Evaluation of the potential of Raman microspectroscopy for prediction of chemotherapeutic response to cisplatin in lung adenocarcinoma

The study of the interaction of anticancer drugs with mammalian cells in vitro is important to elucidate the mechanisms of action of the drug on its biological targets. In this context, Raman spectroscopy is a potential candidate for high throughput, non-invasive analysis. To explore this potential, the interaction of cis-diamminedichloroplatinum(II) (cisplatin) with a human lung adenocarcinoma cell line (A549) was investigated using Raman microspectroscopy. The results were correlated with parallel measurements from the MTT cytotoxicity assay, which yielded an IC(50) value of 1.2 ± 0.2 μM. To further confirm the spectral results, Raman spectra were also acquired from DNA extracted from A549 cells exposed to cisplatin and from unexposed controls. Partial least squares (PLS) multivariate regression and PLS Jackknifing were employed to highlight spectral regions which varied in a statistically significant manner with exposure to cisplatin and with the resultant changes in cellular physiology measured by the MTT assay. The results demonstrate the potential of the cellular Raman spectrum to non-invasively elucidate spectral changes that have their origin either in the biochemical interaction of external agents with the cell or its physiological response, allowing the prediction of the cellular response and the identification of the origin of the chemotherapeutic response at a molecular level in the cell.     

Some Results on Dynamics of Special Double-Loop ΣΔ-Modulators

The dynamic behaviour of a specific two-dimensional state space model with discontinuity is studied. This model arises from the study of double-loop -modulators with constant input. Using mathematical tools we explain certain simulation results, and some properties are derived. Simulations based on time-varying input are also provided.     

Development of an integrated optic oxygen sensor using a novel, generic platform

This paper describes the development of a generic platform for enhanced, integrated optic sensors based on fluorescence detection. The platform employs a novel optical configuration in order to achieve enhanced performance and has inherent multianalyte detection capability. The sensor element comprises a multimode ridge waveguide that has been patterned with an analyte-sensitive fluorescent spot, which is excited directly using a LED. The platform was applied to the detection of gaseous oxygen as a proof of principle. The sol-gel-derived sensor spots were doped with an oxygen-sensitive fluorescent dichlororuthenium dye complex and intensity-based calibration data were generated from the oxygen-dependent waveguide output. The sensor achieved a LOD of 0.62% and a resolution of less than 0.96% gaseous oxygen, which compares favourably with a similar, recently reported system. This device highlights the combination of inexpensive rapid prototyping techniques and a dedicated sensor enhancement strategy that together facilitate the production of an effective prototype sensor platform.     

Sliding in a piecewise-smooth dynamical system with a hold-on effect

In this paper, we study a piecewise-smooth dynamical system of a Filippov type that has a specific discontinuity in the form of a hold-on term. The system resembles a driven dry-friction oscillator with the difference that the magnitude of the friction depends on the value of a local maximum of the oscillator displacement. Due to the hold-on term, the definition of the sliding region is not trivial. Along with a sliding region that is found analytically and is valid for any orbits, there exists a sliding region that we name ‘virtual’ because it is specific for each particular orbit. The existence of the virtual sliding region is explained by the specific discontinuity — the hold-on term — and the behavior associated with the sliding region and its boundaries can be considered as a new type of sliding-associated behavior.     

Expanded scope of heterocyclic biaryl synthesis via a palladium-catalysed thermal decarboxylative cross-coupling reaction

The palladium-catalysed decarboxylative cross-coupling of heterocyclic aromatic carboxylates and aryl halides is described. The cross-coupling proceeds under relatively mild conditions using catalytic Pd(0) and tetrabutylammonium bromide (TBAB). Utilizing a mixed solvent system consisting of N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP), the cross-coupling system operated at temperatures ranging from 80 to 140 °C.     

On the Chaotic Behavior of a Third-Order Log-Domain Filter

Operation of log-domain filters revolves around the large-signal forward-active mode exponential current-voltage relationship of the bipolar junction transistor, which is used to map the input currents to the logarithmic domain, where the analog processing takes place, and to convert the filtered voltage waveforms back to the linear domain. Sometimes, the inherent internal nonlinearity of such circuits is the cause of unwanted externally-nonlinear effects. In this paper a differential third-order log-domain Chebyshev low-pass filter is designed by applying the method of operational simulation of doubly-terminated LC ladders. When the six grounded shunt capacitors of this filter are properly replaced with three half-sized floating capacitors, as is common practice in internally-linear fully-differential capacitively-loaded circuits, under particular conditions the resulting system exhibits limit-cycle oscillations, period-doubling bifurcations and chaotic behavior for zero-input. The presence of chaos is confirmed by extracting the spectrum of Lyapunov exponents of the system from the time series of the output voltage.     

