Synthesis and Profiling of a Diverse Collection of Azetidine-Based Scaffolds for the Development of CNS-Focused Lead-like Libraries

The synthesis and diversification of a densely functionalized azetidine ring system to gain access to a wide variety of fused, bridged, and spirocyclic ring systems is described. The in vitro physicochemical and pharmacokinetic properties of representative library members are measured in order to evaluate the use of these scaffolds for the generation of lead-like molecules to be used in targeting the central nervous system. The solid-phase synthesis of a 1976-membered library of spirocyclic azetidines is also described.     

Synthesis and characterisation of the ethylene bridged permethylindenyl cerium complex [(EBI*)CeI(THF)

Synthesis, magnetic properties, NMR spectroscopy, and crystallographic details of an ethylene bridged hexamethylindenyl (EBI*) cerium iodide complex [(EBI*)CeI(THF)] are reported.     

Analytical Solution Incorporating History-Dependent Processes for Quick Assessment of Capillary Trapping During CO<Subscript>2</Subscript> Geological Storage

Carbon storage in saline formations is considered as a promising option to ensure the necessary decrease of CO₂ anthropogenic emissions. Its industrial development in those formations is above all conditioned by its safety demonstration. Assessing the evolution of trapped and mobile CO₂ across time is essential in the perspective of reducing leakage risks. In this work, we focus on residual trapping phenomenon occurring during the wetting of the injected CO₂ plume. History dependent effects are of first importance when dealing with capillary trapping. We then apply the classical fractional flow theory (Buckley–Leverett type model) and include trapping and hysteresis models; we derive an analytical solution for the temporal evolution of saturation profile and of CO₂ trapped quantity when injecting water after the gas injection (“artificial imbibition”). The comparison to numerical simulations for different configurations shows satisfactory match and justifies, in the case of industrial CO₂ storage, the assumptions of incompressible flow with no consideration of capillary pressure. The obtained analytical solution allows the quick assessment of both the quantity and the location of mobile gas left during imbibition.     

Intercalation and grafting of benzene derivatives into zinc-aluminum and copper-chromium layered double hydroxide hosts: an XPS monitoring study

We report an original strategy to describe, via X-ray photoelectron spectroscopy (XPS) measurements, the interactions between the organic and the mineral sub-systems within a multifunctional hybrid material. A tunable layered double hydroxide (LDH) host system, either a Zn(2)Al- or Cu(2)Cr-hydrotalcite like compound, is modified with the insertion of the organic guest entities, 4-phenol-sulfonate (HBS) or -carboxylate (HBC). The resulting interactions are studied at two levels: after the organic molecules' insertion in the host LDH (ionic exchange between the LDH counter-ions and the organic anions) and after the condensation (grafting) of the organic species onto the mineral layers when thermally treated. For the inserted material, the main XPS results show a stabilization of the organic molecules within the mineral sheets via H bonding as found elsewhere with FTIR study, the mineral matrix being unchanged. The XPS signal of the organic molecules slightly changes with a widening of core peaks, attesting to some local surrounding modifications. When heating up the Zn(2)Al hybrid material, stronger interactions between organic and inorganic systems appeared from around 80 °C with some obvious electronic changes as monitored with the XPS S2p signal of the HBS guest molecules. At the same time, the PXRD pattern clearly shows a decrease of the basal spacing according to a two step contraction process which could be interpreted as a progressive organic molecule condensation onto the inorganic layers via iono-covalent bonds. A copper-chromium LDH is also studied to probe the same kind of interactions with the HBS molecules. The ability of distortion of such mineral material involves a peculiar process of contraction from 40 °C with the immediate and effective anchorage of organic molecules.     

Phase equilibria modeling of biodiesel related mixtures using the GCA-EoS model

In this work, a group-contribution equation of state that takes into account association effects (GCA-EoS) is extended to model the phase behavior of fatty esters (biodiesel) in binary mixtures with glycerol, alcohols and water and ternary mixtures with glycerol and methanol. A new associating group (glycerol hydroxyl group: OH^Gly) was defined to take into consideration the association effects in the glycerol molecule. Self-association of methanol, water and glycerol and cross-association between methanol–glycerol, alcohol–ester, water–ester and glycerol–ester groups were considered. New pure-group, binary interaction and association parameters have been determined. The correlations and predictions of the model are found in acceptable agreement with selected experimental data reported in the literature.     

