl acetate and 3α,21ß-dihydroxyserrat-14-en-23-oic acid, together with eight known compounds were isolated from two club moss cultivars, Phlegmariurus carinatus (Desv.) Ching and Phlegmariurus nummulariifolius (Blume) Ching. 14α,21ß-Ddihydroxyserrat-3ß-yl acetate (1) was isolated from P. carinatus, and 3α,21ß-dihydroxyserrat-14-en-23-oic acid (2), an undescribed carboxylic group at C-23 position of the serratene triterpenoids, was isolated from P. nummulariifolius. The structures of these new compounds were elucidated by using HR-ESIMS, UV, IR, 1D (1H and 13C NMR spectra), 2D NMR spectra, experimental ECD spectrometry and the single-crystal X-ray analysis. Biological evaluation of 14α,21ß-dihydroxyserrat-3ß-yl acetate (1) and lycoclavanol (8) revealed moderate cytotoxic activity on three tumor cell lines (HepG2, A549 and HuCCA-1) whereas 3α,21ß-dihydroxyserrat-14-en-23-oic acid (2) showed strong inhibitory effect on HuCCA-1 cells with the IC50 of 4.72 µM.

Dual stimuli-responsive phosphorescence of a Pb(II) coordination polymer to acidic vapors and thermal treatment.

We present a new intensely phosphorescent Pb(II) coordination polymer (1) containing a heteroatomic ligand. It has a quantum yield of 21.62% and a lifetime of 25.46 µs. The naked-eye solid-state photoluminescence of 1 significantly changes in response to acidic vapors and thermal treatment, indicating the coexistence of acidochromic and thermochromic luminescence.

Crystal structure of a new europium(III) compound based on thio-phene-acrylic acid.

A europium(III) coordination compound based on thio-phene-acrylic acid (Htpa), tri-aqua-tris-[3-(thio-phen-2-yl)prop-2-enoato-κ2 O,O']europium(III)-3-(thio-phen-2-yl)prop-2-enoic acid (1/3), [Eu(C7H5O2S)3(H2O)3]·3C7H6O2S or [Eu(tpa)3(H2O)3]·3(Htpa) (1), where tpa is the conjugate base of Htpa, has been synthesized and structurally characterized. Compound 1 crystallizes in the trigonal space group R3. The structure of 1 consists of a discrete mol-ecular complex [Eu(tpa)3(H2O)3] species and the Htpa mol-ecule. In the crystal, the two components are involved in O-H⋯O [ring motif R 2 2(8)] and C-H⋯π hydrogen-bonding inter-actions. These inter-actions were further investigated by Hirshfeld surface analysis, which showed high contributions of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H contacts to the total Hirshfeld surfaces.

Crystal structure and Hirshfeld surface analysis of a new mononuclear copper(II) complex: [bis-(pyridin-2-yl-κN)amine](formato-κO)(m-hy-droxy-benzoato-κ2O,O')copper(II).

A new mononuclear copper(II) complex, [Cu(C7H5O3)(HCO2)(C10H9N3)], containing mixed N- and O-donor ligands, 2,2'-di-pyridyl-amine (dpyam) and m-hy-droxy-benzoate (m-OHbenz), has been obtained from a solvent mixture. The coordination environment of the CuII ion is distorted square-pyramidal with a [N2O3] coordination set originating from the chelating dpyam and m-OHbenz ligands in the basal plane and the O atom of a formato ligand at the apical position. The crystal structure of the title complex is stabilized by N-H⋯O, O-H⋯O, C-H⋯O hydrogen-bonding, π-π and C-H⋯π inter-molecular inter-actions, which were qu-anti-fied by Hirshfeld surface analysis.

Crystal structure of catena-poly[[[bis-(1-benzyl-imidazole-κN)copper(II)]-µ-sulfato-κ2 O:O'-[tetra-kis-(1-benzyl-imidazole-κN)copper(II)]-µ-sulfato-κ2 O:O'] N,N-di-methyl-formamide disolvate dihydrate].

The title one-dimensional copper(II) coordination polymer, {[Cu(SO4)(C10H10N2)3]·C3H7NO·H2O} n or {[Cu(bzi)3(µ-O2SO2)]·H2O·DMF} n (bzi = 1-benz-yl-imidazole, C10H10N2; DMF = N,N-di-methyl-formamide, C3H7NO), is constructed by monodentate bzi ligands and bridging sulfate anions, leading to chains propagating parallel to the c axis. Within a chain, there are two crystallographic independent CuII ions, each with site symmetry , which form [CuN2O2] and [CuN4O2] polyhedra alternating along the chain direction. The crystal structure is consolidated by weak hydrogen-bonding, C-H⋯π and π-π inter-actions, leading to the formation of a three-dimensional supra-molecular network.

Discovery of nitric oxide-inducing activities of synthetic LAM glycan motifs prepared by scalable rapid syntheses.

Enhancement of local nitric oxide (NO) concentration is important for the effectiveness of an adjuvant and for both innate and adaptive immunological responses. Currently, the information on the NO-inducing activities of lipoarabinomannan (LAM) glycan motifs on Mycobacterium tuberculosis (Mtb) is not possibly available. Thus, detailed studies on the structure-activity relationship of discrete LAM glycan motifs could provide valuable information towards the development of adjuvants and vaccines against Mtb. Using the newly-designed monomers and linker, the new rapid synthesis strategies demonstrated in this work enabled accessibilities to α(1→6)-D-mannans and α(1→5)-D-arabinans, which are the key LAM glycan motifs, with different controlled-sizes, in a scalable fashion. The glycans were evaluated for their ability to co-stimulate nitric oxide in macrophages. Only short and medium α(1→5)-D-arabinans show distinct abilities to strongly enhance LPS-induced nitric oxide, suggesting their potential use as stronger immunomodulators than α(1→6)-D-mannans, and thus, implying an unknown receptor responsible for this NO-inducing effect.

