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1.
Anal Chem ; 96(13): 5289-5297, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38507224

RESUMO

Paper spray mass spectrometry (PS-MS) has evolved into a promising tool for monitoring reactions in thin films and microdroplets, known as reactive PS, alongside its established role in ambient and direct ionization. This study addresses the need for rapid, cost-effective methods to improve analyte identification in biofluids by leveraging reactive PS-MS in clinical chemistry environments. The technique has proven effective in derivatizing target analytes, altering hydrophobicity to enhance elution and ionization efficiency, and refining detection through thin-film reactions on paper, significantly expediting reaction rates by using amino acids (AAs) as model analytes. These molecules are prone to interacting with substrates like paper, impeding elution and detection. Additionally, highly abundant species in biofluids, such as lipids, often suppress AA ionization. This study employs the Schiff base (SB) reaction utilizing aromatic aldehydes for AA derivatization to optimize reaction conditions time, temperature, and catalyst presence and dramatically increasing the conversion ratio (CR) of formed SB. For instance, using leucine as a model AA, the CR surged from 57% at room temperature to 89% at 70 °C, with added pyridine during and after 7.5 min, displaying a 43% CR compared to the bulk reaction. Evaluation of various aromatic aldehydes as derivatization agents highlighted the importance of specific oxygen substituents for achieving higher conversion rates. Furthermore, diverse derivatization agents unveiled unique fragmentation pathways, aiding in-depth annotation of the target analyte. Successfully applied to quantify AAs in human and rat plasma, this reactive PS-MS approach showcases promising potential in efficiently detecting conventionally challenging compounds in PS-MS analysis.


Assuntos
Aminoácidos , Bases de Schiff , Humanos , Animais , Ratos , Espectrometria de Massas/métodos , Aminas , Aldeídos/análise
2.
Anal Bioanal Chem ; 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38958704

RESUMO

In order to find an explanation for the mechanism in a plasma operated with an alternating voltage, or rather a square wave voltage, such a plasma was investigated. It was found that Penning ionization, charge transfer, and photoionization played a minor or even no role in the soft ionization mechanism of a FµTP. If the collision of plasma gases with air does not contribute to soft ionization, it should also be possible to use a separated plasma for soft ionization. Preliminary investigations show that it is possible to ignite a diagnosis gas with a plasma gas even when there is a barrier such as glass between those gases. A temporally and locally limited potential must be produced at the outer surface to achieve this. This potential should be sufficient to ionize the environment softly and to be able to use this so-called closed µ-tube plasma as a new ionization source.

3.
Anal Chem ; 95(22): 8423-8432, 2023 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-37220280

RESUMO

Electrospray ionization mass spectrometry (ESI-MS) is an established method for the identification of biomarkers. By nano-ESI (nESI), the polar molecular fraction of complex biological samples can be successfully ionized. In contrast, the less-polar free cholesterol, which serves as an important biomarker for several human diseases, is barely accessible by nESI. Although, complex scan functions of modern high-resolution MS devices are able to increase the signal-to-noise ratio, they are limited by the ionization efficiency of the nESI. One possible method to increase the ionization efficiency is the derivatization with acetyl chloride, however interferences with cholesteryl esters must be considered, so chromatographic separation or complex scan functions may be required. A novel approach to increase the yield of cholesterol ions of the nESI could be the application of a second consecutive-ionization process. This publication presents the flexible microtube plasma (FµTP) as a consecutive-ionization source, which allows the determination of cholesterol in nESI-MS analysis. Focusing on the analytical performance, the nESI-FµTP approach increases the cholesterol signal yield in a complex liver extract by a factor of 49. The repeatability and long-term stability could be successfully evaluated. A linear dynamic range of 1.7 orders of magnitude, a minimum detectability of 5.46 mg/L, and a high accuracy (deviation, -8.1%) demonstrates the nESI-FµTP-MS as an excellent approach for a derivatization-free determination of cholesterol.


