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1.
Span J Psychol ; 20: E5, 2017 Feb 06.
Article in English | MEDLINE | ID: mdl-28162134

ABSTRACT

The usual emotional experience of the person (affective style) is an influential factor in therapeutic assimilation. Based on a dynamic model of affect shaped dimensionally by the valence and arousal axes (core affect) that fluctuate over time according to the specific context of the individual, its relationship with different variables was investigated and the changes after a 6-month intervention in a specialized hospital unit (N = 103) were observed. The orthogonal structure of core-affect was confirmed. Emotional valence appeared to be positively related to social skills (r = .375; p < .01) and self-esteem (r = .491; p < .01) and negatively to depressive symptoms (r = -.631; p < .01), general disturbance (r = -.395; p < .01) and suicidality (r = -.490; p < .01). Emotional arousal is associated with impulsivity (r = .345; p < .01). The group of patients with an affective style characterized by negative valence and low arousal core-affect gained less therapeutic benefit compared to those with positive valence core-affect (p < .05). Throughout the treatment, valence became more positive (d = .26; IC 95%: 1.9 - 7.2; p = .001), arousal increased (d = .23; IC 95%: 0.2 - 1.7; p = .015) and variability decreased (d = -.44; IC 95%: (-2.9) - (-1.1); p = .001). Changes in the core-affect are related to therapeutic improvement. Adjusting expectations of change can reduce therapeutic frustration, which is as common as it is harmful in the treatment of severe personality disorders.


Subject(s)
Affect/physiology , Personality Disorders/physiopathology , Personality Disorders/therapy , Psychotherapy/methods , Adult , Female , Humans , Male , Middle Aged , Treatment Outcome , Young Adult
2.
Span. j. psychol ; 20: e5.1-e5.11, 2017. tab, graf
Article in English | IBECS | ID: ibc-160548

ABSTRACT

The usual emotional experience of the person (affective style) is an influential factor in therapeutic assimilation. Based on a dynamic model of affect shaped dimensionally by the valence and arousal axes (core affect) that fluctuate over time according to the specific context of the individual, its relationship with different variables was investigated and the changes after a 6-month intervention in a specialized hospital unit (N = 103) were observed. The orthogonal structure of core-affect was confirmed. Emotional valence appeared to be positively related to social skills (r = .375; p < .01) and self-esteem (r = .491; p < .01) and negatively to depressive symptoms (r = -.631; p < .01), general disturbance (r = -.395; p < .01) and suicidality (r = -.490; p < .01). Emotional arousal is associated with impulsivity (r = .345; p < .01). The group of patients with an affective style characterized by negative valence and low arousal core-affect gained less therapeutic benefit compared to those with positive valence core-affect (p < .05). Throughout the treatment, valence became more positive (d = .26; IC 95%: 1.9 - 7.2; p = .001), arousal increased (d = .23; IC 95%: 0.2 - 1.7; p = .015) and variability decreased (d = -.44; IC 95%: (-2.9) - (-1.1); p = .001). Changes in the core-affect are related to therapeutic improvement. Adjusting expectations of change can reduce therapeutic frustration, which is as common as it is harmful in the treatment of severe personality disorders (AU)


No disponible


Subject(s)
Humans , Male , Female , Young Adult , Adult , Middle Aged , Personality Disorders/epidemiology , Personality Disorders/psychology , Affect/physiology , Expressed Emotion/physiology , Social Skills , Depression/complications , Depression/psychology , Treatment Outcome , Psychopathology/methods , Psychopathology/trends , Surveys and Questionnaires , 28599
3.
Psicol. conduct ; 25(1): 25-45, 2017. tab, graf
Article in Spanish | IBECS | ID: ibc-162152

ABSTRACT

El variado curso que caracteriza la evolución de los trastornos de la personalidad (TP) y la respuesta diversa de los pacientes a las intervenciones terapéuticas hacen que el concepto de gravedad de los TP esté en el debate actual de clínicos e investigadores. En un trabajo previo (Ramos, Sendra, Sánchez y Mena, 2015) propusimos un índice de gravedad basado en el solapamiento de rasgos patológicos; ahora analizamos el cambio en gravedad tras un tratamiento especializado de 6 meses. En 93 pacientes que completaron el programa (51,4% de la muestra total) hallamos una reducción de la perturbación general (d= 1,193) y afectiva (d= 0,990), de rasgos de TP y de gravedad (d= 0,753). Sin embargo, no aparecen efectos de interacción entre cambio y gravedad, ni ésta predice por sí sola el resultado terapéutico. Se discuten los datos a la luz de otros hallazgos. La estabilidad de los TP no parece residir en el cumplimiento de criterios diagnósticos, sino en un núcleo de vulnerabilidad compartido por todos los pacientes, independientemente de su categorización prototípica y de su fluctuación sintomatológica


