Osteoblast cell response to a CO2 laser modified polymeric material

Lasers are an efficient technology, which can be applied for the surface treatment of polymeric biomaterials to enhance insufficient surface properties. That is, the surface chemistry and topography of biomaterials can be modulated to increase the biofunctionality of that material. By employing CO₂ laser patterning and whole area processing of nylon 6,6 this paper details how the surface properties were significantly modified. Samples, which had undergone whole area processing, followed the current theory in which the advancing contact angle, θ, with water decreased and the polar component, γ^p, increased upon an increase in surface roughness. For the patterned samples it was observed that θ increased and γ^P decreased. This did not follow the current theory and can be explained by a mixed-state wetting regime. By seeding osteoblast cells onto the samples for 24 h and 4 days the laser surface treatment gave rise to modulated cell response. For the laser whole area processing, θ and γ^P correlated with the observed cell count and cover density. Owed to the wetting regime, the patterned samples did not give rise to any correlative trend. As a result, CO₂ laser whole area processing is more likely to allow one to predict biofunctionality prior to cell seeding. Moreover, for all samples, cell differentiation was evidenced. On account of this and the modulation in cell response, it has been shown that laser surface treatment lends itself to changing the biofunctional properties of nylon 6,6.     

Autoxidation of 4-amorphen-11-ol and the biogenesis of nor- and seco-amorphane sesquiterpenes from fabiana imbricata

Photooxidation of 4-amorphen-11-ol (1), recently reported as one of the major sesquiterpene natural products from the medicinal plant Fabiana imbricata, results in three allylic hydroperoxides 6, 9 and 10, which are expected from the “ene-type” reaction of molecular oxygen with the tri-substituted double bond in 1. The tertiary allylic hydroperoxide 6 undergoes carbon-carbon bond cleavage and a second autoxidation reaction to yield the more highly oxygenated seco-amorphane 11 under very mild conditions. In acid, this compound may then undergo either a second carbon-carbon bond cleavage reaction to yield nor-sesquiterpenes 2 and 3 (reported as bona fide natural products from F. imbricata, or cyclize to the sesquiterpene peroxofabianane (5), which is a presumed precursor to the natural product fabianane (4). Some mechanistic investigations concerning the two chemical processes: viz:- carbon-carbon bond cleavage and autoxidation which would account for the formation of natural products 2, 3 and 4 from 1 are reported. Tertiary allylic hydroperoxide 32, which lacks the 11-hydroxyl functional group present in 1 undergoes only C-4/C-5 carbon-carbon bond cleavage under more forcing conditions, suggesting a role for this functional group in assisting the autoxidation reactions of 4-amorphen-11-ol.     

Quantum computing based on vibrational eigenstates: pulse area theorem analysis

In a recent paper [D. Babikov, J. Chem. Phys. 121, 7577 (2004)], quantum optimal control theory was applied to analyze the accuracy of quantum gates in a quantum computer based on molecular vibrational eigenstates. The effects of the anharmonicity parameter of the molecule, the target time of the pulse, and the penalty function on the accuracy of the qubit transformations were investigated. We demonstrate that the effects of all the molecular and laser-pulse parameters can be explained utilizing the analytical pulse area theorem, which originates from the standard two-level model. Moreover, by analyzing the difference between the optimal control theory results and those obtained using the pulse area theorem, it is shown that extremely high quantum gate fidelity can be achieved for a qubit system based on vibrational eigenstates.     

A novel 14C-postlabeling assay using accelerator mass spectrometry for the detection of O6-methyldeoxy-guanosine adducts

Accelerator mass spectrometry (AMS) is currently one of the most sensitive methods available for the trace detection of DNA adducts and is particularly valuable for measuring adducts in humans or animal models. However, the standard approach requires administration of a radiolabeled compound. As an alternative, we have developed a preliminary 14C-postlabeling assay for detection of the highly mutagenic O6-methyldeoxyguanosine (O6-MedG), by AMS. Procedures were developed for derivatising O6-MedG using unlabeled acetic anhydride. Using conventional liquid chromatography/mass spectrometry (LC/MS) analysis, the limit of detection (LOD) for the major product, triacetylated O6-MedG, was 10 fmol. On reaction of O6-MedG with 14C-acetic anhydride, using a specially designed enclosed system, the predominant product was 14C-di-acetyl O6-MedG. This change in reaction profile was due to a modification of the reaction procedure, introduced as a necessary safety precaution. The LOD for 14C-di-acetyl O6-MedG by AMS was determined as 79 amol, approximately 18,000-fold lower than that achievable by liquid scintillation counting (LSC). Although the assay has so far only been carried out with labeled standards, the degree of sensitivity obtained illustrates the potential of this assay for measuring O6-MedG levels in humans.     