Assuntos
Colesterol , Espectrometria de Massas por Ionização por Electrospray , Humanos , Espectrometria de Massas por Ionização por Electrospray/métodos , Ésteres do Colesterol , Íons
4.
Anal Chem ; 95(2): 854-861, 2023 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-36538370

RESUMO

Dielectric barrier discharge ionization (DBDI) is a versatile tool for small-molecule mass spectrometry applications, helping cover from polar to low polar molecules. However, the plasma gas-phase interactions are highly complex and have been scarcely investigated. The ionization mechanisms of plasmas have long been assumed to be somewhat similar to atmospheric pressure chemical ionization (APCI). Here, we evaluated the ionization mechanisms of a two-ring DBDI ion source, using different discharge gases to analyze vaporized liquid samples. Polycyclic aromatic hydrocarbons (PAHs) were used as model analytes to assess the mechanisms' dominance: protonation, [M + H]+, or radical ion species formation, [M]·+. In the present work, two different ionization trends were observed for APCI and DBDI during the PAH analysis; the compounds with proton affinities (PA) over 856 kJ/mol were detected as [M + H]+ when APCI was used as ionization source. Meanwhile, independently of the PA, DBDI showed the prevalence of charge exchange reactions. The addition of dopants in the gas-phase region shifted the ionization mechanisms toward charge exchange reactions, facilitating the formation of [M]·+ ion species, showing anisole a significant boost of the PAH radical ion species signals, over nine times for Ar-Prop-DBDI analysis. The presence of high-energy metastable atoms (e.g., HeM) with high ionization potentials (IE = 19.80 eV) did not show boosted PAH abundances or extensive molecule fragmentation. Moreover, other species in the plasma jet region with closer and more appropriate IE, such as N2 B3Πg excited molecules, are likely responsible for PAH Penning ionization.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Humanos , Hidrocarbonetos Policíclicos Aromáticos/análise , Espectrometria de Massas/métodos
5.
J Clin Monit Comput ; 37(6): 1619-1626, 2023 12.
Artigo em Inglês | MEDLINE | ID: mdl-37436599

RESUMO

PURPOSE: Temperature monitoring in the perioperative setting often represents a compromise between accuracy, invasiveness of probe placement, and patient comfort. Transcutaneous sensors using the Zero-Heat-Flux (ZHF) and Double-Sensor (DS) technology have been developed and evaluated in a variety of clinical settings. The present study is the first to compare the performance of both sensors simultaneously with temperature measured by a Swan-Ganz catheter (PAC) in patients admitted to the intensive care unit (ICU) after cardiac surgery. METHODS: In this monocentric prospective observational study patients were postoperatively transferred to the ICU and both sensors were placed on the patients' foreheads. Core body temperature measured by intraoperatively placed PAC served as gold standard. Measurements were recorded at 5-minute intervals and up to 40 data sets per patient were recorded. Bland and Altman's method for repeated measurements was used to analyse agreement. Subgroup analyses for gender, body-mass-index, core temperature, airway status and different time intervals were performed. Lin's concordance correlation coefficient (LCCC) was calculated, as well as sensitivity and specificity for detecting hyperthermia (≥ 38 °C) and hypothermia (< 36 °C). RESULTS: Over a period of six month, we collected 1600 sets of DS, ZHF, and PAC measurements, from a total of 40 patients. Bland-Altman analysis revealed a mean bias of -0.82 ± 1.27 °C (average ± 95% Limits-of-Agreement (LoA)) and - 0.54 ± 1.14 °C for DS and ZHF, respectively. The LCCC was 0.5 (DS) and 0.63 (ZHF). Mean bias was significantly higher in hyperthermic and hypothermic patients. Sensitivity and specificity were 0.12 / 0.99 (DS) and 0.35 / 1.0 (ZHF) for hyperthermia and 0.95 / 0.72 (DS) and 1.0 / 0.85 (ZHF) for hypothermia. CONCLUSION: Core temperature was generally underestimated by the non-invasive approaches. In our study, ZHF outperformed DS. In terms of agreement, results for both sensors were outside the range that is considered clinically acceptable. Nevertheless, both sensors might be adequate to detect postoperative hypothermia reliably when more invasive methods are not available or appropriate. TRIAL REGISTRATION: German Register of Clinical Trials (DRKS-ID: DRKS00027003), retrospectively registered 10/28/2021.


