Synthesis and Properties of Complexes of Lead(II), Cadmium(II), and Zinc(II) with N-Phosphonomethylglycine

Summary.  Sparingly water soluble complexes of lead(II), cadmium(II), and zinc(II) with N-phosphonomethylglycine (glyphosate, NPMG) of the general formulae C₃H₆O₅NPPb, C₃H₆O₅NPCdċ2H₂O, and C₃H₆O₅NPZn were synthesized. The complexes were also precipited from a dilute Roundup solution, and their solubility in water was determined. Thermal, diffractometric, and IR spectrophotometric analyses were carried out. It was found that the metal is bonded to glyphosate through the oxygen atoms of the carboxylic and phosphonate groups; metal-nitrogen binding is absent in the above compounds. Studying the complexing behaviour in solution by UV spectrophotometry pointed out that a complex of the composition Pb(II) : NPMG=1:1 with an absorption band at 232 nm is formed. Its stability constant as determined by Job’s method is logK=5.9±0.1. Using potentiometric techniques, the dissociation constant of N-phosphonomethylglycine and the stability constants of its complexes with cadmium (II) and zinc (II) were determined. Received June 30, 1999/Accepted July 21, 1999.     

Phosphaguanidines as scaffolds for multimetallic complexes containing metal-functionalized phosphines

Phospha(III)guanidines, R2PC{NR'}{NHR'}, have been used to synthesize multimetallic compounds containing combinations of aluminum with platinum or copper, in which the main-group metal is N,N'-bound by an amidinate moiety, thereby generating a metal-functionalized phosphine that bonds to the transition metal through phosphorus.     

Parameterization of the approximate valence bond (AVB) method to describe potential energy surface in the reaction catalyzed by HIV‐1 protease

The approximate valence bond (AVB) method was parameterized to obtain the potential energy surface for ongoing classical and further quantum classical molecular dynamics simulations describing the enzymatic reaction of the human immunodeficiency virus type 1 protease (HIV‐1 PR). The parameterized AVB method allows to describe the complete enzymatic reaction, including a proton transfer between a water molecule and an aspartic acid, nucleophilic attack of a hydroxy anion on the substrate peptide bond, conformational changes of an intermediate, two proton transfers between the intermediate and aspartic acids, and cleavage of the intermediate into reaction products. The AVB method was parameterized based on density functional theory (DFT) calculations performed for small molecular systems. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 86–103, 2001     

Synthetic oligosaccharides as tools to demonstrate cross-reactivity between polysaccharide antigens

Escherichia coli O148 is a nonencapsulated enterotoxigenic (ETEC) Gram negative bacterium that can cause diarrhea, hemorrhagic colitis, and hemolytic uremic syndrome in humans. The surface-exposed O-specific polysaccharide (O-SP) of the lipopolysaccharide of this bacterium is considered both a virulence factor and a protective antigen. It is built up of the linear tetrasaccharide repeating unit [3)-α-L-Rhap-(1→2)-α-D-Glcp-(1→3)-α-D-GlcNAcp-(1→3)-α-L-Rhap-(1→] differing from that of the O-SP of Shigella dysenteriae type 1 (SD) only in that the latter contains a D-Galp residue in place of the glucose moiety of the former. The close similarity of the O-SPs of these bacteria indicated a possible cross-reactivity. To answer this question we synthesized several oligosaccharide fragments of E. coli O148 O-SP, up to a dodecasaccharide, as well as their bovine serum albumin or recombinant diphtheria toxin conjugates. Immunization of mice with these conjugates induced anti-O-SP-specific serum IgG antibody responses. The antisera reacted equally well with the LPSs of both bacteria, indicating cross-reactivity between the SD and E. coli O148 O-SPs that was further supported by Western-blot and dot-blot analyses, as well as by inhibition of binding between the antisera and the O-SPs of both bacteria.     

