Synthesis, Characterization, and Biological Activity of n-Tributyltin Derivatives of Pharmaceutically Active Carboxylates

Summary.  Tributyltin(IV) derivatives of six different pharmaceutically active carboxylates were synthesized. The complexes were characterized by different analytical techniques (elemental analysis; infrared, NMR, and mass spectroscopy). ¹¹⁹Sn NMR data were also recorded in six different coordinating and non-coordinating solvents. The antibacterial activities of the compounds were tested using ten different bacteria relative to the reference drugs ampicillin and cephalexin. Received September 20, 2001. Accepted (revised) December 6, 2001     

A resonance Raman,surface-enhanced resonance Raman,IR, and ab initio vibrational spectroscopic study of nickel(II) tetraazaannulene complexes

The IR and resonance Raman spectra of the nickel(II) complexes of dibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TAA) and 5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TMTAA) have been measured and compared with ab initio calculations of the vibrational wavenumbers at the B3-LYP level using the LanL2DZ basis set. An excellent fit is found between the experimental and calculated data, enabling precise vibrational assignments to be made. Surface-enhanced resonance Raman spectra were obtained following adsorption on Ag electrodes, with potentials in the range -0.1 to -1.1 V vs Ag/AgCl. There is evidence for contributions from both the electromagnetic and charge transfer (CT) surface enhancement mechanisms. The data indicate that variations in band intensities with electrode potential can be interpreted in terms of the CT mechanism.     

Organotin(IV) Complexes of 2-[(2′,4′,6′- Trichlorophenylamido)]benzoic Acid: Synthesis,Coordination Chemistry,and Semi-Empirical Study

A new series of organotin(IV) complexes of aniline derivatives, R₂SnL₂ and R₃SnL [where R = Me, n-Bu, n-Oct, and Ph], have been synthesized by the reaction of ligand acid with respective organotin halides in the presence of triethylamine as base or dioctyltin oxide using a Dean–Stark trap for the removal of water under reflux conditions. Experimental details for the preparation and characterization, including elemental analysis, IR, semi-empirical study, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn spectra and EI mass spectral studies) of all reported complexes are provided. The IR data indicate that in both di- and triorganotin(IV) carboxylates, the ligand moiety ?COO acts as a bidentate group in the solid state. Multinuclear NMR data show that triorganotin complexes exhibits a four-coordinated geometry, while diorganotin(IV) complexes show a coordination number greater than four, probably five or six, in solution state.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Polymeric Three-Dimensional Crystal Structure of a Tributyltin(IV) Derivative with Acetylene Dicarboxylic Acid

Abstract

A novel polymeric complex has been synthesized by refluxing disodium acetylene dicarboxylate with tributyltin chloride in dry methanol. The solid-state structure of the complex has been determined by single-crystal X-ray analysis. The tin(IV) metal exhibits distorted trigonal bipyramidal geometry. Each carboxylate group of the ligand acts in a bidentate fashion, linking adjacent metal atoms to produce polymeric chains, which are cross-linked into a three-dimensional network.     

Synthesis,Characterization, and Semi-Empirical Study of Organotin(IV) Complexes with 4-(Hydroxymethyl)piperidine-1-carbodithioic Acid: X-Ray Structure of Chlorodimethyl-(4-hydroxymethyl piperidine-1-carbodithioato-S,S′)tin(IV)

Abstract

Organotin complexes with the general formulae R₂SnL₂, R₂Sn(Cl)L, and R₃SnL have been synthesized where R = CH₃, n-C₄H₆, C₆H₅, C₆H₁₁, and L = 4-(hydroxy methyl)piperidine-1-carbodithioic acid. The newly synthesized complexes have been characterized by elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn), and, for one example, a single crystal x-ray structure. The FT-IR data shows the bidentate nature of the ligand. This coordination behavior is also confirmed by semi-empirical study. In the solid state, diorganotin complexes exhibit the penta/hexacoordinated geometry, whereas the triorganotin(IV) complexes show the five coordinated geometry. ¹¹⁹Sn NMR data reveal that triorganotin(IV) complexes exhibit the four coordinated geometry in solution, whereas the diorganotin(IV) compounds show the higher coordination, probably five or six. X-ray diffraction analysis of complex (2) shows a square pyramidal geometry around the tin atom on the basis of τ value.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Effect of carbon chain length of monocarboxylic acids on cloud point temperature of poly(2-ethyl-2-oxazoline)

