A new cotton functionalized with iron(III) trimer-like metal framework as an effective strategy for the adsorption of triarylmethane dye: An insight into the dye adsorption processes.

A new Cotton@Fe-BTC composite formed by Fe-BTC (BTC-H3: trimesic acid) metal framework (Fe-BTC MOF loading as high 38 wt %) supported by cellulose fiber is synthesized in aqueous media using a simple and green preparation method, described for the first time in this manuscript. This new strategy relies on the synergetic effect of the pure cellulose and MOFs frameworks resulting in hybrid nanofibers of MOFs@cellulose composite. A complete characterization of the composite material reveals its structural similarity to MIL-100(Fe), a Fe-BTC material. The Cotton@Fe-BTC composite potential use as an eco-friendly and low-cost adsorbent was evaluated for its adsorptive performance for the removal of dye belonging to the triarylmethane dye family (Malachite Green (MQ), Brilliant Green (BG), Pararosaniline (PR), Basic Fuchsine (BF), Crystal Violet (CV), Methyl Green (Met-G), Victoria Blue B (VB), Acid Fuchsin (AF) and Aniline Blue (AB)) in aqueous solution. The fast kinetics and high dye removal efficiencies (>90%) obtained in aqueous solutions. The structure of Cotton@Fe-BTC network, contributed to the remarkable adsorption properties towards a variety of triphenylmethanedye. The interparticle studies showed two main steps in the dye adsorption processes, with the exception of AF and BG. The equilibrium adsorption capacities qe (mg/g) follow the order: AF (3.64)

Metal organic framework composite, nano-Fe3O4@Fe-(benzene-1,3,5-tricarboxylic acid), for solid phase extraction of blood lipid regulators from water.

The magnetic metal-organic framework Fe3O4@(Fe-(benzene-1,3,5-tricarboxylic acid) (MMOF) was prepared, characterized and studied as a magnetic sorbent for the dispersive solid-phase extraction (DSPE) of several widely used blood lipid regulators (i.e., bezafibrate, clofibric acid, clofibrate, gemfibrozil and fenofibrate) from water samples. Characterization of the synthesized Fe3O4@Fe-BTC magnetic nanomaterial was performed by Fourier transform infrared spectroscopy, powder X-ray diffractometry, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. The magnetic nanocomposite was found to be chemically stable and to possess a large surface area (803.62 m2/g) and pore volume (0.59 cm³/g). The concentrations of fibrates in different water samples were determined using HPLC-UV-Vis and confirmed by UPLC-MS/MS. Parameters affecting the extraction efficiency of magnetic-DSPE were studied and optimized. The maxima absorption capacities (Qmax) were determined to be (in mg/g) 197.0 for bezafibrate, 620.3 for clofibric acid, 537.6 for clofibrate, 288.7 gemfibrozil and 223.2 for fenofibrate. Validations of the optimized magnetic DSPE method for analyses at two fibrate concentrations in spiked water samples produced relative recovery values ≤ 70% for clofibrate and within the range of 80-100% for bezafibrate, clofibric acid, gemfibrozil and fenofibrate. LODs ranging from 4 µg/L for fenofibrate to 99 µg/L for gemfibrozil were obtained. The validated methodology produced recovery values ranging from 70 to 112% (relative standard deviations < 7%).

PRAS40 promotes NF-κB transcriptional activity through association with p65.

PRAS40 has been shown to have a crucial role in the repression of mammalian target of rapamycin (mTOR). Nonetheless, PRAS40 appears to have an oncogenic function in cancer cells. Whether PRAS40 mediates signaling independent of mTOR inhibition in cancer cells remains elusive. Here PRAS40 overexpression in lung adenocarcinoma and cutaneous melanoma was significantly correlated to worse prognosis. And we identified an unexpected role for PRAS40 in the regulation of nuclear factor (NF)-κB signaling. P65, a subunit of the NF-κB transcription factor complex, was confirmed to associate with PRAS40 by glutathione S-transferase co-precipitation. Importantly, we found that PRAS40 can enhance NF-κB transcriptional activity in a manner dependent upon PRAS40-P65 association. Furthermore, we found that a small p65-derived peptide can disrupt the PRAS40-P65 association and significantly decrease NF-κB transcriptional activity. These findings may help elucidate the pleiotropic functions of PRAS40 in cells and suggest a novel therapeutic strategy in cancer patients with high expression of PRAS40 and NF-κB.

