Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 70
Filter
1.
Anal Chem ; 96(26): 10756-10764, 2024 Jul 02.
Article in English | MEDLINE | ID: mdl-38952275

ABSTRACT

This work introduces a new element-selective gas chromatography detector for the accurate quantification of traces of volatile oxygen-containing compounds in complex samples without the need for specific standards. The key to this approach is the use of oxygen highly enriched in 18O as the oxidizing gas in a combustion unit (800 °C) that allows us to directly and unambiguously detect the natural oxygen present in the GC-separated compounds through its incorporation into the volatile species formed after their combustion and their subsequent degradation to 16O in the ion source. The unspecific signal due to the low 16O abundance in the oxidizing gas could be compensated by measuring the m/z 12 that comes as well from the CO2 degradation. Equimolarity was proved with several O-containing compounds with different sizes and functionalities. A detection limit of 28 pg of injected O was achieved, which is the lowest ever reported for any GC detector, which barely worsened to 55 and 214 pg of O when the oxygenate partially or completely coeluted with a very abundant matrix compound. Validation was attained by the analysis of a SRM to obtain accurate (99-103%) and precise (1-4% RSD) results. Robustness was tested after spiking a hydrotreated diesel with 10 O-compounds at the ppm level, which could be discriminated from the matrix crowd and quantified (mean recovery of 102 ± 9%) with a single generic standard. Finally, it was also successfully applied to easily spot and quantify the 33 oxygenates naturally present in a complex wood bio-oil sample.

2.
J Surg Educ ; 2024 Jun 06.
Article in English | MEDLINE | ID: mdl-38849229

ABSTRACT

OBJECTIVE: Analyze the learning curve of medical students when they are trained with a laparoscopic box trainer and are presented with different modes of real-time feedback on their performance in the laparoscopic suturing procedure. DESIGN: A prospective randomized controlled trial (RTC) was performed. Three groups were proposed: control, visual, and haptic. The block randomization technique was used to assign the participants to one of the three groups. Each group trained the intracorporeal square flat knot task in a standardized FLS box simulator. A total of 11 sessions were programmed for this study: a pre-training session, eight training sessions, a post-training session, and a follow-up session. Measurement of the generated reaction force during the task were taken weekly for the first 10 sessions (pre-training, training, and post-training); then, the follow-up measurement was taken a month after. SETTING: This study was carried out in a single center at the Unidad de Simulación de Posgrado (USIP) of the postgraduate medicine program of the Universidad Nacional Autónoma de México (UNAM) between May and August 2023. PARTICIPANTS: The eligible participants were medical students without experience in minimally invasive surgery. All social service intern medics doing their social service in the USIP were invited to participate. A total of 20 participants entered the study from which 18 of them finished all the programmed sessions. RESULTS: A total of ten metrics were extracted from the reaction force signal measured at each session. All metrics are directly proportional to the reaction force and low magnitudes imply high tissue-handling proficiency. All groups improved their tissue handling skills, being the visual group the one who achieved better performance, followed by the haptic group and lastly the control group. CONCLUSION: The use of real time feedback, especially visual feedback can help novices to shorten the learning process of tissue handling and achieve a better proficiency in advanced tasks in shorter training periods.

3.
Ophthalmologica ; 2024 Mar 17.
Article in English | MEDLINE | ID: mdl-38493775

ABSTRACT

INTRODUCTION: The choroid and its role in posterior segment pathology has become an increasing subject of study. The objective of the present study was to analyze choroidal thickness (CT) in healthy eyes by widefield (WF) optical coherence tomography (OCT) up to the periphery and to compare the reliability of manual versus automatic measurement. METHODS: Cross-sectional and non-interventional study conducted on 191 healthy eyes of 101 patients. All patients were scanned by using WF-OCT (Xephilio WF-OCT S1; Canon Corp, Tokyo, Japan). CT was measured in 2000 µm intervals automatically using the built-in software and manually by two masked observers. All analyses were performed using the IBM-PSSS statistical software program (IBM-SPSS, v. 28.0.0.0, Chicago, IL, USA). RESULTS: CT was measured in 100% of the sample. The mean age of the study cohort was 39.05±19.06 years old. Mean subfoveal (SF)CT measured automatically was 343.67±84.18 µm and manually was 336.55±75.57 µm. The thickest point was located 2000 µm from the fovea in the superior sector in 62.83% of the subjects. According to age distribution, mean CT became significantly thinner from 40 years of age. When comparing automatic and manually measuring, the intraclass correlation coefficient was excellent (p<0.01) in all quadrants. Moreover, manual measurement interobserver agreement was excellent in all quadrants (p<0.01). CONCLUSION: The automatic system is valid and serves as the basis of choroid measurement. In more than 50% of the healthy subjects, superior CT is thicker than subfoveolar CT and mean CT became significantly thinner from 40 years of age.

