A pulsed EPR study of surfactant layer structure in composites of a synthetic layered silicate with polystyrene and polycaprolactone

Double electron electron resonance (DEER), deuterium electron spin-echo envelope modulation (ESEEM) spectroscopy and 31P electron nuclear double resonance (ENDOR) spectroscopy were applied to site-specifically spin-labeled surfactants in the organically modified layered silicate magadiite and its composites with polystyrene (PS) and polycaprolactone (PCL). The organomagadiite consist of stacks of silicate platelets with surfactant layers between these platelets. In PS composites the stacks are dispersed in the polymer matrix as a whole, while melt processing with PCL leads to intercalation of polymer chains into the galleries between the platelets. The DEER data prove that even in the case of the non-intercalated PS composites the density of surfactant molecules changes drastically during composite formation on length scales of a few nanometers. Deuterium ESEEM data demonstrate that spin labels attached both in the middle and at the end of the alkyl chain have contact with the headgroups of neighboring surfactant molecules. By analysis of the 31P ENDOR spectra, two characteristic distances are found between the spin labels and the headgroups of phosphonium surfactants. The shorter, proximal distance can be assigned to headgroups in the same surfactant layer. By comparison with the basal spacing between consecutive silicate platelets the longer, distal distance is assigned to a layer of surfactants that is not attached to the surface of the next platelet but rather located between platelets. Altogether the data support a picture of trilayers of disordered surfactant molecules with their alkyl chains oriented nearly parallel to the surface.     

Diverging Rh(I)-catalyzed carbocylization strategy to prepare a library of unique cyclic ethers

A library of 90 carboxamide-containing oxepines and pyrans was synthesized. A dual-branching strategy was used where a common intermediate, an allenyl-hydroxy ester, was either allylated or propargylated then subjected to rhodium(I)-catalyzed carbocyclization reaction conditions to afford an oxepine- or triene-containing pyran, respectively. The oxepines were selectively reduced to afford two functionally unique scaffolds using complementary hydrogenation conditions. Diversification of the oxepines and pyrans involved conversion of the methyl carboxylate group to a carboxamide via either a microwave-assisted amidation using polymer-bound carbodiimide (DCC) and 1-hydroxybenzotriazole (HOBt) or a NaCN-catalyzed aminolysis. The scope of a rarely used carbonyl-yne reaction was expanded to the preparation of 10 new allenyl-hydroxy esters using microwave irradiation. Finally, a cell-based diversity analysis using BCUT (Burden (B) CAS (C) Pearlman at the University of Texas (UT)) metrics calculations and two-dimensional fingerprint similarity approaches shows that when compared to the 100,000 Pittsburgh Molecular Library Screening Center (PMLSC) compound database and PubChem the new compound library occupies a unique chemical space.     

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cr...     

Easily prepared high-quantum-yield CdS quantum dots in water using hyperbranched polyethylenimine as modifier

Some research has reported interaction between polyamidoamine dendrimers or polyethylenimine and quantum dots causing a quantum yield decrease of quantum dots. In this work, however, polyethylenimines of different molecular weight that were used to modify CdS quantum dots gave rise to the enhancement of CdS quantum yield to nearly 100%. Herein, we present the synthesis of a kind of easily prepared high-quantum-yield CdS quantum dot in aqueous solution and the study of the interaction between CdS and polyethylenimine.     

A novel one-step method for the synthesis of C-5-substituted Omicron6,5'-cyclopyrimidine nucleoside analogues in ammonia water

A novel one-step method for preparing C-5-substituted Omicron(6),5'-cyclopyrimidine nucleoside analogues is reported. This method employs molecular iodine to mediate the cyclization from the 5'-Omicron-hydroxyl group of the sugar ring and C-6 at the position of the nitrogen base in ammonia water under mild conditions without any other aprotic organic solvent.     

Synthesis, crystal structures, and luminescent properties of two types of lanthanide phosphonates

Hydrothermal reactions of different lanthanide(III) salts with an amino-diphosphonate ligand (H₄L=C₆H₅CH₂N(CH₂PO₃H₂)₂) led to two series of lanthanide phosphonates, namely, Ln(H₂L)(H₃L) (Ln=La, 1; Pr, 2; Nd, 3; Sm, 4; Eu, 5; Gd, 6; Tb, 7). Compounds 1-5 feature a one-dimensional (1D) chain structure in which dimers of two edge-sharing LnO₈ polyhedra are interconnected by bridging phosphonate groups, such 1D arrays are further interlinked via strong hydrogen bonds between non-coordinated phosphonate oxygen atoms into a two-dimensional (2D) layer with the phenyl groups of the ligands orientated toward the interlayer space. Compounds 6 and 7 also show a different 1D array in which the LnO₆ octahedra are bridged by phosphonate groups via corner-sharing, such chains are also further interlinked by hydrogen bonds into a 2D supramolecular layer. Compounds 5 and 7 emit red and green light with a lifetime of 2.1 and 3.7 ms, respectively.     

