Dual template synthesis of a highly mesoporous SSZ-13 zeolite with improved stability in the methanol-to-olefins reaction

The dual template synthesis of zeolite SSZ-13 by use of trimethyl-adamantanammonium hydroxide and a diquaternary-ammonium mesoporogen induces considerable mesoporosity without impeding zeolite microporosity. The strongly improved accessibility of Br?nsted sites in mesoporous SSZ-13 increases its stability during application as an acid catalyst in the methanol-to-olefins reaction.     

Metabolic profiling of mouse cerebrospinal fluid by sheathless CE-MS

The need for sensitive analytical technologies applicable to metabolic profiling of volume-restricted biological samples is high. Here, we demonstrate feasibility of capillary electrophoresis (CE) coupled to electrospray ionization mass spectrometry (MS) with sheathless nano-electrospray interface for non-targeted profiling of ionogenic metabolites in body fluids of experimental animals. A representative mixture of the metabolites and body fluids of mice such as cerebrospinal fluid (CSF), urine and plasma were used as examples of low-volume biological samples for method evaluation. An injection volume of only 9?nL resulted in limits of detection between 0.7 and 12?nM for the metabolite mixture. The method allowed the detection of ～350 molecular features in mouse CSF (an injection volume of ca. 45?nL), while ～400 features were observed in mouse plasma and ～3,500 features in mouse urine (an injection volume of ca. 9?nL). The low-volume body fluid samples were analyzed directly after only 1:1 dilution with water, thereby fully retaining sample integrity, which is of crucial importance for non-targeted metabolic profiling. As little is known about the metabolic composition of mouse CSF, we identified a fraction of the molecular features in mouse CSF using accurate mass information, migration times, MS/MS data, and comparison with authentic standards. We conclude that sheathless CE-MS can be used for sensitive metabolic profiling of volume-restricted biological samples.     

Arago's best paper

The year 2011 is the bicentennial of François Arago’s discovery of optical rotation. The immediate usurpation of the study of optical activity by Jean‐Baptiste Biot led to the first well‐known judgments of the arrangements of atoms in space. Scientists are less aware that Arago achieved something far greater than his contributions to optics, by signing the 1848 decree that abolished slavery throughout the French Empire. Opposing attitudes of Arago and Biot toward abolition, foreshadowed in their early rift over optical rotation, were surprisingly exposed in mid‐century developments in chiroptics. As shown in a recent book by Levitt, Arago sought a reinvention of the whole colonial plantation system consistent with Republican principles, while Biot tried to place the cane sugar industry and slave‐based economy on the quantitative foundation of saccharimetry. A reevaluation of the circumstances of abolition can celebrate both societal evolution and optical rotation on the 200th birthday of the latter. Episodes from Arago’s life that arguably created his predisposition toward abolition are emphasized: He was imprisoned several times as a young man and knew the loss of liberty, his brother Jacques witnessed slavery in Brazil and advocated abolition in travel books prepared with François, and finally, in writing the biography of the Marquis de Condorcet, the spirit behind the first, albeit impermanent French abolition of slavery in 1794, Arago found proof of concept for his comparable challenge. Curiously, the measurement of the optical rotation of crystals and sugar, the foci of Arago and Biot, respectively, remain among the greatest challenges in polarimetry. Current developments are reviewed with respect to chiroptical anisotropy and in vivo glucose detection driven by the pandemic of diabetes, a disease diagnosed polarimetrically by Biot that claimed the life of Arago.     

Continuous Synthesis of Peralkylated Imidazoles and their Transformation into Ionic Liquids with Improved (Electro)Chemical Stabilities

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one‐pot modified Debus–Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non‐substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable.     

Chiral nickel(II) complexes in the preparation of 11C- and 18F-labelled enantiomerically pure α-amino acids

Positron emission tomography (PET) utilises positron emitting radiopharmaceuticals in the study of metabolic and physiological processes. FDG-PET is a useful technique for tumour detection; however FDG has disadvantages. The incorporation of labelled amino acids into brain tumours and into some other organs with high physiological consumption of glucose is a superior diagnostic method due to its much higher selectivity compared to FDG. A Ni(II) complex with a Schiff base of BPB and glycine was one of the first glycine synthons used for asymmetric synthesis of carbon-11 and fluorine-18 labelled α-amino acids. A similar complex was employed for routine preparation of [(18)F]FET. Physico-chemical investigations allowed us to design modified complexes with much stronger stereodiscriminative power including stereospecific ones. Chiral nickel complexes are also used for the preparation of tailored amino acids for the incorporation into peptides followed by labelling the peptides with fluorine-18 labelled "click" reagents. This review covers PET applications of Ni(II) complexes of Schiff base of BPB and α-amino acids from 1989 to date.     