Assuntos
Procedimentos Cirúrgicos Cardíacos , Hipotermia , Humanos , Temperatura Corporal , Hipotermia/diagnóstico , Unidades de Terapia Intensiva , Termômetros , Estudos Prospectivos
6.
J Sep Sci ; 45(16): 3105-3114, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35801641

RESUMO

Dielectric barrier discharge ionization has gained attention in the last few years due to its versatility and the vast array of molecules that can be ionized. In this study, we report on the assessment of liquid chromatography coupled to dielectric barrier discharge ionization with mass spectrometry for neutral lipid analysis. A set of different neutral lipid subclasses (triacylglycerides, diacylglycerides, and sterols) were selected for the study. The main species detected from our ionization source were [M-H2 O+H]+ , [M+H]+ or [M-R-H2 O+H]+ , attributed to sterol dehydration, protonation or the fragmentation of an acyl chain accompanied by a water loss of the glycerolipids, respectively. In terms of sensitivity, the dielectric barrier discharge displayed overall improved abundances and comparable or better limits of quantitation than atmospheric pressure chemical ionization for both acylglycerols and sterols. As a case study, different archaeological samples with variable content in neutral lipids, particularly triacylglycerides, were studied. The identification was carried out by combining accurate mass and the tentative formula associated with the exact mass, retention time matching with standards, and additional structural information from in-source fragmentation. The high degree of unsaturation and the presence of sterols revealed the potential vegetal origin of the material stored in the analyzed samples.


Assuntos
Pressão Atmosférica , Esteróis , Cromatografia Líquida de Alta Pressão , Cromatografia Líquida , Espectrometria de Massas , Espectrometria de Massas por Ionização por Electrospray
7.
Anal Chem ; 92(22): 15212-15220, 2020 11 17.
Artigo em Inglês | MEDLINE | ID: mdl-33135875

RESUMO

Ionization mechanisms of different lipid classes and other hydrophobic compounds have been evaluated in an ambient air laser-desorption flexible microtube plasma ionization (LD-FµTPi) setup, without sample manipulation. Lipids require a minimum laser fluency of 27 W/mm2 for efficient desorption and detection, providing the possibility for temperature-programmed laser desorption of different lipid classes. The flexible microtube plasma (FµTP) produces oxygen addition to double bonds, even to polyunsaturated molecules. The characteristic fragmentation pattern of phospholipids consisting of the neutral loss of the phosphocholine head group was verified. The formation of dimers due to hydrogen bonding and dispersion forces was observed as well. In this sense, soft ionization capabilities of the FµTP were proven in both ion modes. Ambient air mass spectrometry methods often suffer from decreased reproducibility, for instance, due to changing atmospheric conditions or sensitive positioning of the ion source. It was shown that neutrals become increasingly unstable above a distance of 7 ± 1 mm to the spectrometer's inlet, providing estimates for the free volume in LD-FµTPi MS. In this sense, no guided transport is required. The ion plume ejected from the plasma can be altered by applying a bias voltage to the copper substrate. Ions can be detected at -950 V, 300 V (negative ion mode) and -400 V, 900 V (positive ion mode), respectively. The ions are guided through an internal electric field gradient of the FµTP that arises from charged capillary walls, ideal for ion detection. In conclusion, this makes the method fast, robust, and flexible.


