Exploring new synthetic strategies in the development of a chemically activated Ru-based olefin metathesis catalyst

The objective of this work was to develop an industrially relevant olefin metathesis initiator, which circumvents the expensive, patent protected, often cumbersome preparative routes via Grubbs benzylidene complexes. Upon coordination of a Schiff base ligand to a second-generation ruthenium allenylidene complex, the formation of three catalyst isomers was observed. The major isomer was successfully isolated, and tested in a few olefin metathesis reactions. Acids such as HCl and HSiCl(3) were found to boost the metathesis reaction but the in situ formation of a neutral Ru carbyne complex restricted the catalytic capacity. Using the Lewis acid PhSiCl(3), the formation of a carbyne species was avoided, and turnover numbers up to 30,000 were reached in the ring-opening metathesis polymerisation of cycloocta-1,5-diene.     

Method for Quantitative Evaluation of Kinetic Constants in Olefin Polymerizations, 3

A method for the quantitative evaluation of kinetic constants in Ziegler–Natta and metallocene olefin homopolymerizations presented previously (V. Matos, A. G. M. Neto, J. C. Pinto, J. Appl. Polym. Sci. 2001 , 79, 2076; V. Matos, A. G. M. Neto, M. Nele, J. C. Pinto, J. Appl. Polym. Sci. 2002 , 86, 3226) is extended to allow for estimation of model parameters in copolymerization reactions. The method is used to estimate kinetic parameters of ethylene/propylene copolymerization during the synthesis of high impact poly(propylene) in a train of cascade reactors. Process models were developed to describe the reaction rate profile, reactor solubles, molecular weight distribution of the total polymer, xylene solubles, and insoluble polymer. The process models and the estimated parameters were inserted into a process simulator that successfully described the industrial process.

     

A new recyclable Pd catalyst supported on vertically aligned carbon nanotubes for microwaves-assisted Heck reactions

Palladium supported on vertically aligned multi-walled carbon nanotubes (Pd/VA-CNTs) is used as catalyst for the C-C coupling reactions of p-iodonitrobenzene with styrene and ethyl acrylate under microwaves irradiation. Pd/VA-CNTs catalyst exhibits higher activity compared to Pd supported on activated charcoal, under the same reaction conditions. Due to the microwaves irradiation, the kinetics of the reaction is strongly accelerated compared to that obtained with a traditional heating mode. The macroscopic form of aligned CNTs support allows an easy recovery of the catalyst, avoiding a costly post-reaction filtration. In addition, the interaction between the active phase and the support leads to the negligible leaching of palladium during recycling tests. The observed results indicate that Pd/CNTs is a recyclable and stable heterogeneous catalytic system.     

Preparation of PMMA Nanoparticles Loaded with Benzophenone-3 through Miniemulsion Polymerization

Summary: The present paper analyzes the production of poly(methyl methacrylate) – PMMA – nanoparticles loaded with benzophenone-3 through miniemulsion polymerization. The obtained product is homogeneous and stable, allowing for preparation of photo-protective formulations. It is observed in particular that bezophenone-3 interacts with the reacting system, promoting the growth of the PMMA chains produced in miniemulsion.     

In Situ Incorporation of Doxorubicin in Copolymer Particles During Suspension Polymerization

Summary: This work reports the kinetic behavior and the molecular properties of obtained copolymers during vinyl acetate and methyl methacrylate suspension copolymerizations in presence of doxorubicin. The obtained spherical particles are intended for use as chemoembolization agents. It is shown that the presence of doxorubicin in the reaction medium promotes significant changes in the copolymerization kinetics and final molecular weight averages of the polymer product.     

Novel heterometal-organic complexes as first single source precursors for up-converting NaY(Ln)F4 (Ln = Yb, Er, Tm) nanomaterials