Adsorption of silver nanoparticles from aqueous solution on copper-based metal organic frameworks (HKUST-1).

Silver nanoparticles (AgNP) are emerging pollutants. The use of novel materials such as Cu-(benzene 1,3,5-tricarboxylate, BTC) Metal-Organic Framework (MOFs), for AgNP adsorption and their removal from aqueous solutions has been studied. The effect of different parameters was followed and isotherm model was suggested. MOFs adsorbed fast and efficiently AgNP in the range C0 < 10 mg L(-1), being Freundlich isotherm (R = 0.993) these data fitted to. Among studied parameters a remarkable effect of chloride on sorption was found, thus their possible interactions were considered. The high adsorption efficiency of AgNP was achieved and it was found to be very fast. The feasibility of adsorption on Cu-(BTC) was proved in spiked waters. The results showed the potential interest of new material as adsorbent for removing AgNP from environment.

Nuclear PRAS40 couples the Akt/mTORC1 signaling axis to the RPL11-HDM2-p53 nucleolar stress response pathway.

The ribosomal protein (RP)-HDM2-p53 pathway has been shown to have key roles in oncogene-induced apoptosis and senescence, but the mechanism regulating this pathway remains elusive. The proline-rich Akt substrate of 40 kDa (PRAS40) has recently been identified as a binding partner and inhibitor of the mechanistic (formerly referred to as mammalian) target of rapamycin complex 1 (mTORC1). Although other inhibitors of mTORC1 are known tumor suppressors, PRAS40 promotes cell survival and tumorigenesis. Here we demonstrate that Akt- and mTORC1-mediated phosphorylation of PRAS40 at T246 and S221, respectively, promotes nuclear-specific association of PRAS40 with ribosomal protein L11 (RPL11). Importantly, silencing of PRAS40 induces upregulation of p53 in a manner dependent on RPL11. This effect is rescued by wild-type PRAS40, but not by the RPL11-binding-null PRAS40T246A mutant. We found that PRAS40 negatively regulates the RPL11-HDM2-p53 nucleolar stress response pathway and suppresses induction of p53-mediated cellular senescence. This work identifies nuclear PRAS40 as a dual-input signaling checkpoint that links cell growth and proliferation to inhibition of cellular senescence. These findings may help to explain the protumorigenic effect of PRAS40 and identify the PRAS40-RPL11 complex as a promising target for p53-restorative anticancer drug discovery.

Polyphasic approach applying artificial neural networks, molecular analysis and postabdomen morphology to West Palaearctic Tachina spp. (Diptera, Tachinidae).

Artificial neural networks (ANN) methodology, molecular analyses and comparative morphology of the male postabdomen were used successfully in parallel for species identification and resolution of some taxonomic problems concerning West Palaearctic species of the genus Tachina Meigen, 1803. Supervised feed-forward ANN with back-propagation of errors was applied on morphometric and qualitative characters to solve known taxonomic discrepancies. Background molecular analyses based on mitochondrial markers CO I, Cyt b, 12S and 16S rDNA and study of male postabdominal structures were published separately. All three approaches resolved taxonomic doubts with identical results in the following five cases: case 1, the four presently recognized subgenera of the genus Tachina were confirmed and the description of a new subgenus was recommended; case 2, the validity of a new boreo-alpine species (sp.n.) was confirmed; case 3, the previously supposed presence of T. casta (Rondani, 1859) in central Europe was not supported; case 4, West Palaearctic T. nupta (Rondani, 1859) was contrasted with East Palaearctic specimens from Japan, which seem to represent a valid species not conspecific with central European specimens; T. nupta needs detailed further study; case 5, T. nigrohirta (Stein, 1924) resurrected recently from synonymy with T. ursina Meigen, 1824 was confirmed as a valid species. This parallel application of three alternative methods has enabled the principle of 'polyphasic taxonomy' to be tested and verified using these separate results. For the first time, the value of using the ANN approach in taxonomy was justified by two non-mathematical methods (molecular and morphological).

Artificial neural networks for classification in metabolomic studies of whole cells using 1H nuclear magnetic resonance.

We report the successful classification, by artificial neural networks (ANNs), of (1)H NMR spectroscopic data recorded on whole-cell culture samples of four different lung carcinoma cell lines, which display different drug resistance patterns. The robustness of the approach was demonstrated by its ability to classify the cell line correctly in 100% of cases, despite the demonstrated presence of operator-induced sources of variation, and irrespective of which spectra are used for training and for validation. The study demonstrates the potential of ANN for lung carcinoma classification in realistic situations.