Assuntos
Interações Hidrofóbicas e Hidrofílicas , Lipídeos/análise , Lipídeos/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Limite de Detecção , Oxigênio/química , Gases em Plasma/química
8.
Anal Chem ; 92(6): 4663-4671, 2020 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-32106668

RESUMO

This study introduced sandwich-structured copper-glass substrates for standardization of laser desorption and plasma ionization. For standardized quantitative analysis, cavities were constructed which allow better reproducibility in droplet deposition and for laser application. Applying the diode laser, molten substrate material is incorporated into the glass, being trapped inside. Therefore, this method can be separated from laser ablation, achieving high ion signals without ablating material from the surface. Flexible microtube plasma (FµTP) was selected as the ionization source, this being the first time that laser desorption and FµTP ionization are coupled. This laser-plasma interface was applied to the detection of cholesterol, which showed a significantly improved limit of detection of 0.46 ng and linear dynamic range of 3 orders of magnitude in positive ion mode compared to other (ambient air mass spectrometry) methods. The main reason was the change of phase on the copper surface. The dehydrated molecule [M-H2O+H]+ was the base peak of the spectrum and no further dissociation or fragmentation was observed. Blood plasma was spiked with cholesterol. In a 1:100 chloroform dilution, the presence of the plasma was neglectable and led to the same detection limits and linear dynamic range as in the cholesterol standard. No sample preparation or internal standards were needed for calibration. The physical effects of the surface modification were investigated, including the calculation of the laser beam waist to simplify the comparison and reproducibility of results.


Assuntos
Colesterol/sangue , Cobre/química , Lasers , Colesterol/normas , Cobre/normas , Vidro/química , Vidro/normas , Humanos , Lasers/normas , Estrutura Molecular , Tamanho da Partícula , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/instrumentação , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/normas , Propriedades de Superfície
9.
Anal Chem ; 92(14): 9722-9729, 2020 07 21.
Artigo em Inglês | MEDLINE | ID: mdl-32579344

RESUMO

A new soft ionization device for mass spectrometry is presented using the flexible microtube plasma under controlled atmospheric conditions. The controlled atmosphere flexible microtube plasma consists of the plasma source itself connected to a gas chromatograph and a mass spectrometer using a borosilicate glass cross piece. Controlled atmosphere, for example, nitrogen and/or an oxygen mixture, is introduced to the system to create a clean ionization environment. Reproducibility issues are discussed, and solutions are presented manipulating the gas flow in the cross piece. A proof of concept is shown using a ketone mixture introduced to the mass spectrometer to optimize atmospheric conditions. Furthermore, application of the presented device for the sensitive and nonfragmenting ionization of volatile organic biomarkers relevant for cancer is carried out. Sample treatment for human saliva is described, and relevant candidate biomarkers are measured in the saliva matrix, showing a very good ionization efficiency and neglectable matrix effects with limits of detection below 80 ppt.


Assuntos
Biomarcadores Tumorais/química , Espectrometria de Massas/instrumentação , Espectrometria de Massas/métodos , Neoplasias/diagnóstico , Saliva/química , Compostos Orgânicos Voláteis/química , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Reprodutibilidade dos Testes
10.
Rev Med Chil ; 148(11): 1614-1618, 2020 Nov.
Artigo em Espanhol | MEDLINE | ID: mdl-33844767

RESUMO

BACKGROUND: Patient Health Questionnaire (PHQ-9) has nine questions and is used in diabetic or hypertensive patients to detect depressive symptoms. The PHQ-2 uses the first two questions of the PHQ-9 to rapidly detect those patients that should answer the whole questionnaire. AIM: To validate the PHQ-2 to detect depressive symptoms in diabetic or hypertensive patients consulting at Primary Health Care (PHC). MATERIAL AND METHODS: Secondary analysis of data obtained during the baseline assessment of a clinical trial. Diabetic and hypertensive patients aged 18 years or more, attending a public health care clinic of Metropolitan Santiago, were invited to participate. Those accepting, answered the Patient Health Questionnaire (PHQ-9), consisting in nine questions about depressive symptoms. Demographics and health data were also collected. The PHQ-2 capacity to discriminate PHQ-9 scores equal or higher than 10 and 15 and the correlation between both versions, were assessed. RESULTS: Ninety-four participants aged 64 ± years (73% women) answered the questionnaire. A cut-off score of 3 or more points in the PHQ-2 achieved the best tradeoff between sensitivity and specificity for discriminating PHQ-9 scores equal or higher than 10 (area under the receiver operating characteristic curve (ROC) = 0.92, 95% confidence interval [95% CI] = 0.87 to 0.97) and 15 points (area under the ROC curve = 0.95, 95% CI = 0.92 to 0.99). Both versions had a high positive correlation (r = 0.87). CONCLUSIONS: The PHQ-2 allows a stepped, simple and accurate screening for depressive symptoms. Diabetic or hypertensive patients with 3 or more points should be immediately assessed with the remaining questions of the PHQ-9.