First heterometal-organic single source precursors for NaYF(4) nanomaterials as a host matrix for up-conversion emission are reported. These novel heterobimetallic derivatives NaY(TFA)(4)(diglyme) (1), [Na(triglyme)(2)][Y(2)(TFA)(7)(THF)(2)] (2) and Na(2)Y(TFA)(5)(tetraglyme) (3) (TFA = trifluoroacetate), which were fully characterized by elemental analysis, FT-IR and (1)H NMR spectroscopy, TG-DTA data as well as single crystal X-ray structures, are advantageous in terms of being anhydrous and having lower decomposition temperatures in comparison to the homometallic precursor Y(TFA)(3)(H(2)O)(3). In addition, they also contain chelating glyme ligands, which act as capping reagents during decomposition to control the NaYF(4) particle size and render them monodisperse in organic solvents. On decomposition in 1-octadecene, the molecular derivatives 1 and 3 are converted, in the absence of any surfactant or capping reagent, to cubic NaYF(4) nanocrystals at significantly lower temperatures (below 250 °C). At higher temperature, a mixture of the cubic and hexagonal phases was obtained, the relative ratio of the two phases depending on the reaction temperature. A pure hexagonal phase, which is many folds more efficient for UC emission than the cubic phase, was obtained by calcining nanocrystals of mixed phase at 400 °C. In order to co-dope this host matrix with up-converting lanthanide cations, analogous complexes NaLn(TFA)(4)(diglyme) [Ln = Er (4), Tm (5), Yb (6)] and Na(2)Ln(TFA)(5)(tetraglyme) [Ln = Er (7), Yb (8)] were also prepared and characterized. The decomposition in 1-octadecene of suitable combinations and appropriate molar ratios of these yttrium, ytterbium and erbium/thulium derivatives gave cubic and/or hexagonal NaYF(4): Yb(3+), Er(3+)/Tm(3+) nanocrystals (NCs) capped by diglyme or tetraglyme ligands, which were characterized by IR, TG-DTA data, EDX analysis and TEM studies. Surface modification of these NCs by ligand exchange reactions with poly acrylic acid (PAA) and polyethyleneglycol (PEG) diacid 600 was also carried out to render them water soluble. The THF solutions of suitable combinations of the diglyme derivatives were also used to elaborate the thin films of NaYF(4):Yb(3+), Er(3+)/Tm(3+) on a glass or Si wafer substrate by spin coating. The multicolour up-conversion fluorescence was successfully realized in the Yb(3+)/Er(3+) (green/red) and Yb(3+)/Tm(3+) (blue/violet) co-doped NaYF(4) nanoparticles and thin films, which demonstrates that they are promising UC nanophosphors of immense practical interest. The up-conversion excitation pathways for the Er(3+)/Yb(3+) and Tm(3+)/Yb(3+) co-doped materials are discussed.     

Triaryl-1,3,5-triazinane-2,4,6-triones functionalized with electron-rich Fe(II) and Ru(II) acetylide complexes: new organometallic octupoles with large hyperpolarizabilities

The synthesis and study of a series of trinuclear organometallic triaryl-1,3,5-triazinane-2,4,6-triones functionalized by d(6)-transition metal acetylides complexes at their periphery are reported. Remarkably large hyperpolarizabilities, far superior to those of related purely organic derivatives, are measured by hyper-Rayleigh scattering (HRS) for these new octupolar chromophores.     

Measurement of the neutron-induced deuteron breakup reaction cross-section between 5 and 25 MeV

High-spin states in ¹⁸⁷Pt have been studied by means of ??-ray spectroscopy techniques. Known bands have been significantly extended and new bands have been found. The band structures are discussed in the framework of the cranking model and negative-parity states are compared with calculations performed with a semi-microscopic axial-rotor plus one-quasiparticle coupling model. Shape coexistence is observed from low excitation energy.     

Gas Chromatographic Fingerprint Analysis for the Comparison of Seized Cannabis Samples

Cannabis sativa L. is widely used as recreational illegal drugs. Illicit Cannabis profiling, comparing seized samples, is challenging due to natural Cannabis heterogeneity. The aim of this study was to use GC–FID and GC–MS herbal fingerprints for intra (within)- and inter (between)-location variability evaluation. This study focused on finding an acceptable threshold to link seized samples. Through Pearson correlation-coefficient calculations between intra-location samples, ‘linked’ thresholds were derived using 95% and 99% confidence limits. False negative (FN) and false positive (FP) error rate calculations, aiming at obtaining the lowest possible FP value, were performed for different data pre-treatments. Fingerprint-alignment parameters were optimized using Automated Correlation-Optimized Warping (ACOW) or Design of Experiments (DoE), which presented similar results. Hence, ACOW data, as reference, showed 54% and 65% FP values (95 and 99% confidence, respectively). An additional fourth root normalization pre-treatment provided the best results for both the GC–FID and GC–MS datasets. For GC–FID, which showed the best improved FP error rate, 54 and 65% FP for the reference data decreased to 24 and 32%, respectively, after fourth root transformation. Cross-validation showed FP values similar as the entire calibration set, indicating the representativeness of the thresholds. A noteworthy improvement in discrimination between seized Cannabis samples could be concluded.     

Understanding Parahydrogen Hyperpolarized Urine Spectra: The Case of Adenosine Derivatives

Parahydrogen hyperpolarization has emerged as a promising tool for sensitivity-enhanced NMR metabolomics. It allows resolution and quantification of NMR signals of certain classes of low-abundance metabolites that would otherwise be undetectable. Applications have been implemented in pharmacokinetics and doping drug detection, demonstrating the versatility of the technique. Yet, in order for the method to be adopted by the analytical community, certain limitations have to be understood and overcome. One such question is NMR signal assignment. At present, the only reliable way to establish the identity of an analyte that gives rise to certain parahydrogen hyperpolarized NMR signals is internal standard addition, which can be laborious. Herein we show that analogously to regular NMR metabolomics, generating libraries of hyperpolarized analyte signals is a viable way to address this limitation. We present hyperpolarized spectral data of adenosines and give an early example of identifying them from a urine sample with the small library. Doing so, we verify the detectability of a class of diagnostically valuable metabolites: adenosine and its derivatives, some of which are cancer biomarkers, and some are central to cellular energy management (e.g., ATP).