Porous Metal–Organic Framework Nanoparticles

Metal–organic frameworks (MOFs) are hybrid crystalline particles composed of metal cations and organic linkers. Ranging from micro- to nanoscale depending on the preparation conditions, they have achieved a prevalent position among porous materials. The fact that varying either the metal cation or the organic component leads to a wide range of pore sizes and structures has made them very appealing materials in a broad variety of fields, including gas storage, heterogeneus catalysis, separation, imaging, biosensing, agriculture, and biomedicine. By optimizing the internal pore volume, many molecules of different natures can be accommodated within the matrix. For instance, the anticancer drug doxorubicin is well known to enter within iron trimesate MIL-100(Fe) nanoMOF. However, the use of this inclusion complex in biomedicine requires the controlled release of the drug. As reported in one of the articles within this Special Issue [1], this goal can be achieved either by modifying the way the drug is loaded into the MOF or by noncovalently coating the surface with appropriate biocompatible materials. Furthermore, the latter can also lead to a higher colloidal stability of the particles. The innovative use of the ssNMR technique on these inclusion complexes associated with a selective isotope labeling strategy gave the authors deeper insights into both the structure of the complexes as well as to the drug release rates and mechanism

Vinyl sulfone-based ferrocenylation reagents: applications in conjugation and bioconjugation

The easy vinyl sulfone derivatization of ferrocene allows the preparation of some effective, versatile and valuable ferrocenylation reagents. The applicability of such compounds in conjugation and bioconjugation of amine and/or thiol containing molecules and biomolecules through Michael-type addition under mild conditions that preserve the biological function of the latter is described. The feasibility of the methodology is demonstrated by the preparation of a variety of conjugates and bioconjugates (ferrocenyl terminated dendrimers and ferrocene–sugar, ferrocene–cyclodextrin, ferrocene–peptide and ferrocene–protein conjugates).Financial support was provided by Ministerio de Ciencia e Innovación (CTQ2011-29299-CO2-01)

Fluorescent Sensing of Chlorophenols in Water Using an Azo Dye Modified β-Cyclodextrin Polymer

A water soluble azo dye modified β-cyclodextrin polymer 4 was synthesized and used as a chemosensor for the detection of chlorinated phenols, model chlorinated by-products (CBPs) of water treatment for drinking purposes. The characterization of the intermediates and the azo dye modified β-CD polymer was done by UV/Vis Spectrophotometry, FT-IR and 1H-NMR spectroscopies. The chlorophenols were capable of quenching the fluorescence of the polymer. The polymer showed greater sensitivity towards 2,4-dichlorophenol, with a sensitivity factor of 0.35 compared to 0.05 and 0.12 for phenol and 4-chlorophenol, respectively. The stability constants (Ks) of the pollutants were also determined by the Benesi-Hildebrand method to be 2.104 × 103 M−1 for 2,4-dichlorophenol and 1.120 × 102 M−1 for 4-chlorophenol

Reactivity of (1-methoxycarbonylpentadienyl)iron(1+) cations with hydride, methyl, and nitrogen nucleophiles

The reaction of tricarbonyl and (dicarbonyl)triphenylphosphine (1-methoxycarbonyl-pentadientyl)iron(1+) cations 7 and 8 with methyl lithium, NaBH3CN, or potassium phthalimide affords (pentenediyl)iron complexes 9a-c and 11a-b, while reaction with dimethylcuprate, gave (E,Z-diene)iron complexes 10 and 12. Oxidatively induced-reductive elimination of 9a-c gave vinylcyclopropanecarboxylates 17a-c. The optically active vinylcyclopropane (+)-17a, prepared from (1S)-7, undergoes olefin cross-metathesis with excess (+)-18 to yield (+)-19, a C9C16 synthon for the antifungal agent ambruticin. Alternatively reaction of 7 with methanesulfonamide or trimethylsilylazide gave (E,E-diene)iron complexes 14d and e. Huisgen [3 + 2] cyclization of the (azidodienyl)iron complex 14e with alkynes afforded triazoles 25a-e

Efficient synthesis of pyrene-1-carbothioamides and carboxamides. Tunable solid-state fluorescence of pyrene-1-carboxamides