4.
RSC Adv ; 14(3): 1676-1685, 2024 Jan 03.
Article in English | MEDLINE | ID: mdl-38187455

ABSTRACT

Nanosized UiO66 are among the most studied MOF materials. They have been extensively applied in various areas, such as catalysis, gas absorption, electrochemistry, chemical sensing, and biomedical applications. However, the preparation of stable nano-sized UiO66 for drug delivery applications is challenging because of the high tendency of UiO66 to aggregate during storage. To address this issue, we coated UiO66 with oligomers made of crosslinked cyclodextrins. The coated UiO66 exhibited a good stability upon storage for more than three weeks, even for low quantities of coating materials. The resulting core-shell UiO66 were characterized using a set of complementary methods including microscopies, spectroscopies, X-ray diffraction, and thermogravimetric investigations. Size distribution was assessed by orthogonal methods. Cisplatin was loaded in the core-shell nanoparticles, followed by an in-depth analysis by asymmetric flow field-flow fractionation (AF4) hyphenated with inductively coupled plasma-mass spectrometry (ICP-MS). This method combines the extremely high elemental selectivity and ultratrace detection limits of mass spectrometry with the capacity of AF4 to differentiate the diverse populations present in the sample. Free cisplatin and UiO66-associated cisplatin could be well separated by AF4. AF4-ICP-MS/MS analysis provided the exact drug loading, without the need of separating the nanoparticles from their suspension media. These data suggest the potential of AF4-ICP-MS/MS in the optimization of drug delivery systems.

5.
Anal Chim Acta ; 1285: 341999, 2024 Jan 02.
Article in English | MEDLINE | ID: mdl-38057053

ABSTRACT

A major challenge in the 21st century is the development of point-of-care diagnostic tools capable to detect and quantify disease biomarkers in a straightforward, affordable, sensitive, and specific manner. The remarkable plasmonic properties of gold nanoparticles (AuNPs) have promoted their use for development of simple methodologies for nucleic acid detection in combination with a variety of oligonucleotides amplification techniques. Here, assemblies of AuNPs with Multicomponent Nucleic Acid enzymes (MNAzymes) has been successfully used in the design of a highly sensitive and simple bioassay for rapid spectroscopic detection and quantification of miRNA-4739 in blood samples. The miRNA selected is a doxorubicin chemoresistant biomarker in breast cancer which overexpression promotes the proliferation, progression, and survival of cancer cells. In this work, two alternatives experimental designs, based on use of MNAzymes and AuNPs, have been optimized and applied for sensitive miRNA-4739 quantification: one based on a traditional direct measurement of wavelength shift and a second non-conventional simple approach based on isolation and measurement of free nanoparticles absorbance. Improvement in sensitivity and, higher measurement accuracy and precision were achieved with the second approach. The developed bioassay provides a detection limit as low as 7 pmolL-1 for miRNA-4739 quantification and performed satisfactory selectivity and well practical applicability by analysis of the miRNA-4739 in blood, demonstrating that the proposed strategy is a promising and suitable spectroscopic method for breast cancer diagnosis thought liquid biopsy of circulating tumoral cells.


Subject(s)
Biosensing Techniques , Breast Neoplasms , Metal Nanoparticles , MicroRNAs , Nucleic Acids , Humans , Female , MicroRNAs/analysis , Biomarkers, Tumor , Gold/chemistry , Breast Neoplasms/diagnosis , Limit of Detection , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Nucleic Acid Amplification Techniques/methods
6.
Anal Chem ; 95(31): 11761-11768, 2023 Aug 08.
Article in English | MEDLINE | ID: mdl-37490591

