Aliphatic Polyester/polyhedral Oligomeric Silsesquioxanes Hybrid Networks via Copper‐free 1,3‐dipolar Cycloaddition Click Reaction

In this study, we describe the preparation and characterization of a new class of thermoset hybrid networks containing aliphatic polyester and polyhedral oligomeric silsesquioxanes (POSS). The copper‐free 1,3‐dipolar cycloaddition click reaction of internal alkyne functionalized aliphatic polyester and multifunctional azido POSS with different concentrations led to highly crosslinked thermoset networks. The click reactions performed under ambient conditions (i.e., in tetrahydrofuran at room temperature for 1 day) in the absence of any catalyst. The chemical composition of hybrid networks and homogenous distribution of POSS molecules were confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy with energy dispersive spectroscopy. The swelling ratios of hybrid networks were commonly decreased by increasing POSS‐N₃ content and by changing polar solvents to apolar solvents. Thermogravimetric analysis results demonstrated that the thermal stability of hybrid networks increased with higher POSS feeding ratio. Tensile tests were applied to evaluate the mechanical properties of hybrid networks. Compared to neat aliphatic polyester, the mechanical properties of hybrid networks significantly improved. For instance, the tensile strength were enhanced from 5 MPa to 19 MPa by increasing the concentration of azido functionalized POSS from 10 to 40. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2222–2227     

Synthesis of peptide dendrimers with polyhedral oligomeric silsesquioxane cores via click chemistry

Inorganic polyhedral oligomeric silsesquioxane (POSS) was used as the core for the synthesis of poly(Llysine) peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite dendrimer was characterized by MS, 1H NMR, FTIR, GPC and DLS.     

Biological Applications of Macrocyclic Schiff Base Ligands and Their Metal Complexes: A Survey of the Literature (2005–2019)

This article aims to provide a survey of biological applications of Schiff base macrocycles and their metal complexes, with emphasis given to the synthesis of the compounds and to their uses as antibacterial and antifungal agents. The literature on the subject, published during the 2005–2019 period, is shortly reviewed. This is an informed report collecting information on the addressed topic in a concise systematic way, and can be expected to be useful as a fast literature catalogue for researchers working on this and related domains.     

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro-Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low-Pressure CO2

In the present research, the synthesis, spectroscopic characterization, and structural investigations of a unique Zn^II complex of imine-functionalized polyhedral oligomeric silsesquioxane (POSS) is designed, and hereby described, as a catalyst for the synthesis of cyclic carbonates from epoxides and CO₂. The uncommon features of the designed catalytic system is the elimination of the need for a high pressure of CO₂ and the significant shortening of reaction times commonly associated with such difficult transformations like that of styrene oxide to styrene carbonate. Our studies have shown that imine-POSS is able to chelate metal ions like Zn^II to form a unique coordination complex. The silsesquioxane core and the hindrance of the side arms (their steric effect) influence the construction process of the homoleptic Zn₄@POSS-1 complex. The compound was characterized in solution by NMR (¹H, ¹³C, ²⁹Si), ESI-MS, UV/Vis spectroscopy and in the solid state by thermogravimetric/differential thermal analysis (TG-DTA), elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), cross-polarization magic angle spinning (CP MAS) NMR (¹³C, ²⁹Si) spectroscopy, and X-ray crystallography.     

Macrocyclic Polyethers as Enolate Activators in Homogeneous and Heterogeneous Systems

Abstract

The ability of macrocyclic polyethers to activate enolates has been studied in the alkylation of de-oxybenzoin (1) with butyl derivatives nBuY (Y = Br, I, OMes) catalyzed by crown ether PHDB18C6 (7) or cryptand [2.2.2,C10] (8) under phase-transfer catalysis (PTC) and homogeneous (chlorobenzene) conditions. The enolate reactivity is mainly determined by the ligand (cryptand > crown ether) and solvent (increasing with the polarity, in the order: toluene < chlorobenzene < 1,2dichlorobenzene). Regioselectivity of the reaction is also remarkably affected by ligand and alkylating agent.     

