Insight Into the Conformational Arrangement of a Bis-THF Diol Compound Through 2D-NMR Studies and X-Ray Structural Analysis

Abstract  

The conformational arrangement of an all-threo bis-THF diol compound, synthesized through the RuO₄-catalysed oxidative bis-cyclization of farnesyl acetate, was determined via crystallographic analysis and detailed 2D-NMR solution studies. The bis-THF compound crystallizes in the orthorhombic Pbca space group, with unit cell parameters a = 10.496(1), b = 17.974(1), c = 19.777(2) ?, Z = 8. The final refinement converged to R ₁ = 0.0484 for 4714 independent observed reflections having I > 2σ(I). There is a good agreement between the solution molecular conformation determined by 2D-NMR and the X-ray molecular conformation. The molecule adopts a folded, horse shoe-type conformation both in solution and in the crystal, that suggests aptitude to coordinate cations. Additionally, in the crystals, the molecular conformation is stabilized by intramolecular and intermolecular H-bonding.     

Polymers containing substituted 2-phenyl-benzoxazole side-chain groups: Synthesis and phase behavior

The synthesis of substituted 2-phenyl-benzoxazoles has been accomplished by ring closure of Schiff bases. The compounds have been used as precursors of acrylic derivatives displaying LC properties: Four comb-like homopolymers have been obtained by radical catalysis from the acrylic monomers. The polymers have been characterized by ¹H-NMR, DSC, x-ray diffraction, viscometry, and polarizing microscopy. Three of the polymers exhibit liquid crystalline properties of smectic type. © 1996 John Wiley & Sons, Inc.     

Supercritical fluid extraction of atrazine and its metabolites from soil

Soxhlet (methanol) and SFE extraction with carbon dioxide in the presence of modifiers at different temperatures (100–200°C) for the extraction of atrazine and its main metabolites from a soil sample were compared. The most effective extraction conditions for both atrazine and its metabolites (i.e. deethylatrazine and deisopropylatrazine) were Co₂ modified with 20% molar methanol-trifluoroacetic acid (MeOH-TFA) (TFA 0.65M in MeOH) at 100°C, leading to an extraction efficiency comparable with that of Soxhlet extraction with MeOH for atrazine and ca. 20% higher for its main metabolites. The relative standard deviation (RSD) of SFE was lower than that obtained by Soxhlet extraction, probably because of less interference in the cGC-NPD determination. All the other modifiers evaluated (acetone, triethylamine, and methanol) were less effective than MeOH-TFA for the extraction of atrazine and its metabolites from a soil sample, even at high molar concentrations (20%) and use of higher extraction temperatures (200°C). These results indicate the importance of matrix effects and the need of the selection of an appropriate modifier in order to obtain quantitative extractions by SFE.     

Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs

New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 2 ), 1,3‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 3 ), 1,4‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 4 ), 4,4′‐(HNC₄H₃‐C(H)?N)₂‐(C₆H₄‐C₆H₄) ( 5 ), 1,5‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 6 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 7 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₄H₈ ( 8 )) and star‐shaped (1,3,5‐(HNC₄H₃‐C(H)?N‐1,4‐C₆H₄)₃‐C₆H₃ ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph₂B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 10 ), Ph₂B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 11 ), Ph₂B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh₂ ( 12 ), Ph₂B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 13 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 14 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh₂ ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh₂)₃ ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C₆H₅)₃. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m^?2, for single layer devices, increasing to 4400 cd m^?2 when a hole‐transporting layer is used.     

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb3+ Complexes

We used a very simplified electrostatic model based on charge and polarizability of atoms and groups on an organic ligand around a lanthanide ion to predict the near‐infrared electronic circular dichroism (NIR ECD) spectra of Yb³⁺ (a monoelectronic ion). We tuned our method by using two widely different complexes. The first was the heterobimetallic species CsYb(hfbc)₄ [hfbc=(?)‐3‐heptafluorobutyrylcamphorate], in which the ligand is a diketonate and, as such, is endowed with a chromophore with strong UV absorption (π–π^*). Its oxygen atoms define a square antiprism, which provides a symmetric coordination polyhedron. The second system was Yb DOTMA [DOTMA=(1R,4R,7R,10R)‐α,α′,α′′,α′′′‐tetramethyl‐1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid], a chiral Yb analogue of Gd DOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid), in which the ligand lacks relevant electronic transitions and provides a dissymmetric cage. The relative weights of dynamic (ligand polarization) and static contributions to Yb NIR ECD were evaluated, and the spectra appear to have been well predicted by theory through the introduction of a heuristic weight factor. To validate the approach and to confirm the value of the weight factor, we applied it to two other compounds, namely, Na₃Yb(BINOLate)₃ and Yb(BINOLAM)₃ [BINOLate=2,2′‐dihydroxy‐1,1′‐binaphthyl; BINOLAM=3,3′‐bis(diethylaminomethyl)‐1‐1′‐bi‐2‐naphthol].     