ABSTRACT

Here, we show the potential and applicability of the novel GC-combustion-MS approach as a nitrogen-selective GC detector. Operating requirements to achieve reproducible and compound-independent formation of volatile NO species as a selective N-signal during the combustion step are described. Specifically, high temperatures (≥1000 °C) and post-column O2 flows (0.4 mL min-1 of 0.3% O2 in He) turned out to be necessary when using a vertical oven without makeup flow (prototype #1). In contrast, the use of a horizontal oven with 1.7 mL min-1 He as an additional makeup flow (prototype #2) required milder conditions (850 °C and 0.2 mL min-1). A detection limit of 0.02 pg of N injected was achieved, which is by far the lowest ever reported for any GC detector. Equimolarity, linearity, and peak shape were also adequate. Validation of the approach was performed by the analysis of a certified reference material obtaining accurate (2% error) and precise (2% RSD) results. Robustness was tested with the analysis of two complex samples with different matrices (diesel and biomass pyrolysis oil) and N concentration levels. Total N determined after the integration of the whole chromatograms (524 ± 22 and 11,140 ± 330 µg N g-1, respectively) was in good agreement with the reference values (497 ± 10 and 11,000 ± 1200 µg N g-1, respectively). In contrast, GC-NCD results were lower for the diesel sample (394 ± 42 µg N g-1). Quantitative values for the individual and families of N species identified in the real samples by parallel GC-MS and additional GC × GC-MS analyses were also obtained using a single generic internal standard.

7.
Anal Chem ; 95(27): 10430-10437, 2023 Jul 11.
Article in English | MEDLINE | ID: mdl-37367956

ABSTRACT

Herein, we introduce the first relative single-particle inductively coupled plasma mass spectrometry (spICP-MS) approach where size calibration is carried out using the target NP itself measured under different instrumental conditions without external dependence on the complex and prone-to-error determination of transport efficiency or mass flux calibrations, in contrast to most spICP-MS approaches. The simple approach proposed allows determining gold nanoparticle (AuNP) sizes, with errors ranging from 0.3 to 3.1% (corroborated by HR-TEM). It has been demonstrated that the changes observed in the single-particle histograms obtained for a suspension of AuNPs under different sensitivity conditions (n = 5) are directly and exclusively related to the mass (size) of the target AuNP itself. Interestingly, the relative nature of the approach shows that once the ICP-MS system has been calibrated with a generic NP standard, it is no longer necessary to repeat the calibration for the size determination of different unimetallic NPs carried out along time (at least 8 months), independently of their size (16-73 nm) and even nature (AuNP or AgNP). Additionally, neither the NP surface functionalization with biomolecules nor protein corona formation led to significant changes (relative errors slightly increased 1.3- to 1.5-fold, up to 7%) in the NP size determination, in contrast to conventional spICP-MS approaches where relative errors increased 2- to 8-fold, up to 32%. This feature could be especially valuable for the analysis of NPs in real samples without the need of matrix-matched calibration.

8.
Anal Chim Acta ; 1251: 341002, 2023 Apr 22.
Article in English | MEDLINE | ID: mdl-36925291

ABSTRACT

The availability of protein standards and methods for their characterization, quantification, and purity assessment are currently a bottleneck in absolute quantitative proteomics. In this work, we introduce an absolute quantitative analytical strategy based on ICP-MS sulfur detection that uses sulfate as generic standard to quantify and certify the mass purity of protein standards. The methodology combines capillary chromatographic separation with parallel detection with ICP-MS and ESI-MS to determine proteoforms concentration and identity, respectively. The workability of the methodology was demonstrated using recombinant human cytokine standards IP-10 and Flt3L (2 batches), which are relevant biomarkers for carcinoma or inflammatory diseases. Every key factor (transport efficiency, column recovery, signal stability and internal standard suitability) was taken into account and certified BSA standard was used as quality control for validation purposes. Protein quantification values and resulting mass purity certification of IP-10 and one batch of Flt3L were very high (100 and 86%, respectively). Lower mass purity obtained for another batch of Flt3L (<70%) concurred with the finding of significant proteoforms resulted from oxidation processes as observed by parallel ESI-MS.