On enumeration of polynomial equivalence classes and their application to MPKC

The Isomorphism of Polynomials (IP) is one of the most fundamental problems in multivariate public key cryptography (MPKC). In this paper, we introduce a new framework to study the counting problem associated to IP. Namely, we present tools of finite geometry allowing to investigate the counting problem associated to IP. Precisely, we focus on enumerating or estimating the number of isomorphism equivalence classes of homogeneous quadratic polynomial systems. These problems are equivalent to finding the scale of the key space of a multivariate cryptosystem and the total number of different multivariate cryptographic schemes respectively, which might impact the security and the potential capability of MPKC. We also consider their applications in the analysis of a specific multivariate public key cryptosystem. Our results not only answer how many cryptographic schemes can be derived from monomials and how big the key space is for a fixed scheme, but also show that quite many HFE cryptosystems are equivalent to a Matsumoto–Imai scheme.     

Fourier holograms recorded and decoded in polychromatic light

This paper describes a recording and reconstruction method applied to two-dimension Fourier holography, in which the illumination at the recording stage is spatially coherent and temporally incoherent. The various chromatic components of the information to be recorded in the hologram are spread along a direction orthogonal to the entrance slit of a spectroscope that behaves as scanning pupil performing a chromatic coding. The message, both spatially and temporally coded, can be reconstructed by using a conventional process, the light source being still polychromatic.     

as-Triazino[4,5-α] indoles. III. Etude des substitutions électrophiles des triazinoindolones

Electrophilic substitution reactions of the 1- and 4-triazino-indolones were made on lactamic nitrogen with methyl sulphate or benzyl chloride and on the homocycle with bromine or nitric acid. BrominatJon and nitration reactions gave either mono-substitutions on position 10 or disubstitutions on position 7 and 10 or 9 and 10 or polysubstitutions leading to mixtures of tri-and tetrasubstituted compounds. The structure of the derivatives was determined by nmr, study of the NOE effect and unequivocal synthesis.     

Overcoming biofluid protein complexity during targeted mass spectrometry detection and quantification of protein biomarkers by MRM cubed (MRM3)

Targeted mass spectrometry in the so-called multiple reaction monitoring mode (MRM) is certainly a promising way for the precise, accurate, and multiplexed measurement of proteins and their genetic or posttranslationally modified isoforms. MRM carried out on a low-resolution triple quadrupole instrument faces a lack of specificity when addressing the quantification of weakly concentrated proteins. In this case, extensive sample fractionation or immunoenrichment alleviates signal contamination by interferences, but in turn decreases assay performance and throughput. Recently, MRM³ was introduced as an alternative to MRM to improve the limit of quantification of weakly concentrated protein biomarkers. In the present work, we compare MRM and MRM³ modes for the detection of biomarkers in plasma and urine. Calibration curves drawn with MRM and MRM³ showed a similar range of linearity (R ²?>?0.99 for both methods) with protein concentrations above 1 μg/mL in plasma and a few nanogram per milliliter in urine. In contrast, optimized MRM³ methods improve the limits of quantification by a factor of 2 to 4 depending on the targeted peptide. This gain arises from the additional MS³ fragmentation step, which significantly removes or decreases interfering signals within the targeted transition channels.     

Modelling of tuning of an ultra low frequency Roberts Linkage vibration isolator

We present an analytical model for a Roberts Linkage used as an ultra low frequency vibration isolator. The Roberts Linkage is a structure that simulates a very long radius conical pendulum, at a relatively small height. We show through an analytical solution that it is possible to independently tune the centre of percussion and the resonant frequency for arbitrary geometrical configurations. The result is shown to provide a practical tuning solution, which achieves near ideal vibration isolation.