The varied course of evolution of personality disorders (PD) and patients’ different responses to therapeutic interventions position the concept of severity of PD amongst the greatest concerns to clinicians and researchers. In a previous study (Ramos, Sendra, Sánchez, & Mena, 2015) we proposed an index of severity of PD based on the overlap of pathological traits; now we analyze the change in severity after 6 months of specialized treatment. In 93 patients who completed the program (51.4% of the total sample) we found a reduction in general (d=1.193) and affective (d= 0.990) disturbance, also in PD traits and severity (d=0.753). Nevertheless, interaction effects between change and severity did not appear; neither did severity by itself predict therapeutic results. We discuss the data in the light of other findings. The stability of the PD does not seem to reside in the fulfillment of diagnostic criteria, but in a core of vulnerability shared by all the patients, independently of the prototypical categorization and the symptomatology fluctuation


Subject(s)
Humans , Personality Disorders/therapy , Behavioral Symptoms/psychology , Psychotherapy/statistics & numerical data , Severity of Illness Index , Evaluation of Results of Therapeutic Interventions , Psychometrics/methods
4.
Psicol. conduct ; 23(1): 65-83, ene.-abr. 2015. tab, graf
Article in Spanish | IBECS | ID: ibc-139097

ABSTRACT

Diversos modelos centrados en la gravedad del trastorno de personalidad (TP) se erigen como alternativa a los tradicionales planteamientos categoriales, confirmando su alto valor predictivo en la evaluación del funcionamiento social y en la comorbilidad con otros trastornos. En este trabajo examinamos la relación entre gravedad del TP (acumulación de diferentes rasgos de personalidad patológica e intensidad de cada uno de ellos) y grado de malestar sintomático en una muestra de 142 pacientes. El análisis bivariante confirma en el grupo de alta gravedad un mayor nivel de perturbación general (p= 0,013) y afectiva (p= 0,036). El análisis multivariante detecta, sin embargo, que la intensidad de rasgos esquizotípicos, autodestructivos y pasivo-agresivos explica la perturbación sintomática mejor que la acumulación de rasgos de personalidad patológica. Se discuten estos hallazgos en el contexto de la complejidad conceptual y evaluativa del constructo TP. La búsqueda de un índice adecuado de gravedad sigue pendiente en el esfuerzo por mejorar la planificación y una provisión objetiva de recursos sociosanitarios


Several models focused on the severity of personality disorders (PD) have been proposed as an alternative to the traditional categorical approach, confirming their high predictive value in the evaluation of social functioning and comorbidity with other disorders. In this work, we examined the relationship between personality severity (accumulation of different traits of pathological personality and intensity of each of them) and degree of symptomatic disturbance in a sample of 142 patients. The bivariate analysis confirms that the high personality severity group has higher level of affective (p= .036) and general (p=.013) disruption. However, multivariate analysis found that the intensity of schizotypal, self-destructive and passive-aggressive traits explains symptomatic disturbance better than the accumulation of traits. These findings are discussed in the context of conceptual and evaluative complexity of the personality disorder construct. The search for an appropriate index of severity is still pending in the effort to improve the planning and objective provision of social and health resources


Subject(s)
Adult , Female , Humans , Male , Young Adult , Personality Disorders/diagnosis , Personality Disorders/epidemiology , Personality Disorders/therapy , Epidemiological Monitoring/trends , Quality of Life , Social Adjustment , Psychopathology , Millon Clinical Multiaxial Inventory , Psychometrics , Multivariate Analysis , Diagnostic and Statistical Manual of Mental Disorders , Borderline Personality Disorder/diagnosis , Comorbidity , Spain/epidemiology
5.
J Chromatogr A ; 1315: 1-7, 2013 Nov 08.
Article in English | MEDLINE | ID: mdl-24094484

ABSTRACT

A new sensitive multiresidue method based on ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) has been developed for the detection, confirmation and quantification of twenty five carbamates in wine samples. The separation was achieved in 5.5 min, using a Zorbax Eclipse plus RRHD C18 column (50 mm×2.1 mm, 1.8 µm), with a mobile phase of water and methanol, both of them with 0.01% formic acid. The analytes were detected in positive mode with multiple reaction monitoring mode. Ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME), using a low-density extraction solvent has been optimized for the satisfactory extraction of carbamates and clean-up of extracts. The matrix effect was studied, showing that the proposed procedure provides very clean extracts. Under optimum conditions, recoveries for fortified wine samples ranged from 74 to 102%, with relative standard deviations lower than 6%. Limits of quantification ranged from 0.15 to 0.92 µgl(-1), showing the high sensitivity of this fast and simple method and its compliance with current requirements.


