Atomic Force Microscopy and Angular-Dependent X-ray Photoelectron Spectroscopy Studies of Anchored Quaternary Ammonium Salt Biocides on Quartz Surfaces.

A siloxane surface-anchored quaternary ammonium salt (AQAS: BIOSAFE HM4100 in this study) has been chemisorbed onto a quartz substrate. The aim of this study is to elucidate, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), the structure of the chemisorbed AQAS layers. The AQAS biocide includes a C18 alkyl chain previously invoked in lysis potency. The AQAS coverage appears in zones on the surface, which include a first layer (2.6 ± 0.1 nm) and multilayering that were explored using AFM. The XPS data exhibited two N 1s signals at about 402 and 399 eV, with only the former exhibiting angular dependence. This signal at 402 eV was assigned to the first anchored layer with perpendicular orientation determined by the AQAS anchoring to the surface. In preliminary AFM studies of bacteria on these AQAS surfaces, perturbations on the Staphylococcus aureus cells and the degradation of Escherichia coli cells suggest lysis potency.

A Sustained Release Anchored Biocide System Utilizing the Honeycomb Cellular Structure of Expanded Perlite.

The development of a sustained-release biocide system, involving an anchored quaternary ammonium salt (AQAS) embedded in expanded perlite (EP) substrate, is reported. Scanning electron microscopy (SEM) images reveal the well-defined honeycomb cells that are a feature of EP. These honeycomb cells exhibit a variety of polygon shapes, which are filled with the AQAS molecules as evidenced by SEM data. The aqueous leaching of the AQAS from the EP honeycomb cells is monitored by the Fourier transform infrared CH stretching absorbance maxima at 2920 and 2850 cm-1. Solid-state NMR data indicate the formation of three dominant oligomeric forms of the AQAS biocide molecules formed within the EP network by condensation reactions at curing temperatures (160 °C). The various oligomeric species involve different numbers of SiO chains bonded to a central Si atom within the AQAS anchoring groups. Assays confirm the potency of the AQAS oligomers against Staphylococcus aureus and Escherichia coli bacteria.

Molecular Weight and Charge Density Effects of Guanidinylated Biodegradable Polycarbonates on Antimicrobial Activity and Selectivity.

Six guanidine functionalized aliphatic biodegradable polycarbonates with varying molecular weights and charge densities were synthesized via postsynthesis modification of alkyne containing polycarbonates using Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry. The concept of passive diluting group was to modify the cationic charge density of the polycarbonate without changing its hydrophilicity. Within the molecular weight range from 8000 to 30000 g mol-1, these guanidine polycarbonates exhibited broad-spectrum biocidal activity with low toxicity to red blood cells (RBCs). The lowest molecular weight homopolymer sample (PG-8k-100) showed the best antimicrobial activity (MIC = 40 µg/mL against Escherichia coli and MIC = 20 µg/mL against Staphylococcus epidermidis) and least RBC toxicity (0.6% hemolysis at MIC). Within the three guanidine charge densities from 20% to 70%, the low to medium dilution samples (PG-8k-7030 and PG-8k-5050) had no obvious loss in antimicrobial activities compared to the nondiluted control sample PG-8k-100. However, upon further dilution, PG-8k-2080 gave the lowest antimicrobial activity.

Electrospun functionalized polyaniline copolymer-based nanofibers with potential application in tissue engineering.

Nanofibrous blends of HCl-doped poly(aniline-co-3-aminobenzoic acid) (3ABAPANI) copolymer and poly(lactic acid) (PLA) were fabricated by electrospinning solutions of the polymers, in varying relative proportions, in dimethyl sulfoxide/tetrahydrofuran mixture. The morphology, mechanical and electrical properties of the nanofibers were characterized and an assessment of their bioactivity performed. To assess cell morphology and biocompatibility, pure PLA and 3ABAPANI-PLA nanofibrous mats were deposited in the form of three-dimensional networks with a high degree of connectivity, on glass substrates, and their ability to promote proliferation of COS-1 fibroblast cells was determined. The nanofibrous electrospun 3ABAPANI-PLA blends gave enhanced cell growth, potent antimicrobial capability against Staphylococcus aureus and electrical conductivity. This new class of nanofibrous blends can potentially be employed as tissue engineering scaffolds, and in particular have showed promise as the basis of a new generation of functional wound dressings that may eliminate deficiencies of currently available antimicrobial dressings.

Electrochemical detection of DNA hybridization amplified by nanoparticles.

Detection of specific oligonucleotide (ODN) fragments has become an important field in many areas of biomedicine. We describe a novel ODN sensor based on electropolymerization of a conducting polymer (polypyrrole) in the presence of a sample containing ODN(s). The resulting trapped ODN(s) are then probed by addition of complimentary sequence ODN. By incorporating CdS nanoparticles with the probe, a significant improvement in sensor sensitivity was observed. Impedance spectroscopy suggested that optimal detection of hybridization occurred at frequencies>or=3000 Hz (for a 0.07 cm2 85 nm thick film). At these frequencies, the impedance signal was almost linear with the logarithm of ODN concentration in the range 3.7-370 nM with a detection limit of approximately 1 nM ODN (for the sensor fabricated). Importantly, the sensor could be regenerated by removing hybridized ODN with NaOH suggesting possibility of the sensor re-use.

