A two-photon mitotracker based on a naphthalimide fluorophore： Synthesis,photophysical properties and cell imaging

PAHPN. a naphthalimide-based mitotracker with reasonable two-photon excitation emission activity and polarity-sensitive fluorescence properties has been efficiently synthesized and studied in twophoton, co-localization, and FLIM imaging.     

Synthesis,structural characterization,and properties of an entangled metal–organic framework based on a flexible dicarboxylate and a rigid N-donor

Self-assembly of manganese acetate with 1,3-bis(4-carboxy-phenoxy)propane (H₂bcp) and 1,2-bis(4-pyridyl)ethene (bpe) under solvothermal conditions yielded a polymer {[Mn₂(bcp)₂(bpe)(DMF)]} _n (1), which shows 2-D?→?3-D inclined interpenetration with polyrotaxane character. The magnetic behavior of 1 shows antiferromagnetic exchange between Mn magnetic centers.     

Three interpenetrated copper(Ⅱ) coordination polymers based on a V-shaped ligand:Synthesis,structures,sorption and magnetic properties

Three new CuⅡ coordination polymers,[Cu2(oba)2(H2O)(DMF)].3H2O(1),[Cu4(oba)4(DMF)4].4H2O.DMF(2) and [Cu2(oba)(hmp)2](3)(H2oba = 4,4'-oxybis(benzoic acid),Hhmp = 2-pyridine methanol,DMF = N,N'-dimethylformamide) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction.Both complexes 1 and 2 take three-dimensional(3D) three-fold interpenetrating PtS topology with 1D channels.In complex 3,Cu4 clusters were formed by the chelating hmp ligands,and then the clusters were fu...     

Hydrothermal synthesis,characterization and properties of a d10 metal coordination polymer with a layered structure based on carboxyphosphinate ligand, 4,4′-bipyridine and four-coordinated zinc ion

Abstract

Hydrothermal reaction of Zn(NO₃)₂ · 6?H₂O with 2-carboxyethyl(phenyl)phosphinate (H₂L) and 4,4'-bipyridine (4,4′-bipy) led to a novel zinc(II) carboxyphosphinate [ZnL(4,4′-bipy)_0.5]_n (1). The zinc ion is tetrahedrally coordinated by two phosphinate oxygen atoms, one carboxylate oxygen atom, and one nitrogen atom of 4,4′-bipy ligand. The L^2- ligand and zinc ion can be seen as three- and four-connected nodes, respectively. Compound 1 shows a layered network with (3,4)-connected topology. It exhibits a broad blue fluorescent emission band at 459?nm, which can be attributed to 4,4′-bipy intraligand emission as well as to H₂L emission. It is a diamagnetic system between 300?K and 11?K.     

Two d10 metal–organic frameworks based on a novel semi-rigid aromatic biscarboxylate ligand: Syntheses,structures and luminescent properties

Two new d¹⁰ metal–organic frameworks based on a novel semi-rigid aromatic biscarboxylate ligand, namely, [Zn ( RGAA )( BPY )_1/2] ( 1 ) and [Cd₅(μ₃-OH)₂( RGAA )₄] ( 2 ) [H₂ RGAA = 4-(carboxymethyl)-2-ethoxybenzoic acid, BPY = 4,4′-bipyridine], have been synthesized by the hydrothermal reaction, and characterized by Fourier transform-infrared, elemental analyses, X-ray single-crystal diffraction, powder X-ray diffraction and thermogravimetric analyses. Complex 1 displays a three-dimensional (3D) network with a (2,3,4)-connected (6ˆ3.8ˆ2.10)₂(6ˆ3)₂(8) topology, while complex 2 exhibits a 3D framework with a (3,10)-connected (3.4.5)₂(3ˆ4.4ˆ6.5ˆ18.6ˆ14.7ˆ2.8) topology. The luminescent properties of compounds 1 and 2 have been investigated in detail, where the emission maxima are 464 and 349 nm, respectively.     