Assuntos
Depressão/diagnóstico , Diabetes Mellitus , Questionário de Saúde do Paciente , Adolescente , Diabetes Mellitus/psicologia , Feminino , Humanos , Masculino , Programas de Rastreamento , Pessoa de Meia-Idade , Questionário de Saúde do Paciente/normas , Psicometria , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Inquéritos e Questionários
11.
Anal Chem ; 91(5): 3733-3739, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30672695

RESUMO

Plasma sources in atmospheric pressure soft-ionization mass spectrometry have gained significant interest in recent years. As many of these sources are used under ambient air conditions, their interaction with the surrounding atmosphere plays an important role in the ionization pathway. This study focuses on the interaction between the plasma source and the surrounding atmosphere by connecting the plasma source to the mass spectrometer using a 2 mm ID closed reactant capillary supplied by a reactant gas up to 500 mL per minute to gain a controlled atmosphere. Different reactant gases (Ar, He, O2, and N2) and reactant gas mixtures are tested with regard to the DBDI performance and then used to improve the ionization efficiency. Tailoring the controlled atmosphere for a certain analyte, for example, perfluorinated compounds, leads to significantly improved limits of detection up to 2 ppb.

12.
Anal Bioanal Chem ; 411(19): 4785-4796, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30707264

RESUMO

In this work, the multiclass detection of explosives and related compounds has been studied by liquid chromatography-high-resolution mass spectrometry by means of a time-of-flight mass spectrometer (TOFMS) operated in the negative ion mode, using dielectric barrier discharge ionization (DBDI). Reversed-phase high-performance liquid chromatography (HPLC) separation was performed using water-methanol mobile phase without any modifier, although the effect of ammonium acetate was studied. DBD plasma was generated by applying a square wave voltage of 2.5 kV to a 100-mL min-1 He flow. The DBDI probe was adjusted to fit the commercial API source housing so that the HPLC eluent was nebulized and vaporized in the same manner as for atmospheric-pressure chemical ionization (APCI). The ionization process was affected by the temperature of the two nitrogen streams used to vaporize the solvent and the analytes, particularly for RDX and HMX, which are thermolabile compounds. The best approach in terms of sensitivity for all the studied compounds was the use of a gradient of temperatures in the ionization source, starting at 225/200 °C (vaporizer/drying gas temp) for nitramines and ending at 350/325 °C for nitroaromatic compounds. High-resolution full-scan spectra of individual selected compounds were recorded by LC-DBDI-TOFMS, and the results were compared to LC-APCI-TOFMS. A better sensitivity (slope of calibration curve) was obtained by DBDI for more than 70% of the studied compounds in both wastewater and soil extracts. Graphical abstract ᅟ.

13.
Anal Chem ; 90(17): 10111-10116, 2018 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-30063325

RESUMO

Dielectric barrier discharges are used as soft ionization sources for mass spectrometers or ion mobility spectrometers, enabling excellent possibilities for analytical applications. A new robust and small-footprint discharge design, flexible microtube plasma (FµTP), developed as a result of ongoing miniaturization and electrode design processes, is presented in this work. This design provides major safety benefits by fitting the electrode into an inert flexible fused silica capillary (tube). Notably, in this context, the small discharge dimensions enable very low gas flows in the range of <100 mL min-1; portability; the use of hydrogen, nitrogen, and air in addition to noble gases such as helium and argon, including its mixtures with propane; and application in microchip environments. By coupling FµTP with gas chromatography/mass spectrometry, we show that the polarity principle of the new discharge design allows it to outperform established ionization sources such as dielectric barrier discharge for soft ionization (DBDI) and low-temperature plasma (LTP) at low concentrations of perfluoroalkanes in terms of sensitivity, ionization efficiency, chemical background, linear dynamic range, and limit of detection by a large margin. In negative ion mode, the limit of detection is improved by more than 3-fold compared with that of DBDI and by 8-fold compared with that of LTP. The protonation capability was evaluated by headspace measurements of diisopropyl methylphosphonate in positive ion mode, showing low fragmentation and high stability in comparison to DBDI and LTP.