Subject(s)
Carbamates/analysis , Chemical Fractionation/methods , Chromatography, High Pressure Liquid/methods , Tandem Mass Spectrometry/methods , Wine/analysis , Emulsions , Reproducibility of Results , Sensitivity and Specificity , Sonication
6.
J Chromatogr A ; 1247: 26-34, 2012 Jul 20.
Article in English | MEDLINE | ID: mdl-22673815

ABSTRACT

A new analytical method based on micellar electrokinetic chromatography tandem mass spectrometry (MEKC-ESI-MS/MS) employing a MS friendly surfactant (ammonium perfluorooctanoate) is proposed and validated for the identification and simultaneous quantification of 17 N-methylcarbamate pesticides in environmental and drinking water samples. MS/MS detection using an ion trap as analyzer operating in the multiple reaction monitoring mode was used. Different parameters were optimized in order to obtain an adequate CE separation combined with the highest sensitivity in MS/MS. Dispersive liquid-liquid microextraction (DLLME) using a low-density extraction solvent has been proposed for extraction, obtaining a preconcentration factor of 10. Under optimum conditions, recoveries for fortified samples ranged from 83% to 101%, with relative standard deviations lower than 8%. The limits of detection ranged from 1 to 144 ng l⁻¹, demonstrating the sensitivity and applicability of this fast, simple, and environmentally friendly method.


Subject(s)
Carbamates/analysis , Chromatography, Micellar Electrokinetic Capillary/methods , Liquid Phase Microextraction/methods , Spectrometry, Mass, Electrospray Ionization/methods , Caprylates/chemistry , Carbamates/isolation & purification , Fluorocarbons/chemistry , Limit of Detection , Linear Models , Reproducibility of Results , Surface-Active Agents/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/isolation & purification
7.
Anal Chim Acta ; 724: 1-11, 2012 Apr 29.
Article in English | MEDLINE | ID: mdl-22483203

ABSTRACT

The characterization and authentication of fats and oils is a subject of great importance for market and health aspects. Identification and quantification of triacylglycerols in fats and oils can be excellent tools for detecting changes in their composition due to the mixtures of these products. Most of the triacylglycerol species present in either fats or oils could be analyzed and identified by chromatographic methods. However, the natural variability of these samples and the possible presence of adulterants require the application of chemometric pattern recognition methods to facilitate the interpretation of the obtained data. In view of the growing interest in this topic, this paper reviews the literature of the application of exploratory and unsupervised/supervised chemometric methods on chromatographic data, using triacylglycerol composition for the characterization and authentication of several foodstuffs such as olive oil, vegetable oils, animal fats, fish oils, milk and dairy products, cocoa and coffee.


Subject(s)
Fats/analysis , Food Analysis/methods , Oils/analysis , Triglycerides/analysis , Chromatography, Gas , Chromatography, High Pressure Liquid , Chromatography, Thin Layer , Discriminant Analysis , Mass Spectrometry , Principal Component Analysis
8.
Anal Bioanal Chem ; 400(5): 1329-38, 2011 May.
Article in English | MEDLINE | ID: mdl-21279629

ABSTRACT

Dispersive liquid-liquid microextraction (DLLME) has been proposed for the extraction and preconcentration of 12 carbamate pesticides in juice samples, followed by their determination by micellar electrokinetic chromatography with diode-array detection. To improve sensitivity, an on-capillary sample concentration method based on sweeping has been developed. Also, separations were performed in an extended light path fused-silica capillary; the separation buffer consisted of 100 mM borate and 50 mM SDS (pH 9.0) with 5% acetonitrile. Samples were introduced by hydrodynamic injection, dissolved in the separation buffer, but free of micelles. Several parameters of the DLLME procedure (such as type and volume of extraction and dispersive solvents, pH, salt addition, and extraction time) were optimized. Recoveries obtained for fortified juice samples (banana, pineapple, and tomato) at three different concentration levels, ranged from 78% to 105%, with relative standard deviations lower than 9%. The limits of detection ranged from 1 to 7 µg l(-1). Moreover, the method is fast, simple, and environmentally friendly.