Synthesis,characterization and luminescence properties of a coordination polymer based on self-assembly of PrIII with inorganic–organic hybrid bridging ligands

A new coordination polymer having the formula [Pr(μ ₅-S₂O₃)(μ ₄-tp)_0.5(H₂O)] _n (1) (S₂O₃ = thiosulfate dianion; tp = terephthalate dianions) was obtained by in situ reaction of Pr₂(SO₄)₃ · 6H₂O with H₂tp ligands under solvothermal conditions (H₂O/ethanol). The coordination polymer obtained was characterized by elemental analysis, FT-IR, thermogravimetry (TG), fluorescent spectra and single crystal X-ray diffraction analysis. The most intriguing structural feature is that the complex exhibits a 3D open framework resulting from bridge-linking coordination between ligands and praseodymium ions. Additionally, 1 has characteristic emission spectra of Pr^III with good fluorescence properties. This is the first coordination polymer based on thiosulfate/terephthalate ligands and a rare earth metal and has an unprecedented pentadentate-bridge-linking coordination mode of the thiosulfate group.     

Insights into the Gelating Abilities of Ricinelaidic Acid and its Ammonium Salts: How do Stereochemistry,Charge, and Chain Lengths Control Gelation of a Long‐Chain Alkenoic Acid?

The gelating abilities of ricinelaidic acid (d ‐REA), the trans‐isomer of ricinoleic acid (d ‐RA), and a series of its alkylammonium and alkane‐α,ω‐diammonium salts have been examined in a wide range of organic liquids. The gelation efficiency of the trans acid is much better than that of the cis, although neither is as efficient as is the completely saturated molecular gelator analogue, (R)‐12‐hydroxystearic acid (d ‐12HSA). The formation of ammonium salts also improves the gelation ability of d ‐REA in high polarity liquids. The gelating properties are highly dependent upon the chain length of the alkyl group of the alkylammonium salts, but not very dependent on the chain length of the alkane‐α,ω‐diammonium salts. Structural insights from Fourier transform infrared spectroscopy and powder X‐ray diffraction indicate that the absence or presence of unsaturation, the incorporation of (charged) ammonium centers, and the different chain lengths of the alkylammonium salts lead to different packing arrangements and different strengths of H‐bonding interactions within the gel assemblies of the d ‐REA derivatives. Insights into the relationships among the various systematic structural changes to d ‐REA and the properties of their aggregated structures, including the gel states, are provided.     

Total and inorganic arsenic in dietary supplements based on herbs, other botanicals and algae—a possible contributor to inorganic arsenic exposure

The content of total and inorganic arsenic was determined in 16 dietary supplements based on herbs, other botanicals and algae purchased on the Danish market. The dietary supplements originated from various regions, including Asia, Europe and USA. The contents of total and inorganic arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS) and anion exchange HPLC-ICP-MS, respectively, were in the range of 0.58 to 5.0 mgkg^?1 and 0.03 to 3.2 mg?kg^?1, respectively, with a ratio between inorganic arsenic and total arsenic ranging between 5 and 100 %. Consumption of the recommended dose of the individual dietary supplement would lead to an exposure to inorganic arsenic within the range of 0.07 to 13 μg?day^?1. Such exposure from dietary supplements would in worst case constitute 62.4 % of the range of benchmark dose lower confidence limit values (BMDL₀₁ at 0.3 to 8 μg kg bw^?1 kg^?1 day^?1) put down by European Food Safety Authority (EFSA) in 2009, for cancers of the lung, skin and bladder, as well as skin lesions. Hence, the results demonstrate that consumption of certain dietary supplements could contribute significantly to the dietary exposure to inorganic arsenic at levels close to the toxicological limits established by EFSA.     