14.
Anal Chem ; 90(5): 3537-3542, 2018 03 06.
Artigo em Inglês | MEDLINE | ID: mdl-29461807

RESUMO

Dielectric barrier discharges (DBDs) have been used as soft ionization sources (DBDI) for organic mass spectrometry (DBDI-MS) for approximately ten years. Helium-based DBDI is often used because of its good ionization efficiency, low ignition voltage, and homogeneous plasma conditions. Argon needs much higher ignition voltages than helium when the same discharge geometry is used. A filamentary plasma, which is not suitable for soft ionization, may be produced instead of a homogeneous plasma. This difference results in N2, present in helium and argon as an impurity, being Penning-ionized by helium but not by metastable argon atoms. In this study, a mixture of argon and propane (C3H8) was used as an ignition aid to decrease the ignition and working voltages, because propane can be Penning-ionized by argon metastables. This approach leads to homogeneous argon-based DBDI. Furthermore, operating DBDI in an open environment assumes that many uncharged analyte molecules do not interact with the reactant ions. To overcome this disadvantage, we present a novel approach, where the analyte is introduced in an enclosed system through the discharge capillary itself. This nonambient DBDI-MS arrangement is presented and characterized and could advance the novel connection of DBDI with analytical separation techniques such as gas chromatography (GC) and high-pressure liquid chromatography (HPLC) in the near future.

15.
Rapid Commun Mass Spectrom ; 32(13): 1092-1098, 2018 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-29660193

RESUMO

RATIONALE: The potential of an atmospheric pressure ionization source based on a dielectric barrier discharge in helium for the hyphenation of gas chromatography and mass spectrometry (GC/DBDI-MS) has been demonstrated only recently and for a limited range of compounds. Due to its 'soft' ionization properties and the possibility to choose from a variety of atmospheric pressure ionization MS instruments, GC/DBDI-MS has the potential to be an interesting alternative to 'classic' GC/MS techniques. METHODS: The hyphenation of GC with DBDI-MS at atmospheric pressure is used for the determination of semifluorinated n-alkanes in ski wax samples. RESULTS: Different to perfluorinated n-alkanes, which are typically detected as [M - F + O]- and [M - F]- , semifluorinated n-alkanes can be detected both in positive mode as [M - 3H + nO]+ and [M - H + nO]+ (n = 0, 1, 2, and 3) ions, as well as in negative mode as a fragment ion representing the fluorinated part of the respective semifluorinated n-alkane. The method allowed the sensitive detection of semifluorinated n-alkanes with achievable limits of detection (LODs) in the single digit pg range injected on column. To examine the applicability of the GC/DBDI-MS method, semifluorinated n-alkanes were determined in fluorinated ski waxes. Results were confirmed by complimentary GC/electron ionization MS measurements. CONCLUSIONS: The unique SFA ionization patterns serve for complementary unambiguous identification of semifluorinated n-alkane species in positive mode and screening of contained n-alkanes fluorinated chain lengths in negative mode.