Water‐Soluble Luminescent Hybrid Composites Consisting of Oligosilsesquioxanes and Lanthanide Complexes and their Sensing Ability for Cu2+

Water‐soluble hybrid composites with great potential for selective and sensitive sensing and that are obtained through simple, rapid, and environmentally friendly methods are highly desirable and remain a challenging task. Herein, we present luminescent hybrid composites that were realized by linking Na₃[Ln(dpa)₃] (dpa=2,6‐pyridinedicarboxylic acid) to octa‐amino functionalized polyhedral oligomeric silsesquioxane (POSS‐NH₂) through hydrogen‐bonding interactions between the oxygen atoms of the carboxylate groups of dpa and the hydrogen‐bond‐donor amino groups. The resulting hybrid composites Ln(dpa)₃@POSS‐NH₂ are highly soluble in aqueous solutions and the quantum yield of Eu(dpa)₃@POSS‐NH₂ is as high as 56.5 % or 46.3 % in the solid state and in aqueous solution, respectively, as determined by using the integrating sphere method. The novel water‐soluble luminescent hybrid composites exhibit high thermal and photostability, and the emitted colors of the resulting hybrid composite can be finely tuned by changing the Eu³⁺/Tb³⁺ ratio. Interestingly, Eu(dpa)₃@POSS‐NH₂ hybrid composites exhibited an effective switch‐off fluorescence response to Cu²⁺ over other common metal ions in aqueous media.     

Synthesis and Characterization of Some Novel Dialkyldithiophosphate Derivatives of Macrocyclic Complexes of Pb(II) Having N2 S2 Potential Donors in 14- to 20-Membered Rings

Dialkyldithiophosphate derivatives of macrocyclic complexes of Pb(II), having N₂S₂ potential donors, of the general formula, [Pb(L)S₂P(OR)₂] (where L = macrocyclic ligands L¹, L², L³, L⁴ & L⁵ and R = CH₃-, C₃H₇ ⁿ- & C₃H₇ ⁱ-) have been Synthesized from the reactions of [Pb(L)X₂] (where X = Cl, NO₃, or CH₃COO) with sodium dialkyl dithiophosphates in 1:2 molar ratios in THF. Fifteen new derivatives have been synthesized by the combination of five macrocyclic complexes of 14–20 member rings with three different types of dialkyldithiophosphate. These compounds have been characterized by elemental analysis, molar conductance, molecular weight determination, IR, ¹H NMR, ¹³C, and ³¹P NMR. Molecular weight determinations of these complexes indicate their monomeric nature. An octahedral structure is proposed.     

Modification of polyhedral oligomeric silsesquioxane derivatives with heck reaction as possible new bio-hybrid materials

Abstract

The regioselective synthesis of Polyhedral oligomeric silsesquioxane (POSS)-based norbornyl imide derivatives through palladium catalyzed Heck coupling reaction was reported on an effective synthetic method to organic–inorganic bio-hybrids serving as advanced materials. The reaction of POSS-based imide derivatives with various aryl iodides catalyzed by palladium acetate in the presence of triethyl amine, as the base, in DMF afforded the products in moderate yields. All new POSS derivatives were structurally characterized by FTIR, ¹H, ¹³C NMR, HRMS and GC/MS analyses.     

Synthesis of Diquinolineno[1,3,7,9]Tetraazacyclododecine-7, 15 (14H, 16H)-Dibenzene,and DNA Binding Studies of Macrocyclic Co(II), Cu(II) Complexes: As New Class of Antimicrobial Agent

The synthesis of macrocyclic ligand, diquinolineno[1,3,7,9]tetraazacyclododecine-7, 15 (14H, 16H)-dibenzene(L), is described. The metal complexes of the type [MLX₂], where (M = Co(II) (1), Cu(II) (2) and X = (Cl), have been synthesized by the reaction of ligand(L) with the corresponding metal salts, and characterized by elemental analysis, FT-IR, ¹H-NMR and electronic spectra. The binding property of the complexes with CT-DNA was studied by absorption spectra, viscosity measurements, as well as thermal denaturation studies. The absorption spectral results indicate that the complexes (1) and (2) are binds with base pairs of DNA. The intrinsic binding constant K_b had the value 3.8 × 10⁴M ^?1 for (1 Chappell, L. L., Voss, A. D. and Morrow, J. R. 1998. Inorg. Chem., 37(16): 3989–3998.  [Google Scholar]) and 3.3 × 10⁴ M^?1 for (2), respectively, in 5 mM Tris-HCl/50 mM NaCl buffer at pH 7.2. The viscosity measurement results show the viscosity of sonicated rod-like DNA fragments increased when the complex were added to the solution of calf thymus-DNA. The synthesized ligand and its metal complexes have been screened for antibacterial and antifungal activities.