Analysis of basic compounds at high pH values by reversed-phase liquid chromatography

Reversed phase high performance liquid chromatography (RPLC) is currently the method of choice for the analysis of basic compounds. However, with traditional silica materials, secondary interactions between the analyte and residual silanols produce peak tailing which can negatively affect resolution, sensitivity, and reproducibility. In order to reduce these secondary interactions, which comprise ion exchange, hydrogen bonding, and London forces interactions, chromatographic analyses can be carried out at low or high pH values where silanol groups and basic compounds are mostly uncharged. The chromatographic behaviour of a particular bidentate stationary phase, Zorbax Extend C18, was studied with a set of basic and neutral compounds. Thanks to a higher chemical stability than traditional silica based supports, analyses were carried out with a high pH mobile phase, which represents a good alternative to the acidic mobile phases generally used to reduce ion exchange interactions. The performance of this bidentate stationary phase was also compared with that of other supports and it was proved that it is advantageous to work with high pH mobile phases when analyzing basic compounds.     

Das Hexagallan [Ga6{SiMe(SiMe3)2}6] und das closo‐Hexagallanat [Ga6{Si(CMe3)3}4(CH2C6H5)2]2— — der Übergang zu einem ungewöhnlichen precloso‐Cluster

The Hexagallane [Ga₆{SiMe(SiMe₃)₂}₆] and the closo‐Hexagallanate [Ga₆{Si(CMe₃)₃}₄ (CH₂C₆H₅)₂]^2— — the Transition to an Unusual precloso‐Cluster The closo hexagallanate [Ga₆R₄(CH₂Ph)₂]^2— (R = Si^tBu₃) as well as the hexagallane Ga₆R₆ (R = SiMe(SiMe₃)₂) with only six cluster electron pairs were isolated from reactions of “GaI” with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn‐Teller‐distortion and is different from the capped trigonal bipyramidal one expected by the Wade‐Mingos rules. Both compounds were characterized by X‐ray crystallography. The bonding is discussed with simplified Ga₆H₆ and Ga₆H₆^2— models via DFT methods.     

Synthesis,characterization and antimicrobial studies on 13-membered-N6-macrocyclic transition metal complexes containing trimethoprim

Asymmetrical macrocyclic complexes of Mn^II, Co^II, Ni^II, Cu^II and Zn^II have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X₂] (M = Mn^II, Co^II, Ni^II, Cu^II and Zn^II, L = ligand and X = Cl^?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X₂] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X₂] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X₂] complexes exhibit potent broad spectrum antibacterial activity.     

A Novel and Cheap Synthesis of Artemisia Ketone1 (3,3,6-Trimethylhepta-L,5-Dien-4-One)

The Sequential dialkylation of dimethylaminoacetonitrile with first methallylchloride and then prenylbromide is performed at room temperature using K₂CO₃ in DMF. Subsequent hudrolysis and isomerisation offord artemisia ketone in 77% overall yield.     

Stereoselective Cycloaddition of Monosubstituted Ketene to a Methyl Glyoxylate- and Threonine-Derived Imine: Synthesis of Optically Pure β-Lactamic α-Amino Ester with High Functionality

The reaction of chloroacetyl chloride and triethylamine with a chiral imine derived from the combination of methyl glyoxylate and protected L-threonine gave two optically active α-amino acid derivatives with a cis-substituted β-lactam skeleton in a 72:28 ratio. The major product is obtained in 59% yield by simple crystallisation.     

Spectroscopic investigation of fluoroiodomethane, CH2FI: Fourier-transform microwave and millimeter-/submillimeter-wave spectroscopy and quantum-chemical calculations

Guided by theoretical predictions, the rotational spectrum of fluoroiodomethane, CH(2)FI, has been recorded and assigned. Accurate values are reported for the ground-state rotational constants, all quartic, sextic, and two octic centrifugal-distortion constants. The hyperfine structure of the rotational spectrum was thoroughly investigated using a Fourier-transform microwave spectrometer and the Lamb-dip technique in the millimeter-/submillimeter-wave region, thus allowing the accurate determination of the complete iodine quadrupole-coupling tensor and of the diagonal elements of the iodine spin-rotation tensor. Relativistic effects turned out to be essential for the accurate theoretical prediction of the dipole moment and quadrupole-coupling constants and were accounted for by direct perturbation theory and a spin-free four-component treatment based on the Dirac-Coulomb Hamiltonian. The relativistic corrections to the dipole moment amount to up to 34% and to the iodine quadrupole-coupling tensor to about 15-16% of the total values.     

A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II)

The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.     

Claisen rearrangement induced by low-energy collision of ESI-generated, protonated benzyloxy indoles

The Claisen rearrangement is a well-known process occurring in condensed phase. In the gas-phase protonated allyl phenyl ethers, propargyl phenyl ethers, and N-allyl aniline produced by positive ion chemical ionization undergo Claisen rearrangement. This reaction has been observed even in the case of odd-electron molecular ions. Phenyl allenyl ether molecular ions actually undergo Claisen rearrangement, producing intense [M - CO](+*) ions. In this investigation, the behavior of protonated benzyloxy indole and some of its derivatives, obtained in electrospray conditions, is described. Low-energy MS/MS experiments carried out on [M + H](+) species show CO loss and an unexpected water loss: both can be justified only by the occurrence of Claisen rearrangement. Deuterium labeling experiments confirm this mechanism. The influence of different substituents in the indole moiety is discussed.     

Voltammetric Detection of Free Sulfhydryl Compounds in Food Flours

Cyclic voltammetry has been applied to the rapid measurement of free SH‐compounds in food flours samples. The protocol is based on the electrochemical adaptation of the Ellman's test, where the DTNB reacts with SH‐compounds present in food flour extracts, resulting in the equimolar production of the electroactive compound TNBA which, in turns, reacts with phenylendiamine. The reaction is found to provide an analytical signal from which to quantify indirectly free sulfhydryl compounds in flours extracts.     

Novel RPLC stationary phases for lipophilicity measurement: solvatochromic analysis of retention mechanisms for neutral and basic compounds

An RPLC was developed to rapidly determine lipophilicity of neutral and basic compounds using three base deactivated RPLC stationary phases particularly designed for the analysis of basic compounds, namely, Supelcosil ABZ(+)Plus, Discovery RP Amide C16, and Zorbax Extend C18. The work consisted of three sets of experiments. In the first log kw values of neutral compounds were extrapolated using hydroorganic mobile phases at different compositions. Good correlation between log kw and log Poct indicated that the method was appropriate for these supports, without adding a silanol masking agent. In the second set of experiments, isocratic log k values of neutral and basic compounds were measured with three different mobile phases. The best estimation of lipophilicity was obtained for neutral and basic compounds when the secondary interactions were strongly reduced (i. e., when basic compounds were under their neutral form). In the third set of experiments, isocratic retention factors of basic compounds (in their neutral form) were measured with a high-pH mobile phase, on a chemically stable support (Zorbax Extend C18). Under these chromatographic conditions, correlation between the isocratic retention factors and log Poct (log D10.5) for basic compounds was similar to that for neutral compounds.