Syntheses, crystal structures and optical properties of the first strontium selenium(IV) and tellurium(IV) oxychlorides: Sr3(SeO3)(Se2O5)Cl2 and Sr4(Te3O8)Cl4

Two new quaternary strontium selenium(IV) and tellurium(IV) oxychlorides, namely, Sr₃(SeO₃)(Se₂O₅)Cl₂ and Sr₄(Te₃O₈)Cl₄, have been prepared by solid-state reaction. Sr₃(SeO₃)(Se₂O₅)Cl₂ features a three-dimensional (3D) network structure constructed from strontium(II) interconnected by Cl⁻, SeO₃²⁻ as well as Se₂O₅²⁻ anions. The structure of Sr₄(Te₃O₈)Cl₄ features a 3D network in which the strontium tellurium oxide slabs are interconnected by bridging Cl⁻ anions. The diffuse reflectance spectrum measurements and results of the electronic band structure calculations indicate that both compounds are wide band-gap semiconductors.     

Turn-on Circularly Polarized Luminescence in Chiral Indium Chlorides by 5s2 Metal Centers

Introducing chirality into the metal-halide hybrids has enabled many emerging properties including chiroptical activity, spin-dependent transport, and ferroelectricity. However, most of the chiral metal-halide hybrids to date are non-emissive, and the underlying mechanism remains elusive. Here, we show a new strategy to turn on the circularly polarized luminescence (CPL) in chiral metal-halide hybrids. We demonstrate that alloying Sb³⁺ into chiral indium-chloride hybrids dramatically increases the photoluminescence quantum yield in two new series of chiral indium-antimony chlorides. These materials exhibit strong CPL signals with tunable energy and a high dissymmetry factor up to 1.5×10⁻². Mechanistic studies reveal that the emission originates from the self-trapped excitons centered in 5s² Sb³⁺. Moreover, near-ultraviolet pumped white light is demonstrated with a polarization up to 6.0 %. Our work demonstrates new strategies towards highly luminescent chiral metal-halide hybrids.     

Hybrid Double Perovskite Derived Halides Based on Bi and Alkali Metals (K,Rb): Diverse Structures,Tunable Optical Properties and Second Harmonic Generation Responses

Double perovskites (DP) have attracted extensive attention due to their rich structures and wide application prospects in the field of optoelectronics. Here, we report 15 new Bi-based double perovskite derived halides with the general formula of A₂BBiX₆ (A=organic cationic ligand, B=K or Rb, X=Br or I). These materials are synthesized using organic ligands to coordinate with metal ions with a sp³ oxygen, and diverse structure types have been obtained with distinct dimensionalities and connectivity modes. The optical band gaps of these phases can be tuned by changing the halide, the organic ligand and the alkali metal, varying from 2.0 to 2.9 eV. The bromide phases exhibit increasing photoluminescence (PL) intensity with decreasing temperature, while the PL intensity of iodide phases changes nonmonotonically with temperature. Because the majority of these phases are non-centrosymmetric, second harmonic generation (SHG) responses are also measured for selected non-centrosymmetric materials, showing different particle-size-dependent trends. Our findings give rise to a series of new structural types to the DP family, and provide a powerful synthetic handle for symmetry breaking.     

Novel fluorescent chemosensor for Ag^ ＋ based on coumarin fluorophore

A novel chemosensor 1 （CS1） bearing one coumarin and two carbodithioate groups was synthesized and its fluorescent sensing behavior toward metal ions was investigated. Ag^＋ addition to a CH3COCH3/H2O （3：7, v：v） solution of CS1 gave a significantly quenched fluorescence. Other ions including Pb^2＋, Zn^2＋, Cu^2＋, Ca^2＋, Cd^2＋, Co^2＋, Mg^2＋, Mn^2＋, Hg^2＋, Ag^＋, Ni^2＋ induced no or much smaller spectral changes. This constitutes an ON-OFF Ag^＋-selective fluorescent chemosensor.