Subject(s)
Chemokine CXCL10 , Cytokines , Humans , Reference Standards , Quality Control
9.
Talanta ; 256: 124309, 2023 May 01.
Article in English | MEDLINE | ID: mdl-36753887

ABSTRACT

In-depth characterization of functionalized nanomaterials is still a remaining challenge in nanobioanalytical chemistry. In this work, we propose the online coupling of Asymmetric Flow Field-Flow Fractionation (AF4) with UV/Vis, Multiangle Light Scattering (MALS) and Inductively Coupled Plasma-Tandem Mass Spectrometry (ICP-MS/MS) detectors to carry out, in less than 10 min and directly in the functionalization reaction mixture, the complete characterization of gold nanoparticles (AuNPs) functionalized with oligonucleotides and surface-modified with polyethylene glycol (PEG). AF4 separation provided full separation of the bioconjugates from the original AuNPs while P/Au and S/Au ICP-MS/MS ratios in the bioconjugate fractographic peaks could be used to compute the corresponding stoichiometries, oligonucleotide/AuNP and PEG/AuNPs. MALS detection clearly showed the coexistence of two distinct nanoparticulated populations in the bioconjugation mixture, which were demonstrated to be different not only in size but in functionality as well. The major bioconjugate population showed lower hydrodynamic ratios (18 nm) with higher and steadier oligonucleotides/AuNPs (92) and PEG/AuNPs (2350) stoichiometries, in comparison to the minor abundant population (54 nm, 51 and 1877, respectively). Moreover, the ratio between the absorbance signals measured at 520 nm and 650 nm reflects a lower AuNP aggregation in the major (10.5) than in the minor (4.5) population. Results obtained prove the benefits of a detailed characterization to find out if subsequent purification of functionalized AuNP-oligonucleotides is required to design more efficiently their final bioanalytical application.


Subject(s)
Fractionation, Field Flow , Metal Nanoparticles , Gold/chemistry , Metal Nanoparticles/chemistry , Tandem Mass Spectrometry , Spectrum Analysis , Fractionation, Field Flow/methods , Particle Size
10.
Crit Rev Food Sci Nutr ; 63(16): 2790-2839, 2023.
Article in English | MEDLINE | ID: mdl-34590513

ABSTRACT

Proteins are important macronutrients for the human body to grow and function throughout life. Although proteins are found in most foods, their very dissimilar digestibility must be taking into consideration when addressing the nutritional composition of a diet. This review presents a comprehensive summary of the in vitro digestibility of proteins from plants, milk, muscle, and egg. It is evident from this work that protein digestibility greatly varies among foods, this variability being dependent not only upon the protein source, but also the food matrix and the molecular interactions between proteins and other food components (food formulation), as well as the conditions during food processing and storage. Different approaches have been applied to assess in vitro protein digestibility (IVPD), varying in both the enzyme assay and quantification method used. In general, animal proteins tend to show higher IVPD. Harsh technological treatments tend to reduce IVPD, except for plant proteins, in which thermal degradation of anti-nutritional compounds results in improved IVPD. However, in order to improve the current knowledge about protein digestibility there is a vital need for understanding dependency on a protein source, molecular interaction, processing and formulation and relationships between. Such knowledge can be used to develop new food products with enhanced protein bioaccessibility.


Subject(s)
Food Handling , Plant Proteins , Animals , Humans , Plant Proteins/metabolism , Food Handling/methods , Nutrients , Diet , Digestion
11.
J Proteomics ; 256: 104499, 2022 03 30.
Article in English | MEDLINE | ID: mdl-35092838

ABSTRACT

Elemental mass spectrometry is a powerful analytical technique widely established in inorganic analysis. However, despite its quantitative capabilities, it is not yet fully integrated or considered in Life Sciences fields like proteomics. Whereas it is true that ICP-MS has suffered from several instrumental and analytical limitations that have hindered its applicability in protein analysis, significant developments during the last decades have turned ICP-MS into an interesting and, in our opinion, a powerful tool to consider for accurate protein quantification without recourse to specific protein standards. Herein we will try to discuss how these traditional limitations in ICP-MS have been overcome, what further improvements are yet necessary (some of which are shared with MS-based proteomics platforms) and enlighten some of the already existing and potential applications of ICP-MS in absolute quantitative proteomics. SIGNIFICANCE: ICP-MS has the potential to become a complementary tool to help molecular mass spectrometry cope with existing limitations, especially those related to standardization and accuracy, in the absolute proteomics field. It can provide absolute quantification of diverse proteoforms using a single generic compound containing sulfur and/or another target element (e.g., phosphorous). Moreover, its applications in quantitative proteomics are no longer limited to protein standards certification or quantification of simple or purified mixtures. Interestingly, absolute quantification of proteins using ICP-MS is favored when carried out at the intact level, making it very compatible with top-down proteomics approaches. Recent instrumental and methodological advances enable synergic combination of ICP-MS with stablished LC-MS proteomics methodologies, setting the basis for its implementation in quantitative proteomics workflows.