A theoretical investigation of intermolecular interaction of a phthalimide based “on–off” sensor with different halide ions: tuning its efficiency and electro-optical properties

The interaction between chemosensor, N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (1) and different halide ions (F ^? , Cl^? and Br^?) has been investigated using density functional theory (DFT). A clear insight of the sensor anion binding process has been presented. Our calculations revealed that the observed colorimetric and fluorescent signals are induced due to the ground state deprotonation of the sensor molecule caused by F^? which has two times higher binding affinity than other halide ions (Cl^? and Br^?). Derivatives of system 1 have been made to find a better sensor with higher binding affinity and longer wavelength of absorption. All the derivatives are better sensors than the parent 1 except 4-methyl-N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (2). Among these derivatives, trimethyl-[4-(2-methyl-1,3-dioxo-indan-5-ylcarbamoyl)-phenyl]-ammonium (8) and (5-benzoylamino-1,3-dioxo-indan-2-yl)-trimethyl-ammonium (9) showed a change to higher binding energies of about 58 Kcal/mol and longer absorption wavelengths of 53 nm after deprotonation process than the parent system 1 which is highly demanded in selective chemical sensing. Systems 8, 9 and their deprotonated zwitterionic forms (8z and 9z) have also been studied for their nonlinear optical responses. Systems 8, 9 showed significantly good first hyperpolarizability (β) of 84 × 10^?30 and 40 × 10^?30 esu, respectively. These β values increase in zwitterionic states up to 216 × 10^?30 and 109 × 10^?30 esu, respectively after deprotonation with F^?, representing a new signal of deprotonation.     

Synthesis,structure, magnetism and antibacterial properties of a 2-D nickel(II) metal–organic framework based on 3-nitrophthalic acid and 4,4′-bipyridine

A 2-D nickel(II) mixed-ligand metal–organic framework [Ni(NPTA)(4,4′-bipy)(H₂O)]_n (1) was synthesized by reaction of 3-nitrophthalic acid (H₂NPTA) and 4,4′-bipyridine (4,4′-bipy) with Ni(II) under hydrothermal condition and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. Compound 1 possesses a 2-D layer structure constructed from dinuclear nickel(II) building blocks in which two crystallographically equivalent Ni ions are bridged by two NPTA ligands. Furthermore, the layers are connected into 3-D supramolecular network by hydrogen bonds. The magnetism and antibacterial activity of 1 were investigated.     

Ultrasonic synthesis,crystal structure,luminescent, and magnetic properties of a new metal–organic complex based on Ce(IV)–Sr(II)

Research on Chemical Intermediates - This paper presents the sonochemical synthesis of a new hetero-metallic inorganic complex, formulated as [(Sr(OH2)5Ce(dipic)3Sr(OH2)6][Ce(dipic)3]·6H2O...     

A fluorescent “on-off-on” assay for selective recognition of Cu(II) and glutathione based on modified carbon nanodots,and its application to cellular imaging

Carbon nanodots modified with triethylenetetramine (referred to as TCDs) are shown to be viable fluorescent probes for relay recognition of Cu(II) ion and glutathione (GSH). The assay is based on an “on-off-on” mechanism where the “on-off” effect, i.e. quenching by Cu(II) by up to 67%, is exploited to quantify it in concentrations as low as 3.4 nM. The unique quenching of fluorescence (measured at excitation/emission wavelengths of 380/470 nm; quantum yield 16%) is attributed to the fairly selective capture of Cu(II) by the amino and amide groups on the surface of the TCDs. On addition of GSH to the quenched TCD/Cu(II) complex, fluorescence is restored. This effect enables GSH to be quantified in the 0.2 to 175 μM concentration range, with a 0.11 μM detection limit. The turn-on response to GSH is highly selective over other natural amino acids and common anions. Furthermore, the TCDs were successfully applied to image Cu(II) and GSH in living yeast cells.

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Graphical Abstract Carbon nanodots modified with triethylenetetramine show strong blue fluorescence which is quenched by Cu(II) but restored on addition of glutathione. Both Cu(II) (down to 3.4 nM) and glutathione (down to 110 nM) can be detected via these effects.