The temperature-induced phase transition of poly(2-ethyl-2-oxazoline) (PEtOx) aqueous solution under mixing with a series of small carboxylic acids has been studied by turbidity measurements and laser light scattering. It has been found that cloud point temperature (T _cp) of the PEtOx was changed to varying degrees depending upon the pH, ionic strength, molar ratio of acids to 2-ethyl-2-oxazoline unit, and carbon chain length of small carboxylic acids. Significant change in T _cp was observed in the case of hexanoic acid. At acidic pH, an increase in the molar ratio of hexanoic acid to the 2-ethyl-2-oxazoline unit gradually decreased the phase transition temperature of the polymer as compared to the T _cp of pure PEtOx. At original pH 6 (pH?>?pK _a), T _cp shifts to higher value than that of pure PEtOx for lower molar ratios and decreased later on with increasing the molar ratio. The shift in the T _cp is described based on the differences in the driving force of phase transition, including hydrogen bonding between small carboxylic acids and PEtOx polymer and hydrophobic interaction.     

Biomonitoring of infant exposure to phenolic endocrine disruptors using urine expressed from disposable gel diapers

Infant exposure to endocrine disruptors (EDs) may cause adverse health effects because of their fast growth and development during this life stage. However, collecting urine from infants for exposure assessment using biological monitoring is not an easy task. For this purpose, we evaluated the feasibility of using urine expressed from disposable gel absorbent diapers (GADs) as a matrix for biomonitoring selected phenolic EDs. GADs urine was expressed with the assistance of CaCl₂ and was collected using a device fabricated in our laboratory. The analytes were extracted and concentrated using a liquid-liquid method and their hydroxyl groups were modified by dansyl chloride to enhance their chromatography and detection. Finally, the analytes were measured by high-performance liquid chromatography (HPLC) coupled with electrospray ionization (ESI) tandem mass spectrometry (MS/MS). The target chemicals were bisphenol A, triclosan, 17 α-ethynylestradiol, the natural hormone estrone, and 17 β-estradiol. The ratio of the CaCl₂ to the urine-wetted gel absorbent, variation of the inter-urination volume, and analyte deposition bias in the diaper were assessed. Analyte blank values in the diapers, the sample storage stabilities, and recoveries of the analytes were also evaluated. The results showed that 70–80 % of the urine could be expressed from the diaper with the assistance of CaCl₂ and 70.5–124 % of the spiked analytes can be recovered in the expressed urine. The limits of detections (LODs) were 0.02–0.27 ng/mL, well within the range for detection in human populations. Our pilot data suggest that infants are widely exposed to the selected EDs.     

Protease Inhibitors Purified from the Canola Meal Extracts of Two Genetically Diverse Genotypes Exhibit Antidiabetic and Antihypertension Properties

Valorization of vegetable oil waste residues is gaining importance due to their high protein and polyphenol contents. Protease inhibitors (PIs), proteins from these abundantly available waste residues, have recently gained importance in treating chronic diseases. This research aimed to use canola meal of genetically diverse Brassica napus genotypes, BLN-3347 and Rivette, to identify PIs with diverse functionalities in therapeutic and pharmacological applications. The canola meal PI purification steps involved: native PAGE and trypsin inhibition activity, followed by ammonium sulfate fractionation, anion exchange, gel filtration, and reverse-phase chromatography. The purified PI preparations were characterized using SDS-PAGE, isoelectric focusing (IEF), and N terminal sequencing. SDS-PAGE analysis of PI preparations under native reducing and nonreducing conditions revealed three polymorphic PIs in each genotype. The corresponding IEF of the genotype BLN-3347, exhibited three acidic isoforms with isoelectric points (pI) of 4.6, 4.0, and 3.9, while Rivette possessed three isoforms, exhibiting two basic forms of pI 8.65 and 9.9, and one acidic of pI 6.55. Purified PI preparations from both the genotypes displayed dipeptidyl peptidase-IV (DPP-IV) and angiotensin-converting enzyme (ACE) inhibition activities; the BLN-3347 PI preparation exhibited a strong inhibitory effect with lower IC₅₀ values (DPP-IV 37.42 µg/mL; ACE 129 µg/mL) than that from Rivette (DPP-IV 67.97 µg/mL; ACE 376.2 µg/mL). In addition to potential human therapy, these highly polymorphic PIs, which can inhibit damaging serine proteases secreted by canola plant pathogens, have the potential to be used by canola plant breeders to seek qualitative trait locus (QTLs) linked to genes conferring resistance to canola diseases.