Subject(s)
Proteins , Proteomics , Mass Spectrometry/methods , Proteins/analysis , Proteomics/methods , Reference Standards , Workflow
12.
Anal Bioanal Chem ; 414(1): 53-62, 2022 Jan.
Article in English | MEDLINE | ID: mdl-33674934

ABSTRACT

The current trends in modern medicine towards early diagnosis, or even prognosis, of different diseases have brought about the need for the corresponding biomarker detection at ever lower levels in really complex matrices. To do so, it is necessary to use proper extremely sensitive detection techniques such as elemental mass spectrometry. However, target labelling with metals for subsequent sensitive ICP-MS detection falls short nowadays even if resorting to inorganic nanoparticles containing a high number of detectable elements. Thus, new amplification strategies are being proposed to face this analytical challenge that will be critically discussed in this paper. Fundamentals of different novel strategies developed to achieve signal amplification and sensitive elemental mass spectrometry detection are here discussed. Some representative examples of relevant clinical applications are highlighted, along with future prospects and challenges.


Subject(s)
Biomarkers/chemistry , Mass Spectrometry/methods , Metal Nanoparticles/chemistry , Hep G2 Cells , Humans , Sensitivity and Specificity
13.
Semin Thorac Cardiovasc Surg ; 34(2): 783-789, 2022.
Article in English | MEDLINE | ID: mdl-33984479

ABSTRACT

To design and implement multidisciplinary interventions to decrease the interval between when a patient entered the operating room and when skin incision was made during thoracic surgical operations. Thirty-eight steps that occurred during the pre-incision time were identified during meetings with surgery, anesthesia, and nursing teams. Using a critical path method and Pareto analysis, standardization of intubation and positioning techniques as well as establishing strict guidelines to avoid unnecessary urinary catheter and arterial line placement were identified as high-value interventions. The duration of every step, and the total pre-incision time, was recorded during four phases of this project: (1) a pre-intervention period; (2) a run-in period; (3) a post-intervention period; and (4) a follow-up period five months later. 101 cases were analyzed. The median (IQR) pre-incision time dropped from 42.5(36-61) min prior to intervention to 34.5(29-39.5). This improvement persisted at five months (33 (28-41) min). Median positioning time decreased from 9(7-11) min to 4(3-5) min, with improvement persistent at late analysis 5(3.5-6) min. Median intubation times decreased from 7.5(5-15.5) min to 6(5-8) min post-intervention, with persistent improvement at five months 6(4-8). Engagement of a multidisciplinary team to design interventions to streamline pre-incision steps reduced the pre-incision time by 19%. Persistence of this improvement likely reflects the investment each teams' members had in achieving efficiency. Decreasing variability in the processes helped to achieve these benefits.


Subject(s)
Operating Rooms , Thoracic Surgical Procedures , Critical Pathways , Humans , Thoracic Surgical Procedures/adverse effects , Treatment Outcome
14.
J Proteome Res ; 20(11): 5064-5078, 2021 11 05.
Article in English | MEDLINE | ID: mdl-34606723

ABSTRACT

We report a novel hybrid, molecular and elemental mass spectrometry (MS) setup for the absolute quantification of snake venom proteomes shown here for two desert black cobra species within the genus Walterinnesia, Walterinnesia aegyptia and Walterinnesia morgani. The experimental design includes the decomplexation of the venom samples by reverse-phase chromatography independently coupled to four mass spectrometry systems: the combined bottom-up and top-down molecular MS for protein identification and a parallel reverse-phase microbore high-performance liquid chromatograph (RP-µHPLC) on-line to inductively coupled plasma (ICP-MS/MS) elemental mass spectrometry and electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-QToF MS). This allows to continuously record the absolute sulfur concentration throughout the chromatogram and assign it to the parent venom proteins separated in the RP-µHPLC-ESI-QToF parallel run via mass profiling. The results provide a locus-resolved and quantitative insight into the three desert black cobra venom proteome samples. They also validate the units of measure of our snake venomics strategy for the relative quantification of snake venom proteomes as % of total venom peptide bonds as a proxy for the % by weight of the venom toxins/toxin families. In a more general context, our work may pave the way for broader applications of hybrid elemental/molecular MS setups in diverse areas of proteomics.