Binding of β-lactam antibiotics to a bioinspired dizinc complex reminiscent of the active site of metallo-β-lactamases

Metallo-β-lactamases (mβls) cause bacterial resistance toward a broad spectrum of β-lactam antibiotics by catalyzing the hydrolytic cleavage of the four-membered β-lactam ring, thus inactivating the drug. Minutiae of the mechanism of these enzymes are still not well understood, and reports about binding studies of the substrates to the enzymes as well as to synthetic model systems are rare. Here we report a new pyrazolate-based bioinspired dizinc complex (1) reminiscent of the active site of binuclear mβls. Since 1 does not mediate hydrolytic degradation of β-lactams, the binding of a series of common β-lactam antibiotics (benzylpenicillin, cephalotin, 6-aminopenicillanic acid, ampicillin) as well as the inhibitor sulbactam and the simplest β-lactam, 2-azetidinone, to the dizinc core of 1 could now be studied in detail by NMR and IR spectroscopy as well as mass spectrometry. X-ray crystallographic information was obtained for 1 and its complexes with 2-azetidinone (2) and sulbactam (3); the latter represents the first structurally characterized dizinc complex with a bound β-lactam drug. While 2-azetidinone was found deprotonated and bridging in the clamp of the two zinc ions in 2, in 3 and all other cases the substrates preferentially bind via their carboxylate group within the bimetallic pocket. The relevance of this binding mode for mβls and consequences for the design of functional model systems are discussed.     

Predictive model for ice formation on superhydrophobic surfaces

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies.     

Soft-templating synthesis and adsorption properties of mesoporous carbons with embedded silver nanoparticles

Mesoporous carbons containing silver nanoparticles have been successfully synthesized under acidic conditions by employing resorcinol and formaldehyde as carbon precursors and triblock copolymer EO₁₀₁PO₅₆EO₁₀₁ (Lutrol F127) as a soft template. Silver nanoparticles of ∼90 nm were added to the synthesis mixture to achieve 10 wt% and 20 wt% of Ag loading in the carbon. Also, tetraethyl orthosilicate (TEOS) was introduced to the system in order to improve adsorption properties of the silver-carbon composites and to reinforce its structure. The resulting carbons with incorporated silver nanoparticles featured high surface areas, large total pore volumes and primary mesopores in the range between ∼6–7 nm.     

Neue Methode zur Kontrolle der Sulfonierung von einigen aromatischen Kohlenwasserstoffen

Zusammenfassung Es wurde eine schnelle und genaue volumetrische Methode zur Kontrolle des Sulfonierungsverfahrens von Benzol, Toluol und Naphthalin ausgearbeitet.     

Digital model of a vacuum circuit breaker for the analysis of switching waveforms in electrical circuits

The article presents a method of modelling a vaccum circuit breaker in the ATP/EMTPpackage, the results of the verification of the correctness of the developed digitalcircuit breaker model operation and its practical usefulness for analysis of overvoltagesand overcurrents occurring in commutated capacitive electrical circuits and also examplesof digital simulations of overvoltages and overcurrents in selected electricalcircuits.     

Green synthesis and antibacterial effects of aqueous colloidal solutions of silver nanoparticles using clove eugenol

Silver nanoparticles were synthesized using clove extract (CE). Scanning transmission electron microscopy (STEM) revealed the morphology of the metallic Ag nanoparticles obtained via the clove extract synthesis (Ag NPs‐CE), which had a uniform distribution and average sizes varying from 10 nm to 100 nm. Fourier transform infra‐red (FTIR) spectroscopy showed that clove eugenol acts as a capping and reducing agent being adsorbed on the surface of Ag NPs‐CE, enabling their reduction from Ag⁺ and preventing their agglomeration. Formation of the Ag⁰ structure is also confirmed in the FTIR spectrum by the presence in the Ag NPs‐CE sample of the –C=O and –C=C vibrations at wavenumbers 1600 and 2915 cm^‐1, respectively. Antibacterial and antifungal tests using three strains of bacteria and one fungi strain showed that the Ag NPs‐CE performed better compared to pure clove extract (CE) sample.