16.
Can J Anaesth ; 65(7): 766-775, 2018 07.
Artigo em Inglês | MEDLINE | ID: mdl-29484605

RESUMO

PURPOSE: The present study aimed to test the hypothesis that cerebral oxygen saturation (ScO2) measurements with the INVOS-5100-C and the ForeSight-Elite cerebral oximeters vary in their correlation with mixed venous oxygen saturation (SvO2) upon changes in systemic oxygenation in extubated cardiac surgical patients. Additionally, we aimed to elucidate whether the ScO2 measurements of both devices can be used interchangeably to detect reduced SvO2. METHODS: Forty-eight spontaneously breathing patients extubated after cardiac surgery were included in this prospective observational study. The patients were exposed to both high (10 oxygen L·min-1 via face mask) and low (room air) inspiratory oxygen concentrations. Bi-hemispherical ScO2 was determined with the INVOS and ForeSight Elite cerebral oximeters. The SvO2 was measured with a pulmonary artery catheter. RESULTS: Significant changes in oxygen delivery, ScO2 (by both cerebral oximeters), and SvO2 were observed upon variation of oxygenation. The minimum mean (standard deviation) ScO2 (ScO2min) using the INVOS and ForeSight did not differ significantly during high oxygen delivery [63.1 (8.6) % vs 65.8 (4.7) %, respectively; P = 0.07], but during low oxygen delivery, the INVOS value was significantly lower than that of the ForeSight oximeter [56.7 (8.9) % vs 61.3 (4.4) %, respectively; P = 0.003]. Both devices differed in the correlation between ScO2min and SvO2 for the combined oxygenation data (0.59, INVOS vs 0.28, ForeSight; correlation difference, 0.31; Bonferroni-adjusted 95% confidence interval [CI], 0.08 to 0.54; P = 0.008). The receiver-operating curve analysis revealed an area under the curve of 0.83 (95% CI, 0.74 to 0.9; P = 0.005) for detecting an SvO2 below 50% by ScO2min with the INVOS and 0.51 (95% CI, 0.41 to 0.62; P = 0.92), respectively, with the ForeSight. CONCLUSIONS: These findings suggest that the cerebral oximeters tested react differently to variations in systemic oxygenation and in their relationship with SvO2 and thus give different information on cardiopulmonary function. These findings raise doubt about whether these devices should be used interchangeably.


Assuntos
Encéfalo/metabolismo , Oxigênio/metabolismo , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Oximetria , Estudos Prospectivos
17.
Artigo em Alemão | MEDLINE | ID: mdl-29772591

RESUMO

Patients undergoing cardiac surgery are growing older, present with more comorbidities, and are frequently scheduled for more complex and prolonged surgical procedures. Routine application of neurological as well as extended hemodynamic monitoring combined with goal-directed perioperative hemodynamic optimization, targeting optimization of systemic and cerebral oxygen balance, show promise to reduce postoperative complications and to improve mortality in this high risk population. Expert recommendations suggest to avoid synthetic colloids for fluid optimization. Additionally, pathophysiological reasoning and results from recent trials suggest to start inotropic and vasoactive therapy primarily with non-adrenergic drugs like levosimendan and vasopressin and to add classical catecholamines like dobutamine and noradrenalin only if necessary to accomplish hemodynamic goals.


Assuntos
Anestesia/métodos , Procedimentos Cirúrgicos Cardíacos/métodos , Hemodinâmica , Monitorização Intraoperatória/métodos , Ecocardiografia Transesofagiana , Humanos , Masculino , Pessoa de Meia-Idade , Medicação Pré-Anestésica
18.
Anal Chem ; 89(17): 9368-9374, 2017 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-28727447

RESUMO

Dielectric barrier discharge (DBD)-based analytical applications have experienced rapid development in recent years. DBD designs and parameters and the application they are used for can vary considerably. This leads to a diverse field with many apparently unique systems that are all based on the same physical principle. The most significant changes among DBDs used for chemical analysis are in how the discharge electrodes are separated from the ignited discharge gas. While the official definition of a DBD states that at least one electrode has to be covered by a dielectric to be considered a DBD, configurations with both electrodes covered by dielectric layers can also be realized. The electrode surface plays a major role in several plasma-related technical fields, surface treatment or sputtering processes, for example, and has hence been studied in great detail. Analytical DBDs are often operated at low power and atmospheric pressure, making a direct transfer of insight and know-how gained from the aforementioned well-studied fields complicated. This work focuses on comparing two DBD configurations: the low temperature plasma probe (LTP) and the dielectric barrier discharge for soft ionization (DBDI). The LTP is representative of a DBD with one covered electrode and the DBDI of a design in which both electrodes are covered. These two configurations are well suited for a systematic comparison due to their similar geometric designs based on a dielectric capillary.

