9 research outputs found
Present and Future Challenges in Food Analysis: Foodomics
Present and Future Challenges
in Food Analysis: Foodomic
An Extended Chain and Trinuclear Complexes Based on Pt(II)āM (M = Tl(I), Pb(II)) Bonds: Contrasting Photophysical Behavior
The
syntheses and structural characterizations of a PtāTl 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 donorāacceptor Pt ā
M bonds, are reported. The one-dimensional heterometallic chain <b>1</b> is formed by alternate āPtĀ(bzq)Ā(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>ā and āTlĀ(Me<sub>2</sub>CO)ā
fragments, with PtāTl bond separations in the range of 2.961(1)ā3.067(1)
Ć
. 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 āPtĀ(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 PtāM
bonds. The lowest-lying absorption band in the UVāvis 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>Lā²LCT <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 PtāTl 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 PtāM bonds in
THF solutions than in CH<sub>2</sub>Cl<sub>2</sub>, where the trinuclear
entities are predominant. The PtāTl chain <b>1</b> displays
in solid state a bright orange-red emission ascribed to <sup>3</sup>MMā²CT (Mā² = 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 PtāTl 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+Lā²)ĀMMā²CT]. <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>MMā²CT <sup>3</sup>[PtĀ(d) ā
PbĀ(sp)] with some metal-mediated intraligand (<sup>3</sup>ĻĻ/<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
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
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 Ć
; 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
Genetic strain variations in the metaphase-II phenotype of mouse oocytes matured in vivo or in vitro
Untargeted Metabolomics in Doping Control: Detection of New Markers of Testosterone Misuse by Ultrahigh Performance Liquid Chromatography Coupled to High-Resolution Mass Spectrometry
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
āLong-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
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 < 0.001) and ASA III-IV (HR = 2.0; 95%-CI 1.4-2.9; p < 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