     

Synthesis,structures, and properties of lead(II) and cobalt(II) metal-organic frameworks based on a flexible benzophenone-2,4′-dicarboxylic acid (H2bpdc)

Two new coordination polymers, [Pb(bpdc)] _n (1) and [Co(bpdc)(phen)] _n (2) [H₂bpdc?=?benzophenone-2,4′-dicarboxylic acid, phen?=?1,10-phenanthroline], have been synthesized and structurally characterized. Hydrogen bonding and π?···?π stacking extend 1 and 2 into 3-D supramolecular architectures, where 1 exhibits a 3-D framework with 1-D hairpin-like helicates based on Pb–O covalent bonds and 2 displays a 3-D network with 1-D zipper-like chains based on Co–O and Co–N covalent bonds. The FT-IR spectra, PXRD and TG analyses are discussed for 1 and 2. Fluorescence spectra and luminescent lifetime are studied for 1.     

Synthesis,structure and dielectric properties of a novel Gd coordination polymer based on 2-（ pyridin-4-yl ）- 1H-i midazole-4,B -dicarboxylate

A new Gd coordination polymer based on 2-（pyridin-4-yl）-I H-imidazole-4,5-dicarboxylate （H3PIDC） has been synthesized under hydrothermal conditions, formulated as {[Gd3（HPIDC）3（PIDC）（H2O）4].3H2O}n （1）. The compound crystallizes in the monoclinic system, space group C2/c with a=20.951（7）, b = 9.515（3）, c = 27.483（10） A,β= 106.176（6）°, Z = 4, V= 5262（3） A3, C40 H45 Gd3 N12 O30, Dc = 2.071 g/cm3, Mr=1645.63, λ （MoKa）=0.71073A, μ=3.846mm-1, F（000）=3204, the final R=0.0390 and wR= 0.1332. Complex 1 is a two-dimensional MOF built up from T-shaped 3-connected HPIDC2 , PIDC3 and 4-connected metal nodes. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.     

3D Heterometallic 3d–4f coordination polymers based on organodisulfonate ligand with isonicotinic acid as a co-ligand: synthesis,crystal structures,photoluminescent and magnetic properties

The hydrothermal reaction of rare earth nitrates, CuCN, 2,7-naphthalenedisulfonate (2,7-nds), and isonicotinic acid (Hina) affords a new family of 3-D heterometallic 3d–4f coordination polymers, [Ln₂Cu(2,7-nds)₂(ina)₄(H₂O)₄]·4H₂O (Ln = Nd (1), Sm (2), Eu (3), Gd (4); 2,7-nds = 2,7-naphthalenedisulfonate, Hina = isonicotinic acid). Complexes 1–4 are structurally characterized by single crystal X-ray diffraction, elemental analysis, FT-IR spectroscopy (IR), powder X-ray diffraction, and thermogravimetric analyses. X-ray crystal structure analyses reveal that 1–4 are isomorphous with dinuclear subunit [Sm₂(ina)₄] binding Cu ions to generate 2-D networks. Such 2-D networks are pillared by linking 2,7-nds ligands to result in the 3-D layer-pillared Ln(III)–Cu(II) coordination architectures. The valence of Cu salts changed in the reaction. In addition, the luminescence properties of 1–3 and the magnetic properties of 3 and 4 have also been investigated.     

