Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up

The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI.     

New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Facile and efficient synthesis of fluorinated fullerene-fused 1,3-dioxolanes: reaction of C60 with fluorinated aromatic aldehyde mediated by lithium perchlorate

A series of fluorinated fullerene-fused 1,3-dioxolanes have been facilely and efficiently synthesized in the presence of easily available LiClO₄·3H₂O. The influences of the number of fluoro-substituents and their positions linked to the phenyl ring on the isolated yield of fullerene-fused 1,3-dioxolanes have been studied in detail. Based on reaction facts, a possible reaction mechanism for the formation of fluorinated fullerene-fused 1,3-dioxolanes has been proposed. Furthermore, detailed ultraviolet absorption spectra, fluorescence emission spectra, and cyclic voltammogram further explain the optical properties and electronic transmission capabilities of the products.     

Chiral sensing of Eu(III)‐containing achiral polymer complex from chiral amino acids coordination induction

The β‐diketonate‐based achiral polymer P‐1 could be synthesized by the polymerization of 3,7‐dibromo‐2,8‐dimethoxy‐5,5‐dioctyl‐5H‐dibenzo[b,d]silole ( M1 ) with (Z)?1,3‐bis(4‐ethynylphenyl)?3‐hydroxyprop‐en‐1‐one ( M2 ) via typical Sonogashira coupling reaction. The β‐diketonate unit in the main chain backbone of P‐1 can further coordinate with Eu(TTA)_x [TTA^? = 4,4,4‐trifluoro‐1‐(thiophen‐2‐yl)butane‐1,3‐dionate anion, X = 1, 2, 3] to afford corresponding Eu(III)‐containing polymer complexes. The resulting achiral polymer complex P‐2 (X = 2) can exhibit strong circular dichroism (CD) response toward both N‐Boc‐l and d‐ proline enantiomers. The CD signal was preliminarily attributed to coordination induction between chiral N‐Boc‐proline and the Eu(III) complex moiety. The linear regression analysis of CD sensing shows a good agreement between the magnitude of molar ellipticity and concentration of chiral N‐Boc‐l or d‐ proline, which indicates this kind Eu(III)‐containing achiral polymer complex can be used as a chiral probe for enantioselective recognition of N‐Boc‐l or d‐ proline enantiomers based on Cotton effect of CD spectra. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3080–3086     

聚乙烯基吡啶高氯酸盐作为高效固体酸催化剂在无溶剂条件下催化醛化学选择性制备二乙酸盐(英文)

Poly(4-vinylpyridinium) perchlorate has been used as a supported,recyclable,environmentally-benign catalyst for the formation of acylals from aliphatic and aromatic aldehydes in good to excellent yields under solvent-free conditions.Notably,the reaction conditions were tolerant of ketones.This methodology offers several distinct advantages,including its operational simplicity and high product yield,as well as being green in terms of avoiding the use of toxic catalysts and solvents.Furthermore,the catalyst can be recovered and reused several times without any loss in its activity.     

Enhanced Thermal Decomposition Properties and Catalytic Mechanism of Ammonium Perchlorate over CuO/MoS2 Composite

In this report, CuO/MoS₂ composites were successfully prepared by the hydrothermal method where nano‐sized CuO was uniformly distributed on the surface of hierarchical MoS₂ substrates (CuO/MoS₂ composites). Their physicochemical properties and catalytic performance in ammonium perchlorate (AP) decomposition were investigated and characterized by XRD, SEM, TEM, BET, XPS, TG/DSC and combustion measurement. The results showed that it could decrease AP decomposition temperature at high decomposition stage from 416.5 °C to 323.5 °C and increase the heat release from 378 J/g (pure AP) to 1340 J/g (AP with catalysts), which was better than pure CuO nanoparticles (345.5 °C and 1046 J/g). Meanwhile, it showed excellent performance in combustion reaction either in N₂ or air atmosphere. The results obtained by photocurrent spectra, photoluminescence spectra and time‐resolved fluorescence emission spectra indicated that loading CuO mediated the generation rate and combination rate of electrons and holes, thus tuning the catalytic performance on AP decomposition. This study proved that employing the supports that can synergistically interact with CuO is an efficient strategy to enhance the catalytic performance of CuO.     

Stark Hole-Burning Spectroscopy of Cresylviolet Perchlorate in Amorphous Hosts

Stark hole-burning spectroscopy is used to investigate the effective dipole moment change of cresylviolet perchlorate (CVP) in various glass and polymer hosts such as ethanol:methanol (EM), polyvinyl alcohol (PVA), poly (2-hydroxyethyl) methacrylate (PHEMA), polyvinylbutyral (PVB), and formamide. The strong correlation between effective dipole moment change of the guest molecule and the holeburning efficiencies of the host matrices illustrates the sensitivity of the dipole moment change as a direct measure of guest-host interactions. Hole-burning is found to be more efficient as the dipole induced reaction field increases. This relationship is discussed in terms of the unusual hole-burning mechanism suggested for this molecule. The effective dipole moment change of cresylviolet perchlorate ranges from 0.14 to 0.59 Debye.     

Synthesis and Application of N-Tosyl Piperidinyl-Containing α-Aminophosphonates

Abstract

A series of novel (4′-tosyl) piperidin-4-yl containing α-aminophosphonates were synthesized by a one-pot reaction, efficiently catalyzed by magnesium perchlorate, under solvent-free conditions from 1-tosylpiperidin-4-one, substituted aromatic amines, and diethyl phosphite (DEP). The synthesized compounds were characterized by IR, ¹H NMR, ¹³C NMR, ³¹P NMR, and HRMS spectroscopy. A single-crystal X-ray structure of diethyl 4-(2-chlorophenyl) amino-1-(4’-methylbezenesulfonyl) piperidin-4-yl-phosphonate (2a) was obtained, and some of the title compounds displayed insecticidal activities against Plutella xylostella.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.