Plasma pharmacokinetics of oral chlortetracycline in group fed, ruminating, Holstein steers in a feedlot setting.

Chlortetracycline HCl (CTC) has impacted profitable livestock production since 1945. However, pharmacokinetic parameters for CTC in ruminating cattle are unavailable in peer-reviewed literature. A total of 18 steers were randomized to 4.4, 11, or 22 mg/kg/day p.o. CTC treatment groups (n = 6). Chlortetracycline treatment was offered as one-half of the daily dose b.i.d. (160 total doses/group) for 80 days. Blood samples were collected at selected time points throughout an 83-day study and analyzed with a solid phase extraction technique and novel ultrahigh performance liquid chromatography-mass spectroscopy/mass spectroscopy analytical method. Noncompartmental analysis (NCA) determined individual pharmacokinetic parameters by treatment group with coefficient of variation (CV %) estimates. A one-compartment open model with first order absorption and elimination, where absorption rate constant was equal to elimination rate constant, was fitted using nonlinear mixed effects modeling (NLMEM). NLMEM determined the primary pharmacokinetic parameters: volume of distribution (V/F, 40.9 L/kg) and rate constant (k, 0.0478 h(-1)), and the secondary parameters: dose-normalized area under the curve (AUC/D, 0.29 h x microg/L), clearance (Cl/F, 1.8 L/kg/h), elimination half-life (t(1/2), 16.2 h), C(max/Dose) (4.5 ng/mL), and time of C(max) (T(max), 23.3 h) with improved CV estimates over NCA. Dose linearity was confirmed by anova of parameters derived from NCA by treatment group. Further studies are necessary for determining absolute bioavailability and pharmacokinetic-pharmacodynamic relationships of CTC in group fed, ruminating cattle.

Thrips (Thysanoptera) identification using artificial neural networks.

We studied the use of a supervised artificial neural network (ANN) model for semi-automated identification of 18 common European species of Thysanoptera from four genera: Aeolothrips Haliday (Aeolothripidae), Chirothrips Haliday, Dendrothrips Uzel, and Limothrips Haliday (all Thripidae). As input data, we entered 17 continuous morphometric and two qualitative two-state characters measured or determined on different parts of the thrips body (head, pronotum, forewing and ovipositor) and the sex. Our experimental data set included 498 thrips specimens. A relatively simple ANN architecture (multilayer perceptrons with a single hidden layer) enabled a 97% correct simultaneous identification of both males and females of all the 18 species in an independent test. This high reliability of classification is promising for a wider application of ANN in the practice of Thysanoptera identification.

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI TOF MS) study of Huperzine A, a natural anti-Alzheimer's disease product, its derivatization and its detection by highly sensitive laser induced fluorescence (LIF).

Huperzine A, a reversible acetylcholinesterase inhibitor for the treatment of Alzheimer disease (HupA), was studied using an (MALDI TOF MS) instrument in MALDI mode. The formation of a HupA dimmer in a vacuum was observed and several matrices were found that were able to inhibit its formation. The structures of the neutral and protonated form of the HupA molecule were calculated and optimized using a Hyperchem program. Detection limit using MALDI TOF MS in the model sample was 5.3pg. MALDI TOF MS was also applied to the direct detection of the drug in medical preparations and in human serum. The limit of detection in plasma was 14.2pg with a signal-to-noise ratio of 3:1. However, the sensitivity was not as high as it usually is in MALDI. Therefore, a new method for the derivatization of HupA was developed using fluorescent labelling with rhodamine B isothiocyanate (RBITC). A limit of detection using capillary electrophoresis laser induced fluorescence detection (CE-LIF) equal to 4x10(-9)moll(-1) was reached.

[Using of scanning electron microscopy for detection of gunshot residue]. / Pouzití skenovací elektronové mikroskopie pri detekci povýstrelových cástic.

Scanning electron microscope improves the possibility of investigation of surroundings near of gunshot wounds in forensic medicine, it is the next subsequent method for differentiating of area of entrance and exit wound, supplemental method for determination of firing distance, permit of detection (GSR) on the hand of shooter and ensured describing of samples and their stored. Detection of GSR provides many information about composition of bullet and primer. Authors are demonstrating the possibility of detection of GSR on experimental shooting to the krupon (pigs' skin) in different situation (such as in a room and in outside area) and using of different weapon (hand gun CZ No.75 and machine gun No.58).

