Transition metal complexes with long-chain amines thermal behaviour and crystal structure of (n-CaH2a+1NH2)2ZnCl2

The thermal behaviour of (n-C_aH_2n+1NH₂)₂ZnCl₂ complexes with n = 6, 8, … 16 has been investigated by DSC and by temperature variable IR and X-ray powder diffraction techniques. Complexes with n = 12,14,16 show solid—solid phase transition which are “melting” transitions of the hydrocarbon regions of the structure. The crystal structure of both the low and the high temperature polymorphs is characterized by the piling of sandwiches, each formed by an “inorganic” layer sandwiched between two alkylammonium layers.     

The enthalpies of combustion and formation of <Emphasis Type="Italic">L</Emphasis>-α-glutamic and 6-aminohexanoic acids

Summary The energies of combustion of crystalline L-α-glutamic and 6-aminohexanoic acids were measured in a static bomb adiabatic calorimeter, in pure oxygen at 3040 kPa. Corrections were made for the heats due to the ignition of sample and for the nitric acid formation. The derived enthalpies of formation for L-α -glutamic and 6-aminohexanoic acids are Δ_fH_cr⁰= -1002.6±1.1 kJ mol^-1and Δ_fH_cr⁰= -641.6±1.2 kJ mol^-1, respectively. The data of enthalpy of formation are compared with literature values and with estimated values by means of group additivity, using parameters recommended by Domalski and Hearing.     

HPLC monitored synthesis of R2NCH2 substituted benzene derivatives used as (C,N)-ligands for organometallic compounds

2-(Diethylaminomethyl)phenyl bromide and 1,3-bis(dimethylaminomethyl)-benzene, useful ligands for the synthesis of hypervalent organometallic compounds, were prepared and characterized by NMR (¹H, ¹³C, 2D experiments) spectroscopy. Their synthesis was monitored by the HPLC method. The compounds were eluted on a Nucleosil 120 Si column (5 μm, 25×0.4 cm) with n-hexane at room temperature using a 1.0 ml/min flow-rate. The maximum values of absorbance for the studied compounds, excepting the diethylamine, were located in a narrow range around 212 nm, the wavelength used for their UV detection. The diethylamine was detected at 190 nm. The calibration curves are straight lines with correlation factors r>0.995. The HPLC data are in good agreement with those provided by NMR spectroscopy.     

Regioselective Synthesis and Molecular Docking Studies of 1,5-Disubstituted 1,2,3-Triazole Derivatives of Pyrimidine Nucleobases

1,2,3-triazoles are versatile building blocks with growing interest in medicinal chemistry. For this reason, organic chemistry focuses on the development of new synthetic pathways to obtain 1,2,3-triazole derivatives, especially with pyridine moieties. In this work, a novel series of 1,5-disubstituted-1,2,3-triazoles functionalized with pyrimidine nucleobases were prepared via 1,3-dipolar cycloaddition reaction in a regioselective manner for the first time. The N1-propargyl nucleobases, used as an alkyne intermediate, were obtained in high yields (87–92%) with a new two-step procedure that selectively led to the monoalkylated compounds. Then, FeCl₃ was employed as an efficient Lewis acid catalyst for 1,3-dipolar cycloaddition between different aryl and benzyl azides and the N1-propargyl nucleobases previously synthesized. This new protocol allows the synthesis of a series of new 1,2,3-triazole derivatives with good to excellent yields (82–92%). The ADME (Absorption, Distribution, Metabolism, and Excretion) analysis showed good pharmacokinetic properties and no violations of Lipinsky’s rules, suggesting an appropriate drug likeness for these new compounds. Molecular docking simulations, conducted on different targets, revealed that two of these new hybrids could be potential ligands for viral and bacterial protein receptors such as human norovirus capsid protein, SARS-CoV-2 NSP13 helicase, and metallo-β-lactamase.     

Modifying LnHPDO3A Chelates for Improved T1 and CEST MRI Applications

The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. ¹H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, ¹H and ¹⁷O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years.     

Electrically insulated molecular wires

This paper is an up-to-date mini-review based on literature data and own results regarding synthesis and properties of conducting (pseudo)rotaxane supramolecular structures. Conjugated polymers, such as polyarylene, polyheteroarylene, polyaniline, polyarylenevinylene or polyaryleneimine, were used as axle, while the macrocyclic components were cyclodextrins, cucurbiturils, cyclophanes or crown ethers. Properties of the supramolecular structure such as solubility, thermal or chemical stability, conductivity, etc. can be drastically modified by the inclusion of hydrophobic conjugated polymers inside the macrocycle, without any chemical modification. For instance, the photophysical properties (i.e. quantum yield of fluorescence and electroluminescence) of the supramolecular structures were enhanced when compared with uninsulated conjugated polymers. The doping process is also affected, because the access of a dopant to the conjugated chain is limited only to the uncovered domains of the conjugated chain.     

A Convenient Synthesis of Unsymmetrical N,N′-Disubstitutedα,ω-Diaminoalkanes

A general procedure is described for regiospecific construction of unsymmetrical N-alkyl (or aralkyl)-N′-aryl-α,ω-diaminoalkanes 3 (n=2,3,4) by reduction of N-(ω -arylaminoalkyl)amides 2 with borane. Compounds 2 are readily obtained by condensation of N-(ω-haloalkyl)amides 1 with aromatic amines.     

Baroque glass mosaics from the Capela de São João Baptista (Chapel of Saint John the Baptist,Lisbon): unveiling the glassmaking records

For the first time, 18th‐century glass mosaics from the Capela de São João Baptista (Chapel of St. John the Baptist, Lisbon) were analysed by Raman microscopy (RM). This masterpiece in baroque mosaic art had one of its major contributors the most famous glassmaker in Rome, Alessio Mattioli. Mattioli was celebrated because of the opacity of his mosaics and the astonishing number of hues he was able to produce for mosaic decorating Saint Peter's Basilica in Rome. This study had two goals in mind: (1) characterising the materials involved in the manufacture of these glass mosaics and (2) lengthening the understanding of what was left of Mattioli's glassmaking records. As expected the mosaics presented a high ratio of crystalline phases, making RM the ideal technique for non‐destructive analysis. The mosaics contained a white ‘background’ or opacifier added identified as Ca₂Sb₂O₇. The yellow tesserae are opacified with lead antimonate (Pb₂Sb₂O₇) and ternary oxides, structures related to lead antimonate but with other ions entering the position of Sb⁴⁺ (namely Sn⁴⁺). Those ternary oxides are pervasive in most colours, admixed with other colorants. The red, orange, pink and brown colours were accomplished with cuprous oxide (Cu₂O) and admixed with a ternary oxide to create the latter three colours. The red copper‐based colours were made according to the procedure to make a ruby copper glass and with the exception of the red colour; all mosaics exhibited a dark layer on each side of the mosaic, named scorzetta. This layer is the outcome of an oxidation reaction because of a quick cooling process and is composed of CuO. Finally the blue and green colours are accomplished with cobalt oxide and copper oxide, respectively, and the purple/black colour with manganese oxide. Copyright © 2015 John Wiley & Sons, Ltd.