Complexes of Tin(IV) Tetrachloride with 3-Formylpyridine Semicarbazone and Thiosemicarbazones

The reaction of tin(IV) tetrachloride with 3-formylpyridine semicarbazone and different 3-formylpyridine thiosemicarbazones produces [Sn(HL)CL 3 ][SnCl 5 ] where HL stands for the neutral ligand. The tin(IV) complexes were characterized using a variety of spectroscopic techniques. Coordination through the pyridine nitrogen occurs in all cases. Solvation studies in DMSO indicated that dissociation of the ligands and their complete replacement by solvent molecules occurs.     

Tin(IV) complexes with 2-pyridineformamide-derived thiosemicarbazones: Antimicrobial and potential antineoplasic activities

Reaction of tin tetrachloride with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives gave [Sn(2Am4DH)Cl₃] (1), [Sn(2Am4Me)Cl₃] (2), [Sn(2Am4Et)Cl₃] (3) and [Sn(2Am4Ph)Cl₃] (4) as products, in which an anionic thiosemicarbazone coordinates to the metal centre along with three chloride ions. The crystal structures of 1 and 2 were determined. The thiosemicarbazones were moderately active against Candida albicans and Pseudomonas aeruginosa. Upon coordination to tin(IV) the antimicrobial activity of the thiosemicarbazones increases. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors.     

Binuclear zinc(II) complexes with the anti-inflammatory compounds salicylaldehyde semicarbazone and salicylaldehyde-4-chlorobenzoyl hydrazone (H2LASSBio-1064)

Complexes [Zn₂(HL¹)₂(CH₃COO)₂] (1) and [Zn₂(L²)₂] (2) were synthesized with salicylaldehyde semicarbazone (H₂L¹) and salicylaldehyde-4-chlorobenzoyl hydrazone (H₂LASSBio-1064, H₂L²), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn₂(HL²)₂(Cl)₂] (3) in 1:9 DMSO:acetone crystals of [Zn₂(L²)₂(H₂O)₂]·[Zn₂(L²)₂(DMSO)₄] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes.     

Structure-property relations in crystalline L-leucine obtained from calorimetry, X-rays, neutron and Raman scattering

We have studied the amino acid L-leucine (LEU) using inelastic neutron scattering, X-rays and neutron diffraction, calorimetry and Raman scattering as a function of temperature, focusing on the relationship between the local dynamics of the NH(3), CH(3), CH(2) and CO(2) moieties and the molecular structure of LEU. Calorimetric and diffraction data evidenced two novel phase transitions at about 150 K (T(1)) and 275 K (T(2)). The dynamical susceptibility function, obtained from the inelastic neutron scattering results, shows a re-distribution of the intensity of the vibrational bands that can be directly correlated with the phase transitions observed at T(1) and T(2), as well as with the already reported phase transition at T(3) = 353 K. Through the analysis of the Raman modes, the new structural arrangement observed below T(1) was related to conformational modifications of the CH and CH(3) groups, while the behavior of the N-H stretching vibration, ν(NH(3)), gave insight into the intermolecular N-H…O interactions. The observation of changes in the translational symmetry in the crystalline lattice, as well as anharmonic dynamics, allows for localized motions in LEU.     

Electrospun poly(lactic acid) nanofibers loaded with silver sulfadiazine/[Mg–Al]‐layered double hydroxide as an antimicrobial wound dressing

Poly(lactic acid) (PLA) is a versatile, bioabsorbable, and biodegradable polymer with excellent biocompatibility and ability to incorporate a great variety of active agents. Silver sulfadiazine (SDZ) is an antibiotic used to control bacterial infection in external wounds. Aiming to combine the properties of PLA and SDZ, hydrotalcite ([Mg–Al]‐LDH) was used as a host matrix to obtain an antimicrobial system efficient in delivering SDZ from electrospun PLA scaffolds intended for wound skin healing. The structural reconstruction method was successfully applied to intercalate silver sulfadiazine in the [Mg–Al]‐LDH, as evidenced by X‐ray diffraction and thermogravimetric analyses. Observations by scanning electron microscopy revealed a good distribution of SDZ‐[Mg–Al]‐LDH within the PLA scaffold. Kinetics studies revealed a slow release of SDZ from the PLA scaffold due to the intercalation in the [Mg–Al]‐LDH. In vitro antimicrobial tests indicated a significant inhibitory effect of SDZ‐[Mg–Al]‐LDH against Escherichia coli and Staphylococcus aureus. This antibacterial activity was sustained in the 2.5‐wt% SDZ‐[Mg–Al]‐LDH–loaded PLA nanofibers, which also displayed excellent biocompatibility towards human cells. The multifunctionality of the PLA/SDZ‐[Mg–Al]‐LDH scaffold reported here is of great significance for various transdermal applications.     