Development of a fluorescence lifetime-based sol-gel humidity sensor

A sol-gel-based optical sensor for the measurement of relative humidity has been developed. It is based on the changes in fluorescence intensity and/or lifetime of the ruthenium complex, ruthenium(II)diphenylphenanthroline-dipyridophenazinehexafluorophosphate. Sensitivity to relative humidity has been demonstrated over the range 0-100% relative humidity. This sensor has been developed for application in the field of indoor air-quality monitoring and displays a limit of detection of 0.35% relative humidity and a resolution of 1.13% over the concentration range of interest (0-50% relative humidity). The effects of varying process parameters on the sensor performance were studied along with the effects of cross-sensitivity to molecular oxygen.     

Palladium(II) and platinum(II) complexes with tridentate iminophosphine ligands; synthesis and structural studies

The previously synthesised Schiff-base ligands 2-(2-Ph(2)PC(6)H(4)N[double bond, length as m-dash]CH)-R'-C(6)H(3)OH (R'= 3-OCH(3), HL(1); 5-OCH(3), HL(2); 5-Br, HL(3); 5-Cl, HL(4)) were prepared by a faster, more efficient route involving a microwave assisted co-condensation of 2-(diphenylphosphino)aniline with the appropriate substituted salicylaldehyde. HL(1-4) react directly with M(II)Cl(2)(M = Pd, Pt) or Pt(II)I(2)(cod) affording neutral square-planar complexes of general formula [M(II)Cl(eta(3)-L(1-4))](M = Pd, Pt, 1-8) and [Pt(II)I(eta(3)-L(1-4))](M = Pd, Pt, 9-12). Reaction of complexes 1-4 with the triarylphosphines PR(3)(R = Ph, p-tolyl) gave the novel ionic complexes [Pd(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(13-20). Substituted platinum complexes of the type [Pt(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(R = P(CH(2)CH(2)CN)(3)21-24) and [Pt(II)(P(p-tolyl)(3))(eta(3)-L(3,4))]ClO(4)( 25 and 26 ) were synthesised from the appropriate [Pt(II)Cl(eta(3)-L(1-4))] complex (5-8) and PR(3). The complexes are characterised by microanalytical and spectroscopic techniques. The crystal structures of 3, 6, 10, 15, 20 and 26 were determined and revealed the metal to be in a square-planar four-coordinate environment containing a planar tridentate ligand with an O,N,P donor set together with one further atom which is trans to the central nitrogen atom.     

Strip-Loaded Sol-Gel Waveguides: Design and Fabrication

Sol-gel is one of the most attractive techniques for production of silica-on-silicon integrated optical devices. In fact, it combines low cost with flexibility and ease of doping; thus, nonlinear and active compounds can be effectively included in the silica matrix. Here, the feasibility of applying the sol-gel technique to the realization of an erbium-doped optical amplifier is reported on, operating in the third telecommunication window. In particular, the development of an optimum strategy for the design and fabrication of a guiding structure in the strip-loaded configuration is described. Design optimization results, as well as fabrication results and measured characteristics, are described and discussed.     

Catalyst and substituent effects on the rhodium(II)-catalysed intramolecular Buchner reaction

Intramolecular rhodium(II)-catalysed aromatic addition (Buchner) reactions of a range of α- and β-substituted α-diazoketones are reported. Both steric and electronic effects are evident for the aromatic additions investigated. In general, highly efficient aromatic addition is achieved through use of rhodium carboxylates bearing electronegative ligands, such as rhodium trifluoroacetate, while aromatic addition employing rhodium catalysts with more electron-donating ligands, such as rhodium caprolactam, is less efficient. Excellent levels of diastereoselectivity are possible for this process in the presence of rhodium acetate and rhodium caprolactam, however, a reduction in diastereocontrol is generally associated with use of the more reactive, electronegative catalysts. Interestingly, these catalyst effects can be overcome through the steric effects of the substituents on the α-diazoketone substrates, with the presence of sterically bulky substituents at the 2- or 3-position rendering the aromatic addition essentially catalyst independent in terms of efficiency and diastereocontrol.