Label-free electrochemical DNA sensor based on functionalised conducting copolymer.

A simple and label-free electrochemical sensor for recognition of the DNA hybridization event was prepared based on a new functionalised conducting copolymer, poly[pyrrole-co-4-(3-pyrrolyl) butanoic acid]. This precursor copolymer can be easily electrodeposited on the electrode surface and shows high electroactivity in an aqueous medium. An amino-substituted oligonucleotide (ODN) probe was covalently grafted onto the surface of the copolymer in a one step procedure and tested on hybridization with complementary ODN segments. The cyclic voltammogram of ODN probe-modified copolymer showed very little change when incubated in presence of non-complementary ODN, while a significant, and reproducible, modification of the voltammogram was observed after addition of complementary ODN. The AC impedance spectrum showed an increased charge transfer resistance (Rct) and double layer capacitance of the sensor film after hybridisation. Sensors with thinner films showed higher sensitivity than thicker films, suggesting that hybridisation at or near the surface of the film produces a larger change in electrical properties than that within the body of the film.

Vibrational Spectra and Molecular Association of Titanium Tetraisopropoxide.

The Fourier transform-infrared (FT-IR) and polarized FT-Raman spectra of titanium tetraisopropoxide (tetraisopropoxytitanium, TPT), in pure and diluted forms, and of 2-propanol have been investigated in conjunction with previous assignments for related compounds to obtain a comprehensive assignment of the vibrational spectra. Evidence was obtained for the presence of both monomeric and associated species of TPT. The latter are formed by coordination expansion through bridging isopropoxy ligands. For both monomeric and associated TPT species, vibrational modes of isopropoxy ligands with nu(C-O) mode character were coupled to nu(s)(Ti-O) and nu(as)(Ti-O) modes (interligand coupling). The symmetrically coupled ligand modes gave rise to intense, strongly polarized bands in the Raman spectrum. The antisymmetrically coupled ligand modes gave rise to strong bands in the IR spectrum at lower wavenumbers than the corresponding Raman bands. Molecular association of TPT produced negligible shifts in the ligand modes coupled to the nu(s)(Ti-O) mode in the Raman spectrum. In contrast, the degeneracy of the strong ligand modes coupled to the nu(as)(Ti-O) mode was lifted upon molecular association, yielding band shifts and splittings in the IR spectrum of neat TPT.

Electrospray Mass Spectrometry of Thiophenolate-Capped Clusters of CdS, CdSe, and ZnS and of Cadmium and Zinc Thiophenolate Complexes: Observation of Fragmentation and Metal, Chalcogenide, and Ligand Exchange Processes.

Electrospray mass spectrometry provides a rapid, convenient technique for characterizing and studying the chemistry of anionic metal sulfide thiolate clusters. Negative-ion electrospray mass spectra have been recorded for the thiophenolate-capped clusters [Me(4)N](4)[E(4)Cd(10)(SPh)(16)] (E = S, Se), [Me(4)N](4)[S(4)Zn(10)(SPh)(16)], and [Me(4)N](2)[S(4)Cd(17)(SPh)(28)] and of the metal thiophenolate complexes [Me(4)N](2)[M(SPh)(4)], [Me(4)N](2)[M(4)(SPh)(10)] (M = Cd, Zn), and [Et(4)N](2)[Cd(4)X(4)(SPh)(6)] (X= Cl, Br, I). The exchanges of M, E, and X which occur in various mixtures of these clusters and complexes and the fragmentation processes have been investigated. In the clusters the M-E bonds involving the sulfide or selenide core remain intact during the observed fragmentation at low cone voltages. At high cone voltages, monoions are ultimately formed by loss of charged species and neutral M(SPh)(2), resulting in almost complete removal of the SPh(-) ligands from the cluster core. Fragmentation of the ME core unit itself occurs only at very high voltages. The exchange of X in [Et(4)N](2)[Cd(4)X(4)(SPh)(6)] (X = Br, I) gives peaks due to the ions [Cd(4)I(n)()Br(m)()(SPh)(10)(-)(()(n)()(+)(m)()())](2)(-) (n + m = 0-4) and fragment ions with mixed ligands. The nature of the detected species suggests that the halides only exist as terminal ligands. The exchange of M in [Me(4)N](2)[M(4)(SPh)(10)] and [Me(4)N](4)[S(4)M(10)(SPh)(16)] results in the mixed-metal complexes [Cd(4)(-)(n)()Zn(n)()(SPh)(10)](2)(-) (n = 0-4) and the mixed-metal clusters [S(4)Cd(10)(-)(n)()Zn(n)()(SPh)(16)](4)(-) (n = 0-10). The exchange follows random statistics in [M(4)(SPh)(10)](2)(-) but is biased toward equilibrium association of the same metal in [S(4)M(10)(SPh)(16)](4)(-). The rates of exchange within the different structural elements of [S(4)M(10)(SPh)(16)](4)(-) and [S(4)M(17)(SPh)(28)](2)(-) decrease for the atoms located toward the center of the clusters.