Pyrene reacts with potassium thiocyanate and organic isothiocyanates in the presence of trifluoromethanesulfonic acid to afford primary and secondary pyrene-1-carbothioamides in high yields. These compounds were efficiently oxidatively desulfurized with Oxone® to the corresponding carboxamides. The amides display solid-state fluorescence with quantum efficiencies up to 62%, originating from monomers, aggregates (such as preformed dimers), and/or excimers, depending on the substituent at the nitrogen atom. Single crystal X-ray diffraction characterization of one highly emissive compound supports this assumption.Publikacja w ramach programu Royal Society of Chemistry "Gold for Gold" 2014 finansowanego przez Uniwersytet Łódzki

Ionicity-dependent proton-coupled electron transfer of supramolecular self-assembled electroactive heterocycles

Herein, we investigate the electrochemical properties of a class of Supramolecular Self-associated Amphiphilic salts (SSAs). We show that varying ionic strength of an SSA solution can cause a switching of the thermodynamics and kinetics of electron transfer. The effect of self-assembly on proton-coupled electron transfer has implications for the understanding of electron transfer kinetics in aqueous organic redox flow batteries, especially at high concentration where organic–organic intermolecular interactions become dominant even for highly soluble organic species

Functionalization of Pyrene To Prepare Luminescent Materials—Typical Examples of Synthetic Methodology

Pyrene-based π-conjugated materials are considered to be an ideal organic electro-luminescence material for application in semiconductor devices, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), and so forth. However, the great drawback of employing pyrene as an organic luminescence material is the formation of excimer emission, which quenches the efficiency at high concentration or in the solid-state. Thus, in order to obtain highly efficient optical devices, scientists have devoted much effort to tuning the structure of pyrene derivatives in order to realize exploitable properties by employing two strategies, 1) introducing a variety of moieties at the pyrene core, and 2) exploring effective and convenient synthetic strategies to functionalize the pyrene core. Over the past decades, our group has mainly focused on synthetic methodologies for functionalization of the pyrene core; we have found that formylation/acetylation or bromination of pyrene can selectly lead to functionalization at K-region by Lewis acid catalysis. Herein, this Minireview highlights the direct synthetic approaches (such as formylation, bromination, oxidation, and de-tert-butylation reactions, etc.) to functionalize the pyrene in order to advance research on luminescent materials for organic electronic applications. Further, this article demonstrates that the future direction of pyrene chemistry is asymmetric functionalization of pyrene for organic semiconductor applications and highlights some of the classical asymmetric pyrenes, as well as the latest breakthroughs. In addition, the photophysical properties of pyrene-based molecules are briefly reviewed. To give a current overview of the development of pyrene chemistry, the review selectively covers some of the latest reports and concepts from the period covering late 2011 to the present day

Design of engineered cyclodextrin derivatives for spontaneous coating of highly porous metal-organic framework nanoparticles in aqueous media

Nanosized metal-organic frameworks (nanoMOFs) MIL-100(Fe) are highly porous and biodegradable materials that have emerged as promising drug nanocarriers. A challenging issue concerns their surface functionalization in order to evade the immune system and to provide molecular recognition ability, so that they can be used for specific targeting. A convenient method for their coating with tetraethylene glycol, polyethylene glycol, and mannose residues is reported herein. The method consists of the organic solvent-free self-assembly on the nanoMOFs of building blocks based on beta-cyclodextrin facially derivatized with the referred functional moieties, and multiple phosphate groups to anchor to the nanoparticles’ surface. The coating of nanoMOFs with cyclodextrin phosphate without further functional groups led to a significant decrease of macrophage uptake, slightly improved by polyethylene glycol or mannose-containing cyclodextrin phosphate coating. More notably, nanoMOFs modified with tetraethylene glycol-containing cyclodextrin phosphate displayed the most effcient “stealth” effect. Mannose-coated nanoMOFs displayed a remarkably enhanced binding affnity towards a specific mannose receptor, such as Concanavalin A, due to the multivalent display of the monosaccharide, as well as reduced macrophage internalization. Coating with tetraethylente glycol of nanoMOFs after loading with doxorubicin is also described. Therefore, phosphorylated cyclodextrins o er a versatile platform to coat nanoMOFs in an organic solvent-free, one step manner, providing them with new biorecognition and/or “stealth” properties