Hetero-trinuclear Zn(II)-M(II) (M = Sr,Ba) complexes based on a mononuclear Zn(II) complex metallohost: syntheses,structures and fluorescence properties

A new mononuclear Zn(II) complex, [ZnL(HOAc)] (1) (H₂L = 6,6′-diethoxy-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol), was synthesized by reaction of H₂L and Zn(II) acetate under solvothermal conditions. Complex 1 acts as a metallohost possessing a pentadentate O₅ donor. Complex 1 molecules bonded to one Sr(II) or Ba(II) form two new hetero-trinuclear complexes, [(ZnL)₂M(OAc)₂] (M = Sr (2), Ba (3)). In 2 and 3, Zn(II) ions are 5-coordinate, but the Sr(II) or Ba(II) ion is 10-coordinate by four μ-phenolic oxygens from two L^2? units, four oxygens from four ethoxy groups and two oxygens from two μ-acetato ligands. Furthermore, 1–3 exhibit blue emissions with the maximum emission wavelengths λ_max = 477, 500, and 471 nm when excited at 360 nm.     

Oxidation of 1-amino-4,5-bis(dimethylamino)naphthalene as a route to the double ��proton sponges�� based on dibenzo[a,h]phenazine and 1,1��-azonaphthalene

Behavior of 4-amino-1-dimethylamino- and 1-amino-4,5-bis(dimethylamino)naphthalenes sharply differs on their treatment with tosyl chloride and oxidation with the Bu^tOK/O₂ system. While the former upon the action of tosyl chloride in protic media is transformed to sulfonamide, the latter unexpectedly forms 4,5,11,12-tetrakis(dimethylamino)dibenzo[a,h]phenazine in ??20% yield as a product of the competitive reaction, which represents the earlier unknown type of double ??proton sponges??. In contrast to this, the oxidative dimerization of the indicated amines with Bu^tOK/O₂ leads to 5,12-bis(dimethylamino)dibenzo[a,h]phenazine and 4,5,4??,5??-tetrakis(dimethylamino)-1,1??-azonaphthalene, respectively. Possible mechanisms of these reactions were considered, as well as problems of coloring, solvatochromism, and protonation of the compounds obtained.     

Introduction of a novel dicationic Brönsted acidic ionic liquid based on pyrazine and its application in the synthesis of xanthenediones and 3, 4-dihydropyrimidin-2(1H)-ones under solvent-free conditions

Research on Chemical Intermediates - A novel dicationic Brönsted acidic ionic liquid based on pyrazine has been prepared and characterized by FTIR, 1H NMR, 13C NMR, MS, thermal gravimetric and...     

Development of a high-throughput method for the determination of itraconazole and its hydroxy metabolite in human plasma, employing automated liquid–liquid extraction based on 96-well format plates and LC/MS/MS

A semi-automated liquid chromatography–tandem mass spectrometry (LC/MS/MS) method was developed for the simultaneous quantification of the antifungal drug itraconazole (ITZ) and its coactive metabolite hydroxyitraconazole (OH-ITZ) in human plasma. The plasma samples underwent liquid–liquid extraction (LLE) in 2.2 mL 96 deepwell plates. ITZ, OH-ITZ and the internal standard (IS) R51012 were extracted from plasma, using a mixture of acetonitrile (ACN) and methyl t-butyl ether (MTBE) as the organic solvent. This specific mixture, due to its composition, had a significant impact on the performance of the assay. All liquid transfer steps, including preparation of calibration standards and quality control samples as well as the addition of the IS, were performed automatically using robotic liquid handling workstations for parallel sample processing. After vortexing, centrifugation and freezing, the supernatant organic solvent was evaporated. The analytes and IS were dissolved in a small volume of a reconstitution solution, an aliquot of which was analyzed by combined reversed phase LC/MS/MS, with positive ion electrospray ionization and a TurboIonSpray interface, using multiple reactions monitoring (MRM). The method was shown to be sensitive and specific to both ITZ and OH-ITZ, it revealed excellent linearity for the range of concentrations 2–500 ng mL⁻¹ for ITZ and 4–1000 ng mL⁻¹ for OH-ITZ, it was very accurate and it gave very good inter- and intra-day precisions. The proposed high-throughput method was employed in a bioequivalence study after per os administration of two 100 mg tablets of ITZ, and it allowed this study to be completed in under four days.