Subject(s)
Elapid Venoms , Elapidae , Proteome , Animals , Elapid Venoms/chemistry , Proteome/analysis , Proteomics/methods , Tandem Mass Spectrometry
15.
Sensors (Basel) ; 20(22)2020 Nov 23.
Article in English | MEDLINE | ID: mdl-33238544

ABSTRACT

We introduce SodSAR, a fully polarimetric tower-based wide frequency (1-10 GHz) range Synthetic Aperture Radar (SAR) aimed at snow, soil and vegetation studies. The instrument is located in the Arctic Space Centre of the Finnish Meteorological Institute in Sodankylä, Finland. The system is based on a Vector Network Analyzer (VNA)-operated scatterometer mounted on a rail allowing the formation of SAR images, including interferometric pairs separated by a temporal baseline. We present the description of the radar, the applied SAR focusing technique, the radar calibration and measurement stability analysis. Measured stability of the backscattering intensity over a three-month period was observed to be better than 0.5 dB, when measuring a target with a known radar cross section. Deviations of the estimated target range were in the order of a few cm over the same period, indicating also good stability of the measured phase. Interforometric SAR (InSAR) capabilities are also discussed, and as a example, the coherence of subsequent SAR acquisitions over the observed boreal forest stand are analyzed over increasing temporal baselines. The analysis shows good conservation of coherence in particular at L-band, while higher frequencies are susceptible to loss of coherence in particular for dense vegetation. The potential of the instrument for satellite calibration and validation activities is also discussed.

16.
Anal Chem ; 92(19): 13500-13508, 2020 10 06.
Article in English | MEDLINE | ID: mdl-32842726

ABSTRACT

Inductively coupled plasma-mass spectrometry (ICP-MS) has been widely used in Life Sciences for the absolute quantification of biomolecules without specific standards, assuming the same response for generic compounds including complex biomolecules. However, contradictory results have been published on this regard. We present the first critical statistical comparison of the ICP-MS response factors obtained for 14 different relevant S-containing biomolecules (three peptides, four proteins, one amino acid, two cofactors, three polyethylene glycol (PEG) derivatives, and sulfate standard), covering a wide range of hydrophobicities and molecular sizes. Two regular flow nebulizers and a total consumption nebulizer (TCN) were tested. ICP-MS response factors were determined though calibration curves, and isotope dilution analysis was used to normalize the results. No statistical differences have been found for low-molecular-weight biocompounds, PEGs, and nonhydrophobic peptides using any of the nebulizers tested. Interestingly, while statistical differences were still found negligible (96-104%) for the proteins and hydrophobic peptide using the TCN, significantly lower response factors (87-40%) were obtained using regular flow nebulizers. Such differential behavior seems to be related mostly to hydrophobicity and partially to the molecular weight. Findings were validated using IDA in intact and digested bovine serum albumin solutions using the TCN (98 and 100%, respectively) and the concentric nebulizer (73 and 97%, respectively). Additionally, in the case of a phosphoprotein, results were corroborated using the P trace in parallel to the S trace used along the manuscript. This work seems to suggest that ICP-MS operated with regular nebulizers can offer absolute quantification using generic standards for most biomolecules except proteins and hydrophobic peptides.


Subject(s)
Amino Acids/analysis , Biological Science Disciplines , Peptides/analysis , Polyethylene Glycols/analysis , Proteins/analysis , Sulfates/analysis , Mass Spectrometry
17.
Chem Commun (Camb) ; 56(19): 2905-2908, 2020 Mar 05.
Article in English | MEDLINE | ID: mdl-32037422

ABSTRACT

We present a novel and single detection approach that enables sensitive, accurate and compound-independent quantification of N, S and H in the individual compounds present in complex samples. Integration of the whole chromatographic profile gives the total content of the elements. Simultaneous universal detection is also achieved using the C profile.

