9 research outputs found

    An Extended Chain and Trinuclear Complexes Based on Pt(II)ā€“M (M = Tl(I), Pb(II)) Bonds: Contrasting Photophysical Behavior

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    The syntheses and structural characterizations of a Ptā€“Tl chain [{PtĀ­(bzq)Ā­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>}Ā­TlĀ­(Me<sub>2</sub>CO)]<sub><i>n</i></sub> <b>1</b> and two trinuclear Pt<sub>2</sub>M clusters (NBu<sub>4</sub>)Ā­[{PtĀ­(bzq)Ā­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>}<sub>2</sub>Tl] <b>2</b> and [{PtĀ­(bzq)Ā­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>}<sub>2</sub>Pb] <b>3</b> (bzq = 7,8-benzoquinolinyl), stabilized by donorā€“acceptor Pt ā†’ M bonds, are reported. The one-dimensional heterometallic chain <b>1</b> is formed by alternate ā€œPtĀ­(bzq)Ā­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>ā€ and ā€œTlĀ­(Me<sub>2</sub>CO)ā€ fragments, with Ptā€“Tl bond separations in the range of 2.961(1)ā€“3.067(1) ƅ. The isoelectronic trinuclear complexes <b>2</b> (which crystallizes in three forms, namely, <b>2a</b>, <b>2b</b>, and <b>2c</b>) and <b>3</b> present a sandwich structure in which the TlĀ­(I) or PbĀ­(II) is located between two ā€œPtĀ­(bzq)Ā­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>ā€ subunits. NMR studies suggest equilibria in solution implying cleavage and reformation of Ptā€“M bonds. The lowest-lying absorption band in the UVā€“vis spectra in CH<sub>2</sub>Cl<sub>2</sub> and tetrahydrofuran (THF) of <b>1</b>, associated with <sup>1</sup>MLCT/<sup>1</sup>Lā€²LCT <sup>1</sup>[5d<sub>Ļ€</sub>(Pt) ā†’ Ļ€*Ā­(bzq)]/<sup>1</sup>[(C<sub>6</sub>F<sub>5</sub>) ā†’ bzq], displays a blue shift in relation to the precursor, suggesting the cleavage of the chain maintaining bimetallic Ptā€“Tl fragments in solution, also supported by NMR spectroscopy. In <b>2</b> and <b>3</b>, it shows a blue shift in THF and a red shift in CH<sub>2</sub>Cl<sub>2</sub>, supporting a more extensive cleavage of the Ptā€“M bonds in THF solutions than in CH<sub>2</sub>Cl<sub>2</sub>, where the trinuclear entities are predominant. The Ptā€“Tl chain <b>1</b> displays in solid state a bright orange-red emission ascribed to <sup>3</sup>MMā€²CT (Mā€² = Tl). It exhibits remarkable and fast reversible vapochromic and vapoluminescent response to donor vapors (THF and Et<sub>2</sub>O), related to the coordination/decoordination of the guest molecule to the TlĀ­(I) ion, and mechanochromic behavior, associated with the shortening of the intermetallic Ptā€“Tl separations in the chain induced by grinding. In frozen solutions (THF, acetone, and CH<sub>2</sub>Cl<sub>2</sub>) <b>1</b> shows interesting luminescence thermochromism with emissions strongly dependent on the solvent, concentration, and excitation wavelengths. The Pt<sub>2</sub>Tl complex <b>2</b> shows an emission close to <b>1</b>, ascribed to charge transfer from the platinum fragment to the thallium [<sup>3</sup>(L+Lā€²)Ā­MMā€²CT]. <b>2</b> also shows vapoluminescent behavior in the presence of vapors of Me<sub>2</sub>CO, THF, and Et<sub>2</sub>O, although smaller and slower than those of <b>1</b>. The trinuclear neutral complex Pt<sub>2</sub>Pb <b>3</b> displays a blue-shift emission band, tentatively assigned to admixture of <sup>3</sup>MMā€²CT <sup>3</sup>[PtĀ­(d) ā†’ PbĀ­(sp)] with some metal-mediated intraligand (<sup>3</sup>Ļ€Ļ€/<sup>3</sup>ILCT) contribution. In contrast to <b>1</b> and <b>2</b>, <b>3</b> does not show vapoluminescent behavior

