Surface-enhanced vibrational investigation of adsorbed analgesics

Adsorption properties of acetylsalicylic acid (AA), ibuprofen and acetaminophen deposited from volatile solvents with varying protic/aprotic properties on vacuum-evaporated silver films were characterized using surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS). SERS preferentially enhances monolayer Raman shifts, while SEIRA can enhance the infrared absorbance of the monolayer and multilayers. To our best knowledge, this is the first reported study of these molecules using a combination of SERS/SEIRA. SERS revealed that AA and ibuprofen adsorbed ionically in monolayers, independent of the deposition solvents used in the process. SEIRA experiments showed that AA multilayers condensed molecularly using a deposition solvent with polar bonds. However, when an alkane deposition solvent with non-polar bonds such as n-heptane was used, AA adsorbed as acetylsalicylate ions in the first few multilayers, while ibuprofen always adsorbed as the free acid in the multilayer. These ionization trends depend upon the affinity of AA and ibuprofen for the underlying silver film. TPD experiments on silver powders further demonstrated that ibuprofen affinity for silver was less than AA. Furthermore, SEIRA indicated that acetaminophen adsorbed as multilayers of metastable polymorphs using protic or polar aprotic deposition solvents. Protic deposition solvents gave higher quality SERS spectra of an acetaminophen monolayer in comparison to polar aprotic deposition solvents. Such studies could find significant applications in biochemical and nanotechnology processes such as drug delivery, catalysis, and tissue engineering and will contribute to the understanding of the impact and fate of analgesics released into the environment.     

Efficient protocol for quantum Monte Carlo calculations of hydrogen abstraction barriers: Application to methanol

Accurate calculation of hydrogen abstraction reaction barriers is a challenging problem, often requiring high level quantum chemistry methods that scale poorly with system size. Quantum Monte Carlo (QMC) methods provide an alternative approach that exhibit much better scaling, but these methods are still computationally expensive. We describe approaches that can significantly reduce the cost of QMC calculations of barrier heights, using the hydrogen abstraction of methanol by a hydrogen atom as an illustrative example. By analysing the combined influence of trial wavefunctions and pseudopotential quadrature settings on the barrier heights, variance, and time‐step errors, we devise a simple protocol that minimizes the cost of the QMC calculations while retaining accuracy comparable to large‐basis coupled cluster theory. We demonstrate that this protocol is transferable to other hydrogen abstraction reactions.     

Comparison of new and existing algorithms for the analysis of 2D radioxenon beta gamma spectra

The aim of this paper is to compare radioxenon beta–gamma analysis algorithms using simulated spectra with experimentally measured background, where the ground truth of the signal is known. We believe that this is among the largest efforts to date in terms of the number of synthetic spectra generated and number of algorithms compared using identical spectra. We generate an estimate for the minimum detectable counts for each isotope using each algorithm. The paper also points out a conceptual model to put the various algorithms into a continuum. Our results show that existing algorithms can be improved and some newer algorithms can be better than the ones currently used.

     

The S.M.A.R.T. (small mass,affordable, rapid,transfer-less) digestion method for heavy metal determinations

The S.M.A.R.T. (small mass, affordable, rapid, transfer-less) digestion method was developed to determine heavy metal concentrations in small sample masses. The S.M.A.R.T. digestion method is a hot water bath digestion where sample digestion and dilution are performed in the original sample tube. This method is faster than the typical methods used and reduces potential sources of error. Masses as small as 0.01 g have been digested and analysed using this method. The preparation and digestion time is reduced from 10 h to less than 4 h. Acid volumes are reduced from millilitres to microlitres and the only disposable supplies needed are sample tubes and pipette tips. Method accuracy was determined by digesting seven replicates of two standard reference materials using the S.M.A.R.T. method and analysing samples by inductively coupled plasma mass spectrometry. The S.M.A.R.T. digestion method was found to provide excellent recoveries for Al (76 ± 2.7%), Mn (99 ± 11%), Co (92 ± 17%), Ni (93 ± 28%), Cu (109 ± 33%), Zn (97 ± 7.1%), As (108 ± 20%), Sr (90 ± 12%), Mo (84 ± 23%), Ag (91 ± 1.8%), Cd (95 ± 6.2%), Sn (139 ± 52%) and Pb (95 ± 22%). This study has successfully developed an efficient and reproducible digestion method for heavy metal determination in limited biomass samples.     

Determination of Hg and Pb in compact fluorescent lamp by slurry sampling inductively coupled plasma optical emission spectrometry

Mercury and lead were determined in an extraction solution applied to compact fluorescent lamps by axial view inductively coupled plasma optical emission spectrometry (ICP OES). The solution contained 50% v/v HNO₃ and 10% v/v H₂O₂. The compact fluorescent lamps were treated by removing the socket and breaking the rest of the lamp inside the solution, followed by placing the mixture in an ultrasonic bath for 1 h. The mixture was filtrated in a coarse paper filter and the resulting extraction slurry was analyzed. The determination of Pb in the slurry required calibration by the analyte addition technique, while for Hg, external calibration was adequate. The quantification limits (10 s, n = 7), for Hg (194.164 nm) and Pb (220.353 nm) were, respectively, 10 and 30 µg per lamp. Analysis of spiked samples demonstrated reasonable accuracy of the method, with recoveries in the range from 99 to 120% for Hg and from 91 to 107% for Pb. Fifteen analyzed samples showed Hg masses per lamp in the range from 1.6 to 27 mg, and six samples were above the limit allowed by the European Community that is 5 mg per compact lamp. The values for Pb were between 0.07 and 0.75 mg per lamp. By filtrating the slurry in a membrane filter, and analyzing the resulting solution, it was found that all Hg was extracted to the liquid phase of the slurry, while a fraction of about 40% m/v of Pb is retained in the solid particles. The lamp cover glass, after extraction of the phosphor layer, was also analyzed for Hg and Pb. The concentration of Hg in the glass is quite low; however, the Pb content is high.     

VEGFR-2 targeted cellular delivery of doxorubicin by gold nanoparticles for potential antiangiogenic therapy

We report a novel gold nanobioconjugate system that achieves targeted delivery of the small molecule drug doxorubicin to endothelial cells using anti-VEGFR-2 antibody conjugated gold nanoparticles (GNPs). The reported nanobioconjugate system combines the inherent ability of GNPs to undergo high levels of derivatization with the precision of antibody recognition of a cell surface antigen. Transmission electron microscopy (TEM) and surface-enhanced Raman spectroscopy (SERS) confirmed intracellular presence of the GNPs. Using a VEGFR-2 expressing cell line and a cell line that is negative for the receptor, in combination with competition assay we established the cell specific targeted delivery of the nanobioconjugate. The nanobioconjugate system described here may have potential drug delivery applications for antiangiogenic cancer therapy.     

Thermal behavior and structural properites of plant-derived eugenyl acetate

Eugenol is an allyl chain-substituted guaiacol in the biosynthesized phenylpropanoid compound class derived from Syzygium aromaticum L. and widely used in folk medicine. Nonetheless, its pharmacological use is limited by some problems, such as instability when exposed to light and high temperature. In order to enhance stability, the eugenol molecule was structurally modified, resulting in eugenyl acetate. The eugenyl acetate’s thermal behavior and crystal structure was then characterized by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) and compared to a commercial sample.