Siamenflavones A-C, three undescribed biflavonoids from Selaginella siamensis Hieron. and biflavonoids from spike mosses as EGFR inhibitor.

Three undescribed biflavonoids (BFVs), siamenflavones A-C along with twelve BFVs were isolated from Selaginella siamensis Hieron. and Selaginella bryopteris (L.) Baker (Selaginellaceae). The chemical structures of undescribed compounds were established through comprehensive spectroscopic techniques, chemical correlations, and X-ray crystallography. The ten isolated BFVs, siamenflavones A-C, delicaflavone, chrysocauflavone, robustaflavone, robustaflavone-4-methylether, amentoflavone, tetrahydro-amentoflavone, and sciadopitysin were evaluated for the antiproliferative effects against four human cancer cell lines A549, H1975, HepG2 and T47D. Delicaflavone and robustaflavone 4'-methylether exerted strong effects on the four human cancer cell lines. Siamenflavone B, delicaflavone and robustaflavone 4'-methylether showed potent inhibitory activities against wild-type EGFR. The inhibition of the compounds was further supported by molecular docking and predictive intermolecular interactions. Molecular dynamics simulation studies of siamenflavone B and robustaflavone-4'-methylether complexed to EGFR-TK further supported inhibition of the compounds to the ATP binding site. Finally, analysis of pharmacokinetic and electronic properties using density-functional theory and known drug index calculations suggest that the compounds are pharmaceutically compatible for drug administration.

Incorporation of Cation Affects the Redox Reactivity of Fe-NNN Complexes on C-H Oxidation.

Cations such as Lewis acids have been shown to enhance the catalytic activity of high-valent Fe-oxygen intermediates. Herein, we present a pyridine diamine ethylene glycol macrocycle, which can form Zn(II)- or Fe(III)-complex with the NNN site, while allowing redox-inactive cations to bind to the ethylene glycol moiety. The addition of alkali, alkali earth, and lanthanum ions resulted in positive shifts to the Fe(III/II) redox potential. Calculation of dissociation constants showed the tightest binding with a Ba2+ ion. Density functional theory calculations were used to elucidate the effects of redox inactive cations toward the electronic structures of Fe complexes. Although the Fe-NNN complexes, both in the absence and presence of cations, can catalyze C-H oxidation of 9,10-dihydroanthracene, to give anthracene [hydrogen atom transfer (HAT) product], anthrone, and anthraquinone [oxygen atom transfer (OAT) products], highest overall activity and OAT/HAT product ratios were obtained in the presence of dications, that is, Ba2+ and Mg2+, respectively.

Simultaneous Occurrence of Vapochromism and Vapoluminescence in Formaldehyde-Responsive Amino-Functionalized Copper(I) Polymorphic Coordination Polymers.

The use of vapor-responsive chromic materials in sensing applications for the detection of harmful volatile organic chemicals is rapidly expanding. Herein, four new amino-functionalized Cu(I) coordination polymers of [CuI(pyt-NH2)]n (1) and (2) and [CuSCN(pyt-NH2)]n (3) and (4) (where pyt-NH2 = 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) were successfully synthesized. Single-crystal X-ray diffraction analysis reveals that 1 and 2 are iodo-based polymorphs, while 3 and 4 are thiocyanato-based polymorphs. They possess densely diverse crystalline architectures decorated by uncoordinated amino groups as a binding site. Also, 1-4 show a variety of color and luminescence based on the structural diversity. Remarkably, 1 and 2 undergo the change of color and naked-eye solid-state luminescence in response to formaldehyde (FA) vapor, demonstrating simultaneous vapochromism and vapoluminescence. The chromic Cu(I) coordination polymers in this work present for the first time dual-mode vapochromism and vapoluminescence in a highly selective response to FA vapor. The responsive mechanism has been clarified by Fourier transform infrared spectroscopy (FT-IR), electrospray ionization mass spectrometry (ESI-MS), 1H nuclear magnetic resonance (NMR), powder X-ray diffraction (PXRD), and luminescence lifetime measurements, which reveal carbinolamine formation via the specific reaction between FA and the active amino groups of coordinated pyt-NH2. The carbinolamine formation can trigger the structural transformation of 1 and 2, leading to the concurrently selective vapochromism and vapoluminescence induced by FA vapor.

Crystal structure and Hirshfeld surface analysis of tris-(acetohydrazide-κ2 N,O)(nitrato-κO)(nitrato-κ2 O,O')terbium(III) nitrate.

In the title lanthanide(III) compound, [Tb(NO3)2(C2H6N2O)3]NO3, the asym-metric unit contains one Tb3+ ion, three acetohydrazide (C2H6N2O) ligands, two coordinated nitrate anions, and an isolated nitrate anion. The Tb3+ ion is in a ninefold coordinated distorted tricapped trigonal-prismatic geometry formed by three oxygen atoms and three nitro-gen atoms from three different acetohydrazide ligands and three oxygen atoms from two nitrate anions. In the crystal, the complex mol-ecules and the non-coordinated nitrate anions are assembled into a three-dimensional supra-molecular architecture through extensive N-H⋯O hydrogen-bonding inter-actions between the amine NH groups of the acetohydrazide ligands and the nitrate oxygen atoms. Hirshfeld surface analysis was performed to aid in the visualization of inter-mol-ecular contacts.