Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.     

Gold(III) π-Allyl Complexes

Gold(III) π-complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of Pd^II π-allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π-allyl complexes, which have remained elusive so far. The (P,C)Au^III(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air-stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi-symmetric η³-coordination of the allyl moiety. The π-allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β-diketo enolates.     

Oligosaccharides: Defense Inducers,Their Recognition in Plants,Commercial Uses and Perspectives

Plants have innate immune systems or defense mechanisms that respond to the attack of pathogenic microorganisms. Unlike mammals, they lack mobile defense cells, so defense processes depend on autonomous cellular events with a broad repertoire of recognition to detect pathogens, which compensates for the lack of an adaptive immune system. These defense mechanisms remain inactive or latent until they are activated after exposure or contact with inducing agents, or after the application of the inductor; they remain inactive only until they are affected by a pathogen or challenged by an elicitor from the same. Resistance induction represents a focus of interest, as it promotes the activation of plant defense mechanisms, reducing the use of chemical synthesis pesticides, an alternative that has even led to the generation of new commercial products with high efficiency, stability and lower environmental impact, which increase productivity by reducing not only losses but also increasing plant growth. Considering the above, the objective of this review is to address the issue of resistance induction with a focus on the potential of the use of oligosaccharides in agriculture, how they are recognized by plants, how they can be used for commercial products and perspectives.     

Nanoparticles from vesicle polymerization: Characterization and kinetic study

The polymerization of isodecyl acrylate (ISODAC) in vesicles made from an anionic surfactant—sodium di-2-ethylhexyl phosphate (SEHP)—and from water is studied by ¹H-NMR, transmission electron microscopy, and quasielastic light scattering. High polymerization rates and high conversion rates are achieved with both water-soluble initiator, K₂S₂O₈ (potassium persulfate), and oil-soluble initiator, AIBN (azoisobisbutyronitrile). ISODAC is probably located inside the vesicle bilayer(s) because of its high hydrophobicity. Particles stable at room temperature with a mean diameter of about 50 nm are obtained. Kinetic orders of ISODAC polymerization are determined and the characterization of the resulting particles during and after polymerization are studied. © 1996 John Wiley & Sons, Inc.     

A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability

Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.     

Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method

The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG_{(AAB and/or ABA)}]⁺ generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)]⁺ or the neutral TAG molecule (TAG_{(AAB and/or ABA)}) leading to [ref, Li]⁺. The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R_iso), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures.     

Enhancement of temozolomide stability by loading in chitosan-carboxylated polylactide-based nanoparticles

In the presented work, amphiphilic nanoparticles based on chitosan and carboxy-enriched polylactic acid have been prepared to improve the stability of the pro-drug temozolomide in physiological media by encapsulation. The carrier, with a diameter in the range of 150–180 nm, was able to accommodate up to 800 μg of temozolomide per mg of polymer. The obtained formulation showed good stability in physiological condition and preparation media up to 1 month. Temozolomide loaded inside the carrier exhibited greater stability than the free drug, in particular in simulated physiological solution at pH 7.4 where the hydrolysis in the inactive metabolite was clearly delayed. CS-SPLA nanoparticles demonstrated a pH-dependent TMZ release kinetics with the opportunity to increase or decrease the rate. Mass spectroscopy, UV-Vis analysis, and in vitro cell tests confirmed the improvement in temozolomide stability and effectiveness when loaded into the polymeric carrier, in comparison with the free drug.