A Novel One‐Dimensional Copper Mellitate Complex Featured by {Cu(H2O)2(urea)[C6(COO)4(COOH)2]}n2n– Polyanions

Blue monoclinic single crystals of the novel one‐dimensional [H₃N‐(CH₂)₆‐NH₃][Cu(H₂O)₂(urea)(μ₂‐C₆(COO)₄(COOH)₂)] · H₂O coordination polymer were prepared in aqueous solution at room temperature in the presence of 1,6‐diaminohexane and urea [space group P2₁/n (no. 14) with a = 958.48(9), b = 1465.74(11), c = 1821.14(12) pm, β = 97.655(8)°]. The Cu²⁺ cation is coordinated in a square pyramidal manner by two oxygen atoms stemming from the dihydrogen mellitate tetraanion, one oxygen atom from the urea molecule, and two water molecules. The Cu–O distances are in the range of 193.3(2) and 229.4(2) pm. The connection between Cu²⁺ and [C₆(COO)₄(COOH)₂]^4– yields infinite chain‐like polyanions parallel to [1$\bar{}$ 01] with a composition of {Cu(H₂O)₂(urea)[C₆(COO)₄(COOH)₂]}_n^2n–. The dihydrogen mellitate tetraanion adopts a μ₂ coordination mode. The [(H₃N–(CH₂)₆–NH₃)]²⁺ cations are accommodated between the chains as counter cations. The hexane‐1,6‐diammonium cations adopt a partial synclinal conformation. The chains are connected by strong and weak hydrogen bonds. Magnetic measurements reveal a paramagnetic Curie‐Weiss behavior and a magnetic moment of 1.93 μ_B per Cu²⁺. Thermoanalytical investigations in air show that the complex is stable up to 135 °C, and the following decomposition processes yield CuO.     

Host-guest Assembly Based on γ-Cyclodextrin-functionalized Multiwalled Carbon Nanotubes for Rutin Electrochemical Sensing

Here, we report multiwalled carbon nanotubes (MWCNTs) functionalized with γ-cyclodextrins (γCD) as a novel electrochemical strategy for Rutin determination, showing superior performance than β-cyclodextrins (βCD) modified MWCNTs, suggesting an adequate environment for host-guest interactions. Under optimized conditions, the sensor showed a linear range of 39–975 nmol L⁻¹ and a limit of detection of 7 nmol L⁻¹. When tested with quercetin, catechin, and caffeine, the platform presented high selectivity with an interference response <10 %. The method was employed to quantify Rutin in spiked pharmaceutical and herbal extracts, providing recovery of 93–98.4 %. Also, HPLC-PDA confirmed the method‘s accuracy.     

Blue emitting side-chain pendant 4-hydroxy-1,3-thiazoles in polystyrenes synthesized by RAFT polymerization

Blue emitting dyes bearing a luciferin analogous chromophore were attached to a polystyrene backbone. For this purpose, 4-hydroxy-1,3-thiazoles were functionalized with a styrene unit and polymerized using the reversible addition–fragmentation chain transfer (RAFT) polymerization technique. Two different chain transfer agents were investigated and one monomer was studied in terms of its kinetic behavior. The polymerization kinetics are presented and discussed in detail, showing a controlled polymerization behavior, resulting in well-defined copolymers with polydispersity indices below 1.2. The obtained polymers were characterized by size exclusion chromatography (SEC), ¹H NMR, MALDI-TOF MS and UV–vis absorption and fluorescence spectroscopy. In addition, the UV–vis absorption and emission behavior was investigated in thin films.     

Separation and determination of <Superscript>90</Superscript>Sr in low- and intermediate-level radioactive wastes using extraction chromatography and LSC

A methodology for the determination of ⁹⁰Sr in low- and intermediate-level radioactive wastes from nuclear power plants is presented in this work. It is a part of a methodology developed for the sequential radiochemical separation of radionuclides difficult-to-measure directly by gamma spectrometry in these radioactive wastes. The separation procedure was carried out using precipitation and extraction chromatography with Sr Resin, from Eichrom and the ⁹⁰Sr was measured by liquid scintillation counting (LSC). Optimum conditions for the pretreatment, separation and LSC measurements were determined using simulated samples, which were prepared using standard solutions and carriers. The procedure showed to be rapid and achieved a good chemical yield, in the range 60–90%, and a detection limit of 6.0 × 10⁻⁴ Bq g⁻¹. The method was also tested by participation in a national intercomparison program, with aqueous samples, with good agreement of results.