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1.
J Neuroeng Rehabil ; 21(1): 82, 2024 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-38769565

RESUMEN

BACKGROUND: Assessments of arm motor function are usually based on clinical examinations or self-reported rating scales. Wrist-worn accelerometers can be a good complement to measure movement patterns after stroke. Currently there is limited knowledge of how accelerometry correlate to clinically used scales. The purpose of this study was therefore to evaluate the relationship between intermittent measurements of wrist-worn accelerometers and the patient's progression of arm motor function assessed by routine clinical outcome measures during a rehabilitation period. METHODS: Patients enrolled in in-hospital rehabilitation following a stroke were invited. Included patients were asked to wear wrist accelerometers for 24 h at the start (T1) and end (T2) of their rehabilitation period. On both occasions arm motor function was assessed by the modified Motor Assessment Scale (M_MAS) and the Motor Activity Log (MAL). The recorded accelerometry was compared to M_MAS and MAL. RESULTS: 20 patients were included, of which 18 completed all measurements and were therefore included in the final analysis. The resulting Spearman's rank correlation coefficient showed a strong positive correlation between measured wrist acceleration in the affected arm and M-MAS and MAL values at T1, 0.94 (p < 0.05) for M_MAS and 0.74 (p < 0.05) for the MAL values, and a slightly weaker positive correlation at T2, 0.57 (p < 0.05) for M_MAS and 0.46 - 0.45 (p = 0.06) for the MAL values. However, no correlation was seen for the difference between the two sessions. CONCLUSIONS: The results confirm that the wrist acceleration can differentiate between the affected and non-affected arm, and that there is a positive correlation between accelerometry and clinical measures. Many of the patients did not change their M-MAS or MAL scores during the rehabilitation period, which may explain why no correlation was seen for the difference between measurements during the rehabilitation period. Further studies should include continuous accelerometry throughout the rehabilitation period to reduce the impact of day-to-day variability.


Asunto(s)
Acelerometría , Brazo , Rehabilitación de Accidente Cerebrovascular , Humanos , Acelerometría/instrumentación , Masculino , Femenino , Persona de Mediana Edad , Anciano , Rehabilitación de Accidente Cerebrovascular/métodos , Rehabilitación de Accidente Cerebrovascular/instrumentación , Brazo/fisiopatología , Brazo/fisiología , Muñeca/fisiología , Dispositivos Electrónicos Vestibles , Actividad Motora/fisiología , Adulto , Accidente Cerebrovascular/fisiopatología , Accidente Cerebrovascular/diagnóstico , Anciano de 80 o más Años
2.
Artículo en Inglés | MEDLINE | ID: mdl-35329318

RESUMEN

Recently, it was shown that sensory relearning of the upper limb (SENSUPP) is a promising intervention to improve sensorimotor function after stroke. There is limited knowledge, however, of how participants perceive the training. Here, we explored how persons with sensory impairments in the upper limb experienced the SENSUPP protocol (combined sensory- and motor training and home exercises for 5 weeks) and its effect. Fifteen persons (mean age 59 years; 10 men; >6 months post-stroke) were individually interviewed, and data were analyzed with qualitative content analysis. An overall theme 'Sensory relearning was meaningful and led to improved ability to perform daily hand activities' and two categories with six subcategories emerged. The outpatient training was perceived as meaningful, although the exercises were demanding and required concentration. Support from the therapist was helpful and training in small groups appreciated. The home training was challenging due to lack of support, time, and motivation. Small improvements in sensory function were perceived, whereas increased movement control and ability in performing daily hand activities were reported. In conclusion, the SENSUPP protocol is meaningful and beneficial in improving the functioning of the UL in chronic stroke. Improving compliance to the home training, regular follow-ups, and an exercise diary are recommended.


Asunto(s)
Rehabilitación de Accidente Cerebrovascular , Accidente Cerebrovascular , Terapia por Ejercicio , Femenino , Mano , Humanos , Masculino , Persona de Mediana Edad , Accidente Cerebrovascular/terapia , Rehabilitación de Accidente Cerebrovascular/métodos , Resultado del Tratamiento , Extremidad Superior
3.
PM R ; 14(12): 1461-1473, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-35049134

RESUMEN

BACKGROUND: Sensorimotor impairments of the upper limb (UL) are common after stroke, but there is a lack of evidence-based interventions to improve functioning of UL. OBJECTIVE: To evaluate (1) the efficacy of sensory relearning and task-specific training compared to task-specific training only, and (2) the feasibility of the training in chronic stroke. DESIGN: A pilot randomized controlled trial. SETTING: University hospital outpatient clinic. PARTICIPANTS: Twenty-seven participants (median age; 62 years, 20 men) were randomized to an intervention group (IG; n = 15) or to a control group (CG; n = 12). INTERVENTION: Both groups received training twice weekly in 2.5-hour sessions for 5 weeks. The training in the IG consisted of sensory relearning, task-specific training, and home training. The training in the CG consisted of task-specific training. MAIN OUTCOME MEASURES: Primary outcome was sensory function (touch thresholds, touch discrimination, light touch, and proprioception). Secondary outcomes were dexterity, ability to use the hand in daily activities, and perceived participation. A blinded assessor conducted the assessments at baseline (T1), post intervention (T2), and at 3-month follow-up (T3). Nonparametric analyses and effect-size calculations (r) were performed. Feasibility was evaluated by a questionnaire. RESULTS: After the training, only touch thresholds improved significantly from T1 to T2 (p = .007, r = 0.61) in the IG compared to the CG. Within the IG, significant improvements were found from T1 to T2 regarding use of the hand in daily activities (p = .001, r = 0.96) and movement quality (p = .004, r = 0.85) and from T1 to T3 regarding satisfaction with performance in meaningful activities (p = .004, r = 0.94). The CG significantly improved the performance of using the hand in meaningful activities from T1 to T2 (p = .017, r = 0.86). The training was well tolerated by the participants and performed without any adverse events. CONCLUSIONS: Combined sensory relearning and task-specific training may be a promising and feasible intervention to improve UL sensorimotor function after stroke.