Simultaneous on-line pre-concentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using silica gel modified with niobium(V) oxide

This work presents the development of an on-line pre-concentration system for simultaneous determination of Cd, Cu, Ni, V, Zn, Co and Pb in aqueous environmental samples and detection by inductively coupled plasma mass spectrometry. The system is based on cationic retention of the analytes onto a mini-column filled with silica gel modified with niobium(V) oxide. The effects of chemicals and flow variables have been investigated. The optimized operating conditions, selected as a compromise between sensitivity and analytical frequency were: sample pH 7.0, sample flow rate of 6.0mL min(-1), eluent flow rate of 2.0mL min(-1), and eluent (HNO(3)) concentration of 2.5mol L(-1). The relative standard deviation (n=7), enrichment factor and linear working range were 0.8-4.5%, 23.3-37.2 and 0.05-25.0microg L(-1), respectively. Limits of detection were between 0.01 and 0.03microg L(-1). The accuracy of the proposed method was checked with certified materials (NASS-4, NASS-5, CASS-4 and SRM 1643e). Values obtained were in accordance with those reported for the certified materials. Recovery was found to be in the range of 90-110% for a suit of water samples with variable matrices (seawater, tap water and ground water) collected in Florianopolis, Brazil.     

Structural isotopic effects in the smallest chiral amino acid: observation of a structural phase transition in fully deuterated alanine

A first study of possible changes instigated by deuteration in amino acids was carried out using neutron diffraction, inelastic neutron scattering, and Raman scattering in l-alanine, C2H4(NH2)COOH. Careful analysis of the structural parameters shows that deuteration of l-alanine engenders significant geometric changes as a function of temperature, which can be directly related to the observation of new lattice vibration modes in the Raman spectra. The combination of the experimental data suggests that C2D4(ND2)COOD undergoes a structural phase transition (or a structural rearrangement) at about 170 K. Considering that this particular amino acid is a hydrogen-bonded system with short hydrogen bonds (O...H approximately 1.8 A), we evoke the Ubbelohde effect to conclude that substitution of hydrogen for deuterium gives rise to changes in the hydrogen-bonding interactions. The structural differences suggest distinct relative stabilities for the hydrogenous and deuterated l-alanine.     

Structural and Spectral Study of Nickel(II) Complexes of Pyridyl bis{3‐piperidyl‐, bis{hexamethyleneiminyl‐, bis{N(4)‐diethyl‐, and bis{N(4)‐dipropylthiosemicarbazones}

Pyridyl bis(N(4)‐substituted thiosemicarbazones), in which the substituents replacing the NH₂ group on the thiosemicarbazone moieties are piperidyl, H₂Plpip; hexamethyleneiminyl, H₂Plhexim; diethylamino, H₂Pl4DE; and dipropylamino, H₂Pl4DP, have been synthesized. These bis(thiosemicarbazones) and their nickel(II) complexes have been characterized with IR, electronic, mass, and ¹H and ¹³C NMR spectra. Crystal structures have been solved for H₂Plpip and all four nickel(II) complexes. H₂Plpip does not possess hydrogen bonding between the thiosemicarbazone moieties, but is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogen atoms. The nickel(II) complexes possess square‐planar N₂S₂ (i. e., imine nitrogen and thiolato sulfur atoms) centers and the two pyridine ring nitrogen atoms are not coordinated.     

Increasing the antibacterial activity of gallium(III) against Pseudomonas aeruginosa upon coordination to pyridine-derived thiosemicarbazones

Reaction of N(4)-phenyl-2-formylpyridine thiosemicarbazone (H2Fo4Ph), N(4)-phenyl-2-acetylpyridine thiosemicarbazone (H2Ac4Ph) and N(4)-phenyl-2-benzoylpyridine thiosemicarbazone (H2Bz4Ph) with gallium nitrate gave [Ga(H2Fo4Ph)₂](NO₃)₃ (1), [Ga(2Ac4Ph)₂]NO₃ (2) and [Ga(2Bz4Ph)₂]NO₃ (3). In all complexes coordination of the thiosemicarbazone via the N_py–N–S chelating system occurs. In 1 the thiosemicarbazone acts as a neutral ligand while in 2 and 3 the ligand is anionic. Upon slow diffusion of 2 in DMSO [Ga(2Ac4Ph)₂]NO₃·DMSO (2a) was formed. The crystal structure of 2a was determined. Upon coordination the antibacterial activity of both gallium and thiosemicarbazones against Pseudomonas aeruginosa significantly increases.