18.
Talanta ; 206: 120228, 2020 Jan 01.
Article in English | MEDLINE | ID: mdl-31514892

ABSTRACT

The asymmetric flow field-flow fractionation (AF4) coupled on-line with elemental (inductively coupled plasma-mass spectrometry, ICP-MS) and molecular (fluorescence and UV) detection has been investigated as a powerful tool for the characterization of bioinorganic nano-conjugates. In this study, we described methods for the characterization of biotin-antibody complexes bioconjugated with streptavidin quantum dots (QDs-SA-b-Ab). Operating parameters of AF4 separation technique were optimized and two procedures are proposed using a channel thickness of 350 µm and 500 µm. The use of a 500 µm spacer allowed to achieve an efficient AF4 separation of the QDs-SA-b-Ab complexes from the excess of individual species used in the bioconjugation that was required for a proper characterization of the bioconjugates. Optimization of the AF4 allowed a separation resolution good enough to isolate the QDs-SA-b-Ab bioconjugates from the free excess of b-Ab and QD-SA. The efficiency of the bioconjugation process could be then calculated, obtaining a value of 86% for a 1 QDs-SA: 5 b-Ab bioconjugation ratio. In addition, sample recovery around 90% was achieved.


Subject(s)
Quantum Dots/analysis , Water/chemistry , Antibodies/chemistry , Biotin/chemistry , Cadmium Compounds/analysis , Cadmium Compounds/chemistry , Fluorescence , Fractionation, Field Flow/methods , Limit of Detection , Mass Spectrometry/methods , Quantum Dots/chemistry , Scattering, Radiation , Selenium Compounds/analysis , Selenium Compounds/chemistry , Streptavidin/chemistry , Sulfides/analysis , Sulfides/chemistry , Zinc Compounds/analysis , Zinc Compounds/chemistry
19.
Anal Chem ; 91(15): 10088-10094, 2019 08 06.
Article in English | MEDLINE | ID: mdl-31295999

ABSTRACT

An accurate method has been developed to measure, in a single analytical run, δ34S in sulfite, sulfate and thiosulfate in water samples by liquid chromatography combined with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The method is based on the anionic exchange separation of sulfur species prior to their online isotope ratio determination by MC-ICPMS. Mass bias correction was accomplished by a novel approach based on the addition of an internal sulfur-containing standard to the sample. This innovative approach was compared to the sample-standard bracketing procedure. On-column isotopic fractionation was observed and therefore corrected by external calibration. Isotopic ratios were calculated by linear regression slope (LRS), an advantageous method for transient signals, leading to a combined uncertainty of δ34S below 0.25‰ and a reproducibility below 0.5‰ for the injection of 1 µg of S. The method was successfully applied to the measurement of δ34S in synthetic solutions and environmental water samples. Matrix effects leading to δ34S overestimation were observed for sulfate in some samples with high sodium/sulfate mass ratios. The developed analytical procedure simplifies the δ34S analysis of liquid environmental samples since preparation steps are no longer required and allows the analysis of several sulfur-containing species in a single run.

20.
Talanta ; 200: 72-77, 2019 Aug 01.
Article in English | MEDLINE | ID: mdl-31036227

ABSTRACT

The sensitive monitoring of mercury (II) selenide nanoparticles (HgSe NPs) is of great potential relevance in environmental studies, since such NPs are believed to be the ultimate metabolic product of the lifesaving mechanism pathway of Hg detoxification in biological systems. In this context, we take advantage of using gold-nanostructured screen-printed carbon electrodes (SPCE-Au) for the rapid, simple and sensitive electrochemical quantification of engineered water-stable HgSe NPs, as an advantageous alternative to conventional elemental analysis techniques. HgSe NPs are first treated in an optimized oxidative/acidic medium for Hg2+ release, followed by sensitive electrochemical detection by anodic stripping voltammetry (ASV). To the best of our knowledge, this is the first time that water-stable HgSe NPs are quantified using electrochemical techniques. The low limit of detection achieved (3.86 × 107 HgSe NPs/mL) together with the excellent repeatability (RSD: 3%), reproducibility (RSD: 5%) and trueness (relative error: 10%), the good performance in real sea water samples (recoveries of the analytical signal higher than 90%) and the simplicity/low cost of analysis make our method an ideal candidate for HgSe NPs monitoring in future environmental studies.


Subject(s)
Electrochemical Techniques , Environmental Monitoring , Mercury/analysis , Nanoparticles/analysis , Selenium/analysis , Water Pollutants, Chemical/analysis
SELECTION OF CITATIONS
SEARCH DETAIL
...