Synthesis of U(IV) imidos from Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by extrusion of bibenzyl

Addition of organic azides, N(3)R (R = 2,4,6-trimethylphenyl (Mes), phenyl (Ph), 1-adamantyl (Ad)), to a solution of the uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) (1), results in the formation of a family of uranium(iv) imido derivatives, Tp*(2)U(NR) (2-R). Notably, these complexes were synthesized in high yields by coupling of the benzyl groups to form bibenzyl. The uranium(IV) imido derivatives, 2-Mes, 2-Ph, and 2-Ad, were all characterized by both (1)H NMR and IR spectroscopy, and 2-Mes and 2-Ad were also characterized by X-ray crystallography. In the molecular structure of 2-Mes, typical κ(3)-coordination of the Tp* ligands was observed; however in the case of 2-Ad, one pyrazole ring of a Tp* ligand has rotated away from the metal centre, forcing a κ(2)-coordination of the pyrazoles. This results in a uranium-hydrogen interaction with the Tp* B-H. Treating these imido complexes with para-tolualdehyde results in multiple bond metathesis, forming the terminal uranium(IV) oxo complex, Tp*(2)U(O), and the corresponding imine.     

Directed supramolecular surface assembly of SNAP-tag fusion proteins

Supramolecular assembly of proteins on surfaces and vesicles was investigated by site-selective incorporation of a supramolecular guest element on proteins. Fluorescent proteins were site-selectively labeled with bisadamantane by SNAP-tag technology. The assembly of the bisadamantane functionalized SNAP-fusion proteins on cyclodextrin-coated surfaces yielded stable monolayers. The binding of the fusion proteins is specific and occurs with an affinity in the order of 10(6) M(-1) as determined by surface plasmon resonance. Reversible micropatterns of the fusion proteins on micropatterned cyclodextrin surfaces were visualized by using fluorescence microscopy. Furthermore, the guest-functionalized proteins could be assembled out of solution specifically onto the surface of cyclodextrin vesicles. The SNAP-tag labeling of proteins thus allows for assembly of modified proteins through a host-guest interaction on different surfaces. This provides a new strategy in fabricating protein patterns on surfaces and takes advantage of the high labeling efficiency of the SNAP-tag with designed supramolecular elements.     

Tetraphenol-based diphosphite ligands: synthesis, characterization, and application in the rhodium-catalyzed hydroformylation of octenes

A new class of diphosphites is described, based on a tetraphenol backbone. Ligands TP1-TP5 were synthesized and fully characterized and their application in the hydroformylation of octenes was investigated. Ligand TP3, bearing a 1-naphthoxy substituent on the phosphorus, shows the highest regioselectivity toward the linear aldehyde.     

Software Engineering and complexity in effective Algebraic Geometry

One may represent polynomials not only by their coefficients but also by arithmetic circuits which evaluate them. This idea allowed in the past fifteen years considerable complexity progress in effective polynomial equation solving. We present a circuit based computation model which captures all known symbolic elimination algorithms in effective Algebraic Geometry and exhibit a class of simple elimination problems which require exponential size circuits to be solved in this model. This implies that the known, circuit based elimination algorithms are already optimal.     

Study and modelling of two apple quality attributes: the soluble solids content and the firmness

Recently, the basic dynamics of fruit characteristics have been modelled using a stochastic approach. The time evolution of apple quality attributes was represented by means of a system of differential equations in which the initial conditions and model parameters are both random. In this work, a complete study of two apple quality attributes, the soluble solids content and the firmness, is carried out. For each of these characteristics, the system of differential equations is linear and the state variables and the parameters are represented as random variables with their statistical properties (mean values, variances, covariances, joint probability density function) known at the initial time. The dynamic behaviour of these statistical properties is analysed. The variance propagation algorithm is used to obtain an analytical expression of the dynamic behaviour of the mean value, the variance, the covariance and the probability density function. A Monte Carlo method and the Latin hypercube method were developed to obtain a numerical expression of the dynamic behaviour of these statistical quantities and particularly to follow the time evolution of joint probability density function which represents one but the best mean to characterize random phenomena linked with fruit quality attributes.