Construction of 2D zinc(II) MOFs with tricarboxylate and N-donor mixed ligands for multiresponsive luminescence sensors and CO adsorption.

The solvothermal reactions of ZnCl·6HO, benzene-1,3,5-tribenzoic acid (Hbtb), and N-heterocyclic ancillary imidazole (Im) or aminopyrimidine (a mp) ligands led to the creation of two-dimensional (2D) zinc(II) based metal-organic frameworks (MOFs), (MeNH)[Zn(btb)(Im)]·2DMF·3MeOH (1) and (MeNH)[Zn(btb)(amp)]·HO·2DMF·MeOH (2). The btb ligands in 1 and 2 form an anionic 2D layered structure with a (6) honeycomb (hcb) topology by linking to Zn(II) centres through their carboxylate groups. The incorporation of N-heterocyclic auxiliary ligands Im and amp into the hcb nets resulted in the formation of a 2D hydrogen-bonded and covalently pillared bilayer structure featuring two-fold interpenetrating networks.

Cascade Cyclization of -(2-Acyl-1-ethynyl)benzaldehydes with Amino Acid Derivatives: Synthesis of Indeno[2,1-]pyran-3-ones and 1-Oxazolonylisobenzofurans via the Erlenmeyer-Plöchl Azlactone Reaction.

A highly regioselective divergent approach is reported for the synthesis of both indeno[2,1-]pyran-3-one and 1-oxazolonylisobenzofuran derivatives using the Erlenmeyer-Plöchl azlactone (EPA) reaction. This approach involves the synthesis of -(2-acyl-1-ethynyl)benzaldehydes, which reacted with various amino acids. Reaction with -acylglycines resulted in the formation of indeno[2,1-]pyran-3-ones, involving the sequential formation of two C-C bonds and two C-O bonds.

Effects of the ligand linkers on stability of mixed-valence Cu(I)Cu(II) and catalytic aerobic alcohol oxidation activity.

We synthesized a class of ligands that feature single (L1) and dual amine-bis(triazole) chelates (L2 with a 1,3-phenylene linker and L3 with a 1,5-naphthalene linker). Our findings which were derived from UV-Vis titrations, crystal structure analysis of relevant copper complexes, and DFT calculations indicate the formation of both mononuclear CuBr(L1) and dinuclear (μ-Ln)(CuBr) (Ln = L2 and L3) complexes. The catalytic activities of CuBr/Ln, in combination with TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) co-catalyst and NMI (N-methylimidazole) for aerobic alcohol oxidation, reveal the following activity trend: CuBr/L3 > CuBr/L2 > CuBr/L1.

Synthesis, crystal structure and properties of poly[di-μ-chlorido-di-μ-chlorido-bis-[4-methyl--(pyridin-2-yl-methyl-idene)aniline]dicadmium(II)].

The title coordination polymer with the 4-methyl--(pyridin-2-yl-methyl-idene)aniline Schiff base ligand (, CHN), [CdCl(CHN)] (), exhibits a columnar structure extending parallel to [100]. The columns are aligned in parallel and are decorated with chelating ligands on both sides. They are elongated into a supra-molecular sheet extending parallel to (01) through π-π stacking inter-actions involving ligands of neighbouring columns.

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

Reacting trimesic acid (HTMA, CHO) with CaCl and MCl 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)(HO)], 1, and catena-poly[[tetraaquacobalt(II)]-μ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-μ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)(HO)], 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate Ca ions and six-coordinate M ions.

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.

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

A new mononuclear copper(II) complex, [Cu(CHO)(HCO)(CHN)], containing mixed - and -donor ligands, 2,2'-di-pyridyl-amine (dpyam) and -hy-droxy-benzoate (-OHbenz), has been obtained from a solvent mixture. The coordination environment of the Cu ion is distorted square-pyramidal with a [NO] coordination set originating from the chelating dpyam and -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, and C-H⋯ inter-molecular inter-actions, which were qu-anti-fied by Hirshfeld surface analysis.

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.

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 by a C-C bond formation, oxazolone ring-opening, and aromatization in good yields. On the other hand, phosphorylated dihydronaphthylamides were generated by using -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 -carbonylarylacetylenols for the synthesis of cyclopenta[]naphthalenol and 2-phenylnaphthalen-1-ol analogs.

This work demonstrates a new method for the synthesis of cyclopenta[]naphthalenol and 2-phenylnaphthalen-1-ol analogs selective cyclization. -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.