Subject(s)
Beverages/analysis , Carbamates/isolation & purification , Chemical Fractionation/methods , Chromatography, Micellar Electrokinetic Capillary/methods , Pesticides/isolation & purification , Carbamates/analysis , Limit of Detection , Pesticides/analysis
10.
Electrophoresis ; 29(10): 2117-25, 2008 May.
Article in English | MEDLINE | ID: mdl-18409156

ABSTRACT

We have developed and validated a CE-MS/MS method using an in-line SPE device (analyte concentrator, AC) to determine eight quinolones of veterinary use whose maximum residue levels in animal edible tissues are established by the EU Council Regulation 2377/90, i.e., danofloxacin, sarafloxacin, ciprofloxacin, marbofloxacin, enrofloxacin, difloxacin, oxolinic acid, and flumequine. Different parameters affecting the AC performance, such as its design (in this case frit-free), the kind of sorbent (Oasis MCX), sample pH, volume, and composition of the elution plug and injection time were studied. The method was validated using standard solutions obtaining LODs between 17 and 59 ng/L. Finally, a pressurized liquid extraction (PLE) method was developed to determine these antibiotics in chicken muscle samples. The whole analytical method was validated in terms of linearity (r2 >or= 0.992), recoveries (63-112%), repeatability and intermediate precision (RSD

Subject(s)
Drug Residues/analysis , Electrophoresis, Capillary/methods , Meat/analysis , Quinolones/analysis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Animals , Chickens , Electrophoresis, Capillary/instrumentation , Electrophoresis, Capillary/statistics & numerical data , Food Contamination/analysis , Reproducibility of Results , Solid Phase Extraction/instrumentation , Solid Phase Extraction/statistics & numerical data , Spectrometry, Mass, Electrospray Ionization/instrumentation , Spectrometry, Mass, Electrospray Ionization/methods , Tandem Mass Spectrometry/instrumentation , Tandem Mass Spectrometry/statistics & numerical data
11.
Anal Chem ; 78(22): 7665-73, 2006 Nov 15.
Article in English | MEDLINE | ID: mdl-17105157

ABSTRACT

A new analytical method based on capillary zone electrophoresis-tandem mass spectrometry (CZE-MS/MS) is proposed and validated for the identification and simultaneous quantification of eight quinolones for veterinary use in bovine raw milk. The studied quinolones include danofloxacin, sarafloxacin, ciprofloxacin, marbofloxacin, enrofloxacin, difloxacin, oxolinic acid, and flumequine, whose contents are regulated by the EU Council Regulation no. 2377/90 in animal edible tissues. Different parameters (i.e., separation buffer composition and electrospray conditions) were optimized in order to obtain both an adequate CE separation and a high sensitivity, using experimental design methodology to consider the interactions among the studied variables. MS/MS experiments using an ion trap as analyzer operating in the multiple reaction monitoring mode were carried out to achieve the minimum number of identification points according to the 2002/657/EC European Decision. For the quantification in bovine raw milk samples, a two-step solid-phase extraction procedure was developed using Oasis MAX and HLB cartridges without protein precipitation. Satisfactory results were obtained in terms of linearity (r2 between 0.989 and 0.992) and precision (RSD below 18%). The limits of detection and quantification (below 6 and 24 ppb, respectively) were in all cases lower than the maximum residues limits tolerated for these compounds in milk, the recoveries ranging from 81 to 110%, indicating the potential of the CZE-MS/MS for the analysis of regulated quinolone antibiotics in the food quality and safety control areas.