19.
Crit Care ; 21(1): 105, 2017 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-28499395

RESUMO

BACKGROUND: A decrease in blood lactate levels (Lac) >10% during the first hours of resuscitation in sepsis is associated with better outcomes, but the mechanisms are unclear. Our objective was to investigate the relationship between the time course of Lac, inflammatory response, and mitochondrial respiration during experimental sepsis. METHODS: Original data from two previously published studies were reanalyzed. In cohort 1, pigs were randomized to be resuscitated for 48 h starting at 6, 12, and 24 h, respectively, after fecal peritonitis induction (n = 8 each). Animals were categorized according to the decrease in Lac during the first 6 h of resuscitation (early if ≥10% [Lac ≥10%] or late if <10% or increased [Lac <10%]), and systemic hemodynamics, inflammatory parameters, and mitochondrial function were compared between groups. In a second group of animals with fecal peritonitis and 24 h of resuscitation (n = 16, cohort 2), abdominal regional Lac exchange was measured, and animals were categorized according to the decrease in Lac as in cohort 1. RESULTS: Overall mortality was 20% (4 of 20) in the Lac ≥10% group and 60% (12 of 20) in the Lac <10% group (p = 0.022). In cohort 1, systemic hemodynamics were similar in the Lac ≥10% (n = 13) and Lac <10% (n = 11) groups. Plasma interleukin-6 levels increased during unresuscitated sepsis and decreased during resusciation in both groups, but they were lower at study end in the Lac ≥10% group (p = 0.047). Complexes I and II maximal (state 3) and resting (state 4) isolated brain mitochondrial respiration at study end was higher in the Lac ≥10% group than in the Lac <10% group, whereas hepatic, myocardial, and skeletal muscle mitochondrial respiration was similar in both groups. In cohort 2, mesenteric, total hepatic, and renal blood flow at study end was higher in the Lac ≥10% group (n = 7) than in the Lac <10% group (n = 9), despite similar cardiac output. Hepatic lactate influx and uptake in the Lac ≥10% group were approximately 1.5 and 3 times higher, respectively, than in the Lac <10% group (p = 0.066 for both). CONCLUSIONS: A decrease in Lac >10% during early resuscitation (6 h) after abdominal sepsis is associated with lower levels of plasma interleukin-6 and improved brain but not hepatic or muscle mitochondrial respiration. Blood flow redistribution to abdominal organs in animals with early decrease in Lac concentrations increases the potential to both deliver and extract Lac.


Assuntos
Inflamação/metabolismo , Ácido Láctico/análise , Mitocôndrias/metabolismo , Sepse/complicações , Fatores de Tempo , Animais , Gasometria/métodos , Proteína C-Reativa/análise , Estudos de Coortes , Modelos Animais de Doenças , Hemodinâmica/fisiologia , Interleucina-6/análise , Interleucina-6/sangue , Ácido Láctico/sangue , Oxigênio/metabolismo , Peritonite/complicações , Peritonite/fisiopatologia , Distribuição Aleatória , Ressuscitação/métodos , Sepse/mortalidade , Sepse/fisiopatologia , Análise de Sobrevida , Suínos , Fator de Necrose Tumoral alfa/análise , Fator de Necrose Tumoral alfa/sangue
20.
Anal Chem ; 88(10): 5538-41, 2016 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-27121975

RESUMO

Besides the progress of new mass spectrometer technologies, the investigation and development of soft ionization sources play an important key role for analytical sciences. Since the dielectric barrier discharge ionization (DBDI) is identified as two temporally separated events, a selective prevention of the coincident plasma can lead to improved ionization strength. Although a DBDI is known as a soft ionization source, a modulation of the high-voltage amplitude and duty cycle can lead to optimized ionization strength. This is an advantage to cover different types of analytes.

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