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 (Htca) give the complex [NH][UO(L)][UO(tca)]·2HO (1). The two ligands are segregated into different units, an anionic nanotubule for tca and a six-fold interpenetrated cationic framework with topology for L. The entangled framework defines large channels which contain the square-profile nanotubules.

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

In this work, new hybrid catalysts based on molecularly dispersed nickel complexes on N-doped graphene were developed for electrochemical CO reduction (ECR). Nickel(II) complexes (1-Ni, 2-Ni), and a new crystal structure ([2-Ni]Me), featuring N-Schiff base macrocycles, were synthesized and investigated for their potential in ECR. Cyclic voltammetry (CV) in NBuPF/CHCN solution demonstrated that the nickel complexes bearing N-H groups (1-Ni and 2-Ni) showed a substantial current enhancement in the presence of CO, while the absence of N-H groups ([2-Ni]Me) resulted in an almost unchanged voltammogram.

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 O 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.

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 (ipht) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO)(L)(ipht)] () and [(UO)(L)(1,2-pda)]·2HO () 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 , [(UO)(L)(1,3-pda)]·0.

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.

Two new serratene triterpenes from club moss cultivars.

Two new serratene triterpenes, 14α,21β-dihydroxyserrat-3β-yl acetate and 3α,21β-dihydroxyserrat-14-en-23-oic acid, together with eight known compounds were isolated from two club moss cultivars, (Desv.) Ching and (Blume) Ching. 14α,21β-Ddihydroxyserrat-3β-yl acetate () was isolated from , and 3α,21β-dihydroxyserrat-14-en-23-oic acid (), an undescribed carboxylic group at C-23 position of the serratene triterpenoids, was isolated from .

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.

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-κ ,']europium(III)-3-(thio-phen-2-yl)prop-2-enoic acid (1/3), [Eu(CHOS)(HO)]·3CHOS or [Eu(tpa)(HO)]·3(Htpa) (), where tpa is the conjugate base of Htpa, has been synthesized and structurally characterized. Compound crystallizes in the trigonal space group 3. The structure of consists of a discrete mol-ecular complex [Eu(tpa)(HO)] species and the Htpa mol-ecule.

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

The title one-dimensional copper(II) coordination polymer, {[Cu(SO)(CHN)]·CHNO·HO} or {[Cu(bzi)(μ-OSO)]·HO·DMF} (bzi = 1-benz-yl-imidazole, CHN; DMF = ,-di-methyl-formamide, CHNO), is constructed by monodentate bzi ligands and bridging sulfate anions, leading to chains propagating parallel to the axis. Within a chain, there are two crystallographic independent Cu ions, each with site symmetry , which form [CuNO] and [CuNO] 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.

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).

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-NH)] () and () and [CuSCN(pyt-NH)] () and () (where pyt-NH = 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) were successfully synthesized. Single-crystal X-ray diffraction analysis reveals that and are iodo-based polymorphs, while and are thiocyanato-based polymorphs.

Incorporation of Cation Affects the Redox Reactivity of Fe- 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 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.

Four series of lanthanide coordination polymers based on the tetrabromobenzene-1,4-dicarboxylate ligand: structural diversity and multifunctional properties.

Four series of lanthanide-based coordination polymers (LnCPs), namely [Ln(Brbdc)(MeOH)] (1Ln; Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), [Ln(Brbdc)(NO)(MeOH)] (2Ln; Ln = Ce, Pr, Nd, Sm), [Ln(Brbdc)(NO)(MeOH)] (3Ln; Ln = Gd, Tb, Dy), and [Ln(Brbdc)(HO)(MeOH)] (4Ln; Ln = Gd, Tb, Dy) have been synthesized by reacting hydrated lanthanide(III) salts with tetrabromobenzene-1,4-dicarboxylic acid (HBrbdc) in different solvents under solvothermal conditions. The structural diversity found in the system mainly resulted from the effects of anions, solvents, and the variation in the ionic radii of the lanthanide(III) ions. Compounds in series 1Ln feature a two-dimensional (2D) layered structure with sql topology based on {(Ln(COO))(μ-COO)} secondary building units (SBUs).

Crystal structure and Hirshfeld surface analysis of tris-(acetohydrazide-κ ,)(nitrato-κ)(nitrato-κ ,')terbium(III) nitrate.

In the title lanthanide(III) compound, [Tb(NO)(CHNO)]NO, the asym-metric unit contains one Tb ion, three acetohydrazide (CHNO) ligands, two coordinated nitrate anions, and an isolated nitrate anion. The Tb 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.