Subject(s)
Anti-Bacterial Agents/analysis , Electrophoresis, Capillary/methods , Milk/chemistry , Quinolones/analysis , Tandem Mass Spectrometry/methods , 2-Propanol/chemistry , Air Pressure , Animals , Cattle , Nebulizers and Vaporizers , Reference Values , Reproducibility of Results
12.
Electrophoresis ; 27(12): 2348-59, 2006 Jun.
Article in English | MEDLINE | ID: mdl-16718647

ABSTRACT

A CE instrument coupled with chemiluminescence (CL) detection was designed for the determination of promethazine hydrochloride (PTH) and promazine hydrochloride (PMH) in real samples. An important enhancement of the CL emission of luminol with potassium ferricyanide was observed in the presence of these phenothiazines; so this system was selected for their detection after CE separation. Parameters affecting the electrophoretic separation were optimized in a univariate way, while those affecting CL detection were optimized by means of a multivariate approach based on the use of experimental designs. Chemometrics was also employed for the study of the robustness of the factors influencing the postcolumn CL detection. The method allows the separation of the phenothiazines in less than 4 min, achieving LODs of 80 ng/mL for PMH and 334 ng/mL for PTH, using sample injection by gravity. Electrokinetic injection was used to obtain lower LODs for the determination of the compounds in biological samples. The applicability of the CE-CL method was illustrated in the determination of PTH in pharmaceutical formulations and in the analysis of PMH in human urine, using a previous SPE procedure, achieving an LOD of 1 ng/mL and recoveries higher than 85%.


Subject(s)
Antipsychotic Agents/analysis , Electrophoresis, Capillary/methods , Phenothiazines/analysis , Antipsychotic Agents/urine , Chemistry, Pharmaceutical , Dosage Forms , Humans , Luminescent Measurements , Phenothiazines/urine , Sensitivity and Specificity
13.
Talanta ; 69(3): 763-8, 2006 May 15.
Article in English | MEDLINE | ID: mdl-18970635

ABSTRACT

A simple and sensitive procedure for the determination of gentamicin is presented, based on the use of the peroxyoxalate chemiluminescent (PO-CL) system in presence of imidazole as a catalyst. The gentamicin has to be previously derivatized with o-phthaladehyde (OPA) in order to obtain a fluorophore, which participates in the PO reaction, producing a CL emission proportional to the gentamicin concentration. The method is developed by using a particular flow-injection analysis (FIA) manifold, employing sodium dodecyl sulfate (SDS) micellar medium as a carrier in order to avoid the degradation of PO in water. The optimization of the instrumental and chemical variables affecting the CL reaction was rigorously carried out by using experimental design methodology. The method has been successfully applied to pharmaceutical formulations.

14.
Med Clin (Barc) ; 125(17): 641-6, 2005 Nov 12.
Article in Spanish | MEDLINE | ID: mdl-16324492

ABSTRACT

BACKGROUND AND OBJECTIVE: Myocardial infarction is one of the leading causes of death in Spain. This study assesses in-hospital mortality and associated factors. PATIENTS AND METHOD: Mortality of episodes of initial attention of myocardial infarction attended in hospitals was analyzed using the 2001 Minimum Basic Group of Data corresponding to the Community of Madrid in relation with sociodemographic, hospitals, procedures, risk factors and comorbidities. Statistical descriptive techniques and logistic regression analyses were employed to analyze the data. RESULTS: 5,306 cases of myocardial infarction were studied. 71% were men and the mean age was 68 year. 73% were admitted in high technology hospitals, 49% received coronary angiography and 29% received a stent. Mortality rate was 10.8%. Multivariable analysis showed that increase in age, presence of arrhythmias, congestive heart failure, renal failure, cardiogenic shock and cerebrovascular disease were associated with in-hospital mortality, while admission in centers attending between 100 and 300 myocardial infarction cases, use of coronary angiography and stent, and previous history of arterial hypertension, smoking and high lipid levels, appeared to be protective factors. CONCLUSIONS: Mortality estimated with an administrative data-base is similar than the mortality estimated in studies based on clinical data sets. Mortality is associated with several variables; although some of them have been previously reported, others need further investigations to confirm their relevance.


Subject(s)
Hospital Mortality/trends , Myocardial Infarction/mortality , Aged , Aged, 80 and over , Female , Humans , Male , Middle Aged , Risk Factors
15.
Med. clín (Ed. impr.) ; 125(17): 641-646, nov. 2005. tab
Article in Es | IBECS | ID: ibc-041069