Simultaneous determination of molybdenum(VI) and tungsten(VI) and its application in elemental analysis of polyoxometalates.

Spectrophotometric determination of molybdenum(VI) and tungsten(VI) with application of Artificial Neural Networks is proposed and it was applied for elemental analysis of solid polyoxometalates. Better results in comparison with previously those achieved by previous published method were demonstrated. MALDI-TOF Mass Spectrometry was tested for possible determination of molecular weight of polyoxometalates utilizing different matrices. Phenomena observed during desorption-ionisation processes are discussed. LDI-TOF MS was found to be suitable for the determination of Mo:W ratio in polyoxometalates as a rapid screening method to follow synthetic procedure.

A preconcentration system using polyamine Metalfix-Chelamine resin for the on-line determination of palladium(II) and platinum(IV) by inductively coupled plasma optical emission spectrometry.

A new matrix separation/preconcentration method is developed for the on-line determination of palladium(II) and platinum(IV) in complex matrices using a sequential ICP-OES instrument. These metals are preconcentrated in a microcolumn packed with Metalfix-Chelamine, a polymeric functionalised resin containing the tetraethylenepentamine group. The hydrodynamic and chemical conditions of the flow system affecting the loading and elution steps are optimised off-line using a mixture of 1.0molL(-1) thiourea and 2.0molL(-1) NaClO(4) in 4.0molL(-1) HCl which proved to be the most effective solution for the simultaneous elution of Pd(II) and Pt(IV). High enrichment factors of nearly 35 are achieved for both metals and the detection limits (LOD) are 22ngL(-1) for platinum and 2.5ngL(-1) for palladium. The accuracy of the method was tested by analysing a used pellet catalyst (certified reference material NIST 2556) and trace metal solutions resulting from the leaching of this material. Despite the fact that this CRM contains zirconium and large amounts of aluminium and lead, a high level of agreement was achieved demonstrating the efficiency of the resin in eliminating interfering elements.

Classification of some heat-treated liver pastes according to container type, using heavy metals content and manufacturer's data, by principal components analysis and potential curves.

A total of 115 pork liver pastes were randomly collected in local markets from different brands, countries and containers. The concentrations of nine heavy metals (Cu, Ni, Cd, Fe, Mn, Pb, Cr, Co and Zn), determined by atomic absorption spectrometry, and some qualitative variables described on the labelling constituted the data set. Chemometrics analysis was performed combining principal components analysis (PCA), factor analysis (FA) and typical classification techniques, such as linear discriminant analysis (LDA) and potential curves (PoCu) to classify pork liver pastes. Origin of the sample, manufacturer and effect of manufacturing process were taken into account to verify traceability, which is an important issue in food safety policies.

Optimization of the capillary zone electrophoresis method for Huperzine A determination using experimental design and artificial neural networks.

Huperzine A, natural product from Huperzia serrata, is quite an important compound used to treat the Alzheimer's disease as a food supplement and also proposed as a prospective and prophylactic antidote against organophosphate poisoning. In this work, simple and fast capillary electrophoresis (CE) procedure with UV detection (at 230 nm) for determination of Huperzine A was developed and optimized. Capillary electrophoresis determination of Huperzine A was optimized using a combination of the experimental design (ED) and the artificial neural networks (ANN). In the first stage of optimization, the experiments were done according to the appropriate ED. Data evaluated by ANN allowed finding the optimal values of several analytical parameters (peak area, peak height, and analysis time). Optimal conditions found were 50 mM acetate buffer, pH 4.6, separation voltage 10 kV, hydrodynamic injection time 10 s and temperature 25 degrees C. The developed method shows good repeatability as relative standard division (R.S.D. = 0.9%) and it has been applied for determination of Huperzine A in various pharmaceutical products and in biological liquids. The limit of detection (LOD) in aqueous media was 0.226 ng/ml and 0.233 ng/ml for determination in the serum.

Analysis of polyphenols in wines: correlation between total polyphenolic content and antioxidant potential from photometric measurements. Prediction of cultivars and vintage from capillary zone electrophoresis fingerprints using artificial neural network.

