Structural, photolysis and biological studies of the bis(μ2-chloro)-tris(triphenylphosphine)-di-copper(I) and chloro-tris(triphenylphosphine)-copper(I) complexes. Study of copper(I)-copper(I) interactions

Direct reaction of copper(I) chloride with triphenylphosphine (tpp) in molar ratio 2:3 and 1:3, results in the formation of the [(tpp)Cu(μ₂-Cl)₂Cu(tpp)₂] (1) and {[CuCl(tpp)₃]·(CH₃CN)} (2) complexes. The complexes have been characterized by melting point, FT-IR, UV-Vis spectroscopic data and X-ray crystallography. Complex 1 is di-nuclear. Two μ₂-Cl atoms bridge two copper(I) ions with tetrahedral and trigonal geometry respectively. The short copper-copper bond distance of 2.9039(6) ? in case of 1 indicates d¹⁰-d¹⁰ interaction between metal centers. Thus, our studies were extended here in the determination of the quasi-aromaticity, which results in strong Cu-Cu interactions, using the computational method of nucleus-independent chemical shifts (NICS). The NICS calculated at the inner region of the Cu₂Cl₂P₃ core in complex 1 is shielded up to −6.05 ppm. Complex 2 is mono-nuclear where three phosphorus and one chloride atoms form a tetrahedron around the copper(I) ion. Photolysis of both complexes 1 and 2, results in the formation of triphenylphosphine oxide.The complexes 1 and 2, were tested for their in vitro cytotoxic activity against leiomyosarcoma cells (LMS) and human breast adenocarcinoma cells (MCF-7). The type of LMS cell death caused by the complexes was also evaluated by use of a flow cytometry assay. The results show that at concentration of 5 μΜ of complexes 1 and 2, 34.1% (1) and 19.6 (2)% of LMS cells undergo programmed cell death (apoptosis), while at 10 μΜ, 80.4% (1) and 65.2% (2) of LMS cells undergo apoptosis. The light sensitivity of the complex is discussed in relation with the biological activity.     

Femtosecond Laser Axotomy in Caenorhabditis elegans and Collateral Damage Assessment Using a Combination of Linear and Nonlinear Imaging Techniques

In this work highly localized femtosecond laser ablation is used to dissect single axons within a living Caenorhabditis elegans (C. elegans). We present a multimodal imaging methodology for the assessment of the collateral damage induced by the laser. This relies on the observation of the tissues surrounding the targeted region using a combination of different high resolution microscopy modalities. We present the use of Second Harmonic Generation (SHG) and Polarization Sensitive SHG (PSHG) to determine damage in the neighbor muscle cells. All the above is done using a single instrument: multimodal microscopy setup that allows simultaneous imaging in the linear and non-linear regimes and femtosecond-laser ablation.     

A decision tree--based method for the differential diagnosis of Aortic Stenosis from Mitral Regurgitation using heart sounds

Background  

New technologies like echocardiography, color Doppler, CT, and MRI provide more direct and accurate evidence of heart disease than heart auscultation. However, these modalities are costly, large in size and operationally complex and therefore are not suitable for use in rural areas, in homecare and generally in primary healthcare set-ups. Furthermore the majority of internal medicine and cardiology training programs underestimate the value of cardiac auscultation and junior clinicians are not adequately trained in this field. Therefore efficient decision support systems would be very useful for supporting clinicians to make better heart sound diagnosis. In this study a rule-based method, based on decision trees, has been developed for differential diagnosis between "clear" Aortic Stenosis (AS) and "clear" Mitral Regurgitation (MR) using heart sounds.     

One round of SELEX for the generation of DNA aptamers directed against KLK6

Kallikrein-related peptidase 6 (KLK6) is an active serine protease that has been implicated in common pathologies, including neurodegenerative disorders such as Parkinson and Alzheimer disease and certain types of cancer. Antibodies, either polyclonal or monoclonal, that exhibit specificity for distinct members of the extended kallikrein family, including KLK6, were developed. With the exception of KLK3/PSA, the identification and generation of aptamers, as potential new tools with improved characteristics demanded for therapeutic and diagnostic applications, has not been explored for KLKs. Here, we report for the first time the identification of novel DNA aptamers against KLK6 that were isolated using a modified systemic evolution of ligands by exponential enrichment technique. The identified aptamers were characterized using fluorescence spectroscopy, competition ELISA, and quartz crystal microbalance, and two aptamers (008 and 022) were found to exhibit high affinity (K(d) in the low nanomolar range) for KLK6. Aptamers were tested for their ability to bind to serum albumin, to demonstrate their specificity for their target, and the possible involvement of such proteins in the transport of aptamers into the bloodstream. The developed aptamers are expected to assist the development of novel diagnostic, biosensing, and therapeutic strategies.     

Synthesis and characterization of new water stable antimony(III) complex with pyrimidine-2-thione and in vitro biological study

A novel water stable, antimony(III) complex with the heterocyclic thioamide; 2-mercapto-pyrimidine (pmtH), of formula [Sb(pmt)₃] · 0.5(CH₃OH), has been synthesized and characterized by elemental analysis, ¹H, ¹³C NMR and FT-IR spectroscopic techniques. Crystal structure of the molecule has been determined by X-ray diffraction at ambient conditions. The compound [C₁₂H₉N₆S₃Sb · 0.5(CH₃OH)] is monoclinic, space group P2₁/c, a = 7.0646(7), b = 16.3767(14), c = 14.7265(13) Å, β = 92.016(7)°, Z = 4. In complex, three sulfur and three nitrogen atoms from thione ligands form a distorted pendagonal pyramidal geometry around antimony(III). The toxicity of the compound against tumor pleiomorphic cells, which has been isolated from a leiomyosarcoma tumor in the Wistar rat (chemical carcinogenesis using BaP) was studied in vitro. The results show that the compound did not destroy or prevent multiplication in vitro in leiomyosarcoma cells in low doses. The influence of the compound in the platelet aggregation, which correlates with the above tumor cells enhanced metastatic potential, has also been studied. The anti-metastatic capability study shows that the compound inhibited cancer cell induced aggregation up to the value of 10% in all mM concentrations tested.     

On using network RAM as a non‐volatile buffer

File systems and databases usually make several synchronous disk write accesses in order to make sure that the disk always has a consistent view of their data, so that it can be recovered in the case of a system crash. Since synchronous disk operations are slow, some systems choose to employ asynchronous disk write operations that improve performance at the cost of low reliability: in case of a system crash all data that have not yet been written to disk are lost. In this paper we describe a softwarebased NonVolatile RAM system that achieves the high performance of asynchronous write operations without sacrificing the reliability of synchronous write operations. Our system takes a set of volatile main memories residing in independent workstations and transforms it into a nonvolatile memory buffer – much like RAIDS do with magnetic disks. It then uses this nonvolatile buffer as an intermediate storage space in order to acknowledge synchronous write operations before actually writing the data to magnetic disk, but after writing the data to (intermediate) stable storage. We demonstrate the performance advantages of our system using both simulation and experimental evaluation.     

Analysis and interpretation of dynamic FDG PET oncological studies using data reduction techniques

Background  

Dynamic positron emission tomography studies produce a large amount of image data, from which clinically useful parametric information can be extracted using tracer kinetic methods. Data reduction methods can facilitate the initial interpretation and visual analysis of these large image sequences and at the same time can preserve important information and allow for basic feature characterization.