ABSTRACT

Fundamento y objetivo: El infarto de miocardio es una de las principales causas de muerte en España. Este estudio analiza su mortalidad intrahospitalaria y los factores asociados con ella. Pacientes y método: La mortalidad de los episodios de atención inicial de infarto de miocardio asistidos en hospitales se estudia mediante el conjunto mínimo básico de datos de la comunidad de Madrid del año 2001, en función de variables sociodemográficas, hospitalarias, procedimientos, factores de riesgo y comorbilidades. Se utilizan técnicas estadísticas descriptivas y regresión logística uni y multivariante para analizar los datos. Resultados: Se estudian 5.306 casos de infarto de miocardio. El 71% son varones y la edad media es de 68 años. El 73% ingresa en hospitales de alta tecnología. El 49% recibe una coronariografía y el 29% una revascularización percutánea con dispositivo intravascular (stent). La mortalidad es del 10,8%. En el análisis multivariante, el incremento de edad, la presencia de arritmias, la insuficiencia cardíaca congestiva, la insuficiencia renal, el shock cardiogénico y la enfermedad cerebrovascular se asocian con una mayor mortalidad, mientras que el ingreso en centros que atienden entre 100 y 300 infartos, la utilización de coronariografía y stent, y los antecedentes de hipertensión arterial, tabaquismo e hiperlipemia, aparecen como factores protectores. Conclusiones: La mortalidad intrahospitalaria del infarto de miocardio estimada mediante una base de datos administrativa es similar a la detectada por estudios de base clínica. La mortalidad se asocia a un conjunto de variables, algunas ya contrastadas en la literatura médica y otras susceptibles de confirmar en futuros estudios


Patients and method: Mortality of episodes of initial attention of myocardial infarction attended in hospitals was analyzed using the 2001 Minimum Basic Group of Data corresponding to the Community of Madrid in relation with sociodemographic, hospitals, procedures, risk factors and comorbidities. Statistical descriptive techniques and logistic regression analyses were employed to analyze the data. Results: 5,306 cases of myocardial infarction were studied. 71% were men and the mean age was 68 year. 73% were admitted in high technology hospitals, 49% received coronary angiography and 29% received a stent. Mortality rate was 10.8%. Multivariable analysis showed that increase in age, presence of arrhythmias, congestive heart failure, renal failure, cardiogenic shock and cerebrovascular disease were associated with in-hospital mortality, while admission in centers attending between 100 and 300 myocardial infarction cases, use of coronary angiography and stent, and previous history of arterial hypertension, smoking and high lipid levels, appeared to be protective factors. Conclusions: Mortality estimated with an administrative data-base is similar than the mortality estimated in studies based on clinical data sets. Mortality is associated with several variables; although some of them have been previously reported, others need further investigations to confirm their relevance


Subject(s)
Male , Female , Aged , Middle Aged , Humans , Myocardial Infarction/mortality , Hospitalization/statistics & numerical data , Risk Factors , Spain/epidemiology , Homeopathic Clinical-Dynamic Prognosis/methods , Hospital Statistics , Myocardial Ischemia/epidemiology , Myocardial Revascularization , Coronary Disease/diagnosis
16.
Electrophoresis ; 26(12): 2418-29, 2005 Jun.
Article in English | MEDLINE | ID: mdl-15924366

ABSTRACT

A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %).


Subject(s)
Electrophoresis, Capillary/methods , Phenothiazines/isolation & purification , Phenothiazines/urine , Chemical Fractionation , Humans , Microchemistry/methods , Reproducibility of Results , Sensitivity and Specificity
17.
Talanta ; 63(4): 1061-7, 2004 Jul 08.
Article in English | MEDLINE | ID: mdl-18969534

ABSTRACT

A review of the use of the Doehlert matrix as a chemometric tool for the optimization of methods in analytical chemistry and other sciences is presented. The theoretical principles of Doehlert designs are described, including the coded values for the use of this matrix involving two, three, four and five variables. The advantages of this matrix in comparison with other response surface designs, such as central composite and Box-Behnken, designs are discussed. Finally, 57 references concerning the application of Doehlert matrices in the optimization of procedures involving spectroanalytical, electroanalytical and chromatographic techniques are considered.

18.
Anal Sci ; 19(10): 1431-9, 2003 Oct.
Article in English | MEDLINE | ID: mdl-14596412

ABSTRACT

The determination of stoichiometries and stability constants of complexes by means of UV-visible spectrophotometry applying traditional methods does not evaluate the quality of the values obtained, since the classic application of these methods does not provide coverage intervals. However, the use of chemometric techniques in different steps of the application of these methods makes it possible to obtain not only a real value of the characteristics of the complexes but a validation of such a value. In this paper a methodology is proposed that combines some traditional methods, three different regression models (LMSR, LSR and LSPR) and a small number of mathematical algorithms. This methodology is able to estimate, in a simple and rigorous way, the stoichiometry and stability constant of a complex and its corresponding uncertainties.

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