    Simple Monitoring of Cancer Cells Using Nanoparticles

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    Here we present a new strategy for a simple and fast detection of cancer circulating cells (CTCs) using nanoparticles. The human colon adenocarcinoma cell line (Caco2) was chosen as a model CTC. Similarly to other adenocarcinomas, colon adenocarcinoma cells have a strong expression of EpCAM, and for this reason this glycoprotein was used as the capture target. We combine the capturing capability of anti-EpCAM functionalized magnetic beads (MBs) and the specific labeling through antibody-modified gold nanoparticles (AuNPs), with the sensitivity of the AuNPs-electrocatalyzed hydrogen evolution reaction (HER) detection technique. The fully optimized process was used for the electrochemical detection of Caco2 cells in the presence of monocytes (THP-1), other circulating cells that could interfere in real blood samples. Therefore we obtained a novel and simple in situ-like sensing format that we applied for the rapid quantification of AuNPs-labeled CTCs in the presence of other human cells

    Inside out <i>Porphyridium cruentum</i>: Beyond the Conventional Biorefinery Concept

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    Here, an unprecedented biorefinery approach has been designed to recover high-added value bioproducts starting from the culture ofPorphyridium cruentum. This unicellular marine red alga can secrete and accumulate high-value compounds that can find applications in a wide variety of industrial fields. 300 Ā± 67 mg/L of exopolysaccharides were obtained from cell culture medium; phycoerythrin was efficiently extracted (40% of total extract) and isolated by single chromatography, with a purity grade that allowed the crystal structure determination at 1.60 ƅ; a twofold increase in Ī²-carotene yield was obtained from the residual biomass; the final residual biomass was found to be enriched in saturated fatty acids. Thus, for the first time, a complete exploitation ofP. cruentumculture was set up

    Untargeted Metabolomics in Doping Control: Detection of New Markers of Testosterone Misuse by Ultrahigh Performance Liquid Chromatography Coupled to High-Resolution Mass Spectrometry

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    The use of untargeted metabolomics for the discovery of markers is a promising and virtually unexplored tool in the doping control field. Hybrid quadrupole time-of-flight (QTOF) and hybrid quadrupole Orbitrap (Q Exactive) mass spectrometers, coupled to ultrahigh pressure liquid chromatography, are excellent tools for this purpose. In the present work, QTOF and Q Exactive have been used to look for markers for testosterone cypionate misuse by means of untargeted metabolomics. Two different groups of urine samples were analyzed, collected before and after the intramuscular administration of testosterone cypionate. In order to avoid analyte losses in the sample treatment, samples were just 2-fold diluted with water and directly injected into the chromatographic system. Samples were analyzed in both positive and negative ionization modes. Data from both systems were treated under untargeted metabolomic strategies using XCMS application and multivariate analysis. Results from the two mass spectrometers differed in the number of detected features, but both led to the same potential marker for the particular testosterone ester misuse. The in-depth study of the MS and MS/MS behavior of this marker allowed for the establishment of 1-cyclopentenoylglycine as a feasible structure. The putative structure was confirmed by comparison with synthesized material. This potential marker seems to come from the metabolism of the cypionic acid release after hydrolysis of the administered ester. Its suitability for doping control has been evaluated

    ā€œLong-term oncologic outcomes and risk factors for distant recurrence after pathologic complete response following neoadjuvant treatment for locally advanced rectal cancer. A nationwide, multicentre studyā€

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    Background: Pathologic complete response (pCR) after multimodal treatment for locally advanced rectal cancer (LARC) is used as surrogate marker of success as it is assumed to correlate with improved oncologic outcome. However, long-term oncologic data are scarce.Methods: This retrospective, multicentre study updated the oncologic follow-up of prospectively collected data from the Spanish Rectal Cancer Project database. pCR was described as no evidence of tumour cells in the specimen. Endpoints were distant metastases-free survival (DMFS) and overall survival (OS). Multivariate regression analyses were run to identify factors associated with survival.Results: Overall, 32 different hospitals were involved, providing data on 815 patients with pCR. At a median follow-up of 73.4 (IQR 57.7-99.5) months, distant metastases occurred in 6.4% of patients. Abdominoperineal excision (APE) (HR 2.2, 95%CI 1.2-4.1, p = 0.008) and elevated CEA levels (HR = 1.9, 95% CI 1.0-3.7, p = 0.049) were independent risk factors for distant recurrence. Age (years) (HR 1.1; 95% CI 1.05-41.09; p &lt; 0.001) and ASA III-IV (HR = 2.0; 95%-CI 1.4-2.9; p &lt; 0.001), were the only factors associated with OS. The estimated 12, 36 and 60-months DMFS rates were 96.9%, 91.3%, and 86.8%. The estimated 12, 36 and 60-months OS rates were 99.1%, 94.9% and 89.3%.Conclusions: The incidence of metachronous distant metastases is low after pCR, with high rates of both DMFS and OS. The oncologic prognosis in LARC patients that achieve pCR after neoadjuvant chemoradiotherapy is excellent in the long term. (c) 2023 Elsevier Ltd, BASO similar to The Association for Cancer Surgery, and the European Society of Surgical Oncology. All rights reserved
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