The polyphenols (some of them are also called phytoalexins, flavonols, flavanons, flavanonols, flavons, flavanols, and anthocyanines) are usually marked as potent antioxidants or radical scavengers which assist the body cells against oxidation. Polyphenols in wine are also considered to explain so called French paradox (long life aging and low number of coronary diseases despite of high alcohol and fat consumption). The total polyphenolic content (TPC) and total antioxidant potential (TAP) were determined by photometry and found strongly correlated. This finding suggests that the determination of TAP can be replaced by a more simple procedure of TPC determination. Capillary zone electrophoresis (CZE) with preconcentration by solid phase extraction (SPE) was applied for some polyphenols determination and for obtaining electropherograms of the SPE extracts (fingerprints). From mathematical evaluation of the fingerprints, prediction of cultivars and vintage using artificial neural networks (ANN) was done with more than 90% correct prediction. The study was performed on a set of 47 samples of young wines (vintage 1999-2002) from south Moravia (Czech Republic) and New South Wales (Australia).

Mass spectrometry of humic substances of different origin including those from Antarctica A comparative study.

Mass spectra of humic acids (HA) from different sampling sites (Antarctica, Brazil, Czech Republic, Mexico and USA) and origin (plant, soil, peat, and coal derived) were obtained by laser desorption/ionization time of flight mass spectrometry (LDI-TOF MS). Optimisation of the experimental conditions are given as the optimal value of the laser energy at approximately 20-30% higher than the threshold. Under these conditions, reproducible mass spectra of HA samples were obtained. In the mass spectra the majority of the peaks are observed in the m/z region 100-1000Da. Mass spectra fingerprints of HA were analyzed and, in spite of the differences in their origin, a number of common features and profiles (patterns of peaks) were observed in most of the samples. Very similar structural groups (patterns) of the peaks are present in the m/z range 717-918Da for HA samples of quite different origins, countries or continents. The tandem LDI-TOF MS and multivariate statistical tools allowed us to extract and elucidate underlying information contained in the mass spectra of the HA samples under study. Applying principal components and cluster analysis, it was, e.g. demonstrated that most of the Antarctica HA samples show distinguishable differences when compared with humic acids from other continents and of different origin.

Validation of a capillary zone electrophoresis method for determination of rimantadine hydrochloride in Rimantadin100 tablets and the method application to dissolution test monitoring.

A capillary zone electrophoretic method with indirect UV-detection for determination of rimantadine, an antiviral drug against influenza A, in tablets was validated. Instrumental precision, the method precision, accuracy, calibration curve linearity, selectivity, robustness, and time stability of the sample and the standard were tested. The method was also applied to monitor dissolution tests of the tablets. The possibility of addition of an internal standard for improvement of the method precision was discussed.

Advantages of derivatization by osmium tetroxide and 2,2'-bipyridine for matrix-assisted laser desorption/ionization post-source decay fragment ion analysis of peptides.

Matrix-assisted laser desorption/ionization--post-source decay (MALDI-PSD) fragment ion analysis is frequently used for peptide sequence determination. PSD fragmentation is often changed or improved in terms of, e.g., sequence coverage, after derivatization. In this work, the influence of modification by an osmium tetroxide-bipyridine reagent (Os,bipy) on the MALDI-PSD behaviour of peptides is studied. The reagent modifies peptides specifically at tryptophan residues and oxidizes methionine to methionine sulfone and cysteine to cysteic acid. As a result the masses of some of the fragments are specifically shifted in case of peptides containing a methionine by +32 Da and, in cases of peptides containing a cysteine residue, by +48 Da. In addition, due to the change in protonation properties of a peptide after oxidation, fragments containing cysteic acid are in most cases totally suppressed. This effect significantly facilitates peptide sequence determination. Improvement of MALDI-TOFMS and PSD analysis after the reaction with Os,bipy is demonstrated for examples involving derivatives of humanin, a novel neuroprotective peptide.

Content of aliphatic hydrocarbons in limpets as a new way for classification of species using artificial neural networks.

It is demonstrated that biological species like limpets can be classified according to their level of n-alkanes when artificial neural networks are applied. Marine intertidal and subtidal limpets of the Canary Islands (Spain), Patella piperata, Patella candei crenata and Patella ulyssiponensis aspera were selected as bioindicator organisms. Samples were collected at four stations on the coasts of Fuerteventura. Concentration of n-alkanes in the soft tissues of the limpets has been determined by gas chromatography. Data were treated with artificial neural networks (ANNs) and it was found that using suitable architecture of a supervised artificial neural network, the limpets can be successfully distinguished (classified) up to 98%.