Ultraviolet cavity ringdown spectra and the S1(n,pi) ring-inversion potential energy function for 2-cyclohexen-1-one-d0 and Its 2,6,6-d3 isotopomer

The cavity ringdown spectra of 2-cyclohexen-1-one (2CHO) and its 2,6,6-d3 isotopomer (2CHO-d3) have been recorded in the spectral region near their S1(n,pi)<--S0 band origins which are at 26,081.3 and 26,075.3 cm-1, respectively. The data allow several of the quantum states of nu39, the ring inversion, to be determined for both the ground and excited electronic states. These were utilized to calculate the one-dimensional potential energy functions which best fit the data. The barriers to inversion for the S0 and S1(n,pi) states were found to be 1,900 +/- 300 and 3,550 +/- 500 cm-1, respectively. Density functional theory calculations predict values of 2,090 and 2,265 cm-1, respectively.     

Synthesis of 1,3-diamino-7,8,9,10-tetrahydropyrido[3,2-f]-quinazolines. Inhibitors of Candida albicans dihydrofolate reductase as potential antifungal agents

A series of novel 1,3-diamino-7,8,9,10-tetrahydropyrido[3,2-f]quinazolines were synthesized starting from 6-amino-5-cyanoquinoline (4). These compounds inhibited Candida albicans dihydrofolate reductase with K_i values of ≤0.60 aM. One analogue exhibited moderate in vivo efficacy in a C. albicans-infected mouse model.     

Adsorption of organic matter at mineral/water interfaces. 6. Effect of inner-sphere versus outer-sphere adsorption on colloidal stability

The effects of the adsorption modes of several low molecular weight (LMW) organic anions (maleate, oxalate, and citrate) on the colloidal stability of corundum-water suspensions have been examined using electrokinetic and shear yield stress (tau(y)) measurements over a broad range of pH conditions and LMW organic anion concentrations. Consistent with previous studies, increasing concentrations of maleate, oxalate, and citrate progressively shift the electrokinetic isoelectric point and pH of the maximum shear yield stress (tau(y,max)) to more acidic conditions. Due to its predominant electrostatic driving force for adsorption, outer-spherically adsorbed maleate possesses a very limited ability to charge reverse the corundum-water interface or bind to the negatively charged corundum surface. By contrast, inner-spherically adsorbed oxalate and citrate can significantly charge reverse the corundum-water interface, with the extent of charge reversal being related to the relative binding strengths of the oxalate and citrate anions. Adsorbed maleate, oxalate, and citrate generate steric barriers to interparticle approach, leading to substantial reductions in the magnitude of tau(y,max) at low to intermediate concentrations of those LMW anions. At the highest anion concentrations investigated, however, increases in tau(y,max) are observed, and can be attributed to the formation of bridging Al(III)-organic surface precipitates, as suggested by in situ attenuated total reflectance Fourier transform infrared spectroscopic measurements of corundum-oxalate suspensions at high oxalate concentrations. The extent of precipitate formation is greatest for the corundum-oxalate system due to the strong dissolution-enhancing properties of the inner-spherically adsorbed oxalate anion (i.e., its ability to generate enhanced concentrations of dissolved Al(III) which can then participate in precipitate formation). The effects of the LMW organic anion adsorption modes on both the forms of the measured tau(y) versus pH data, and the ability to quantitatively compare tau(y) and zeta potential data measured at different corundum concentrations, are also discussed.     

Direct glycosylation: synthesis of alpha-indoline ribonucleosides

A selective synthesis of α-anomers of indoline nucleosides is described. Ribonucleosides of indoline, dimethylindoline and 5-bromoindoline are readily prepared in good yield by reacting indoline bases directly with the protected sugar, 2,3-O-(1-methylethylidene) 5-O-(triphenylmethyl)-D-ribofuranose in dry ethanol or methylene chloride in presence of molecular sieves at 40-60 °C.     

Determination of Polyvinyl Alcohol Using Gel Filtration Liquid Chromatography

Gel filtration chromatography using a TSKgel G2000 SW column coupled with differential refractive index detection was used to analyse five grades of polyvinyl alcohol. Limits of detection and quantification for the assay were 0.14 mg mL^–1, 0.47 mg mL^–1 respectively. The inter and intra-day co-efficient of variance were both <7%. There was a significant difference (p<0.05, n=5) between the calibration curves across the five grades of PVA due to a refractive index range of 13.0790 –1.3181 (n=3). The assay accuracy was 98.99% ± 8.97% (n=5) and 90.60% ± 7.87% (n=5) of a spiked PVA sample was recovered from a commercial formulation.     

Flash vacuum pyrolysis of 1-propynoylpyrazoles: a new precursor of tricarbon monoxide

Pyrolysis of 3,5-dimethyl-1-propynoylpyrazole (1) at 640°C/0.1 torr gives 2-methyl-1$\text{H}$-pyrazolo[2,3-a]pyridin-5-one (3) with inversion of the propynoyl chain. 1-Ethynylpyrazole and tricarbon monoxide have been identified in pyrolysates formed at 700–1000°C/0.01–0.1 torr from the parent 1-propynoylpyrazole (4).