Asunto(s)
Rehabilitación de Accidente Cerebrovascular , Accidente Cerebrovascular , Masculino , Humanos , Estudios de Factibilidad , Proyectos Piloto , Resultado del Tratamiento , Extremidad Superior , Recuperación de la Función
4.
Trials ; 22(1): 430, 2021 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-34225764

RESUMEN

BACKGROUND: Sensorimotor impairments of upper limb (UL) are common after stroke, leading to difficulty to use the UL in daily life. Even though many have sensory impairments in the UL, specific sensory training is often lacking in stroke rehabilitation. Thus, the aim of this paper is to provide a detailed description of the novel intervention "SENSory re-learning of the UPPer limb after stroke (SENSUPP)" that we have developed to improve functioning in the UL in persons with mild to moderate impairments after stroke. METHODS: The SENSUPP protocol was designed using information from literature reviews, clinical experience and through consultation of experts in the field. The protocol integrates learning principles based on current neurobiological knowledge and includes repetitive intensive practice, difficulty graded exercises, attentive exploration of a stimulus with focus on the sensory component, and task-specific training in meaningful activities that includes feedback. For reporting the SENSUPP protocol, the Template for Intervention Description and Replication (TIDieR) checklist was used. RESULTS: The essential features of the SENSUPP intervention comprise four components: applying learning principles based on current neurobiological knowledge, sensory re-learning (exercises for touch discrimination, proprioception and tactile object recognition), task-specific training in meaningful activities, and home-training. The training is performed twice a week, in 2.5-h sessions for 5 weeks. CONCLUSION: Since there is close interaction between the sensory and motor systems, the SENSUPP intervention may be a promising method to improve UL functioning after stroke. The TIDieR checklist has been very useful for reporting the procedure and development of the training. TRIAL REGISTRATION: ClinicalTrials.gov NCT03336749 . Registered on 8 November 2017.


Asunto(s)
Rehabilitación de Accidente Cerebrovascular , Accidente Cerebrovascular , Lista de Verificación , Terapia por Ejercicio , Humanos , Recuperación de la Función , Accidente Cerebrovascular/diagnóstico , Accidente Cerebrovascular/terapia , Extremidad Superior
5.
Lakartidningen ; 1172020 01 28.
Artículo en Sueco | MEDLINE | ID: mdl-32016923

RESUMEN

The anti-diarrheal drug loperamide is a mu-opioid agonist with poor systemic bioavailability at standard doses. However, at very high doses bioavailability increases, due to saturation of P-glycoprotein and first-pass metabolism, leading both to opioid effects on the central nervous system and possible systemic side effects. There have been several reports in the literature recently regarding life-threatening cardiovascular symptoms after longstanding daily intake of massive loperamide doses. We hereby describe a patient with syncope who displayed wide QRS complexes and prolonged QTc intervals on ECG upon arrival to hospital. The patient developed typical bursts of torsade de pointes during a prolonged hospital course.


Asunto(s)
Antidiarreicos , Cardiopatías , Síndrome de QT Prolongado , Loperamida , Torsades de Pointes , Antidiarreicos/efectos adversos , Arritmias Cardíacas , Electrocardiografía , Humanos , Loperamida/efectos adversos , Torsades de Pointes/inducido químicamente
6.
PM R ; 11(8): 821-827, 2019 08.
Artículo en Inglés | MEDLINE | ID: mdl-30844135

RESUMEN

BACKGROUND: Reduced dexterity is common after stroke, which can affect the ability to perform upper limb daily activities. To improve upper limb function after stroke, it is important to understand which factors are most associated with dexterity. OBJECTIVE: To evaluate how several factors are associated with dexterity after stroke. DESIGN: Cross-sectional study. SETTING: A university hospital. PARTICIPANTS: A convenience sample of 75 persons (54 men and 21 women, mean age 66 years) with mild to moderate impairments of the upper limb after stroke. METHODS: Dexterity and potentially associated factors (age, gender, affected hand, social situation, vocational situation, grip strength, spasticity, sensory function, and pain) were evaluated by linear regression models. MAIN OUTCOME MEASUREMENTS: Dexterity was measured with the mini Sollerman Hand Function Test, sensory function with both the Fugl-Meyer Assessment of the Upper Extremity (to assess light touch and proprioception) and the Shape Texture Identification Test (to assess active discriminative touch), spasticity with the Modified Ashworth Scale, and grip strength with the Grippit dynamometer. RESULTS: Active discriminative touch had the strongest association with dexterity, explaining 46% of the variance. When spasticity and grip strength were added, the explained variance increased to 57% in the final multivariate model. CONCLUSIONS: This study indicates that sensory function in terms of active discriminative touch is a major contributing factor to dexterity in persons with mild to moderate stroke, whereas spasticity and grip strength may be of lesser importance. LEVEL OF EVIDENCE: III.


Asunto(s)
Lateralidad Funcional , Espasticidad Muscular/diagnóstico , Accidente Cerebrovascular/complicaciones , Tacto/fisiología , Extremidad Superior/fisiopatología , Anciano , Estudios Transversales , Evaluación de la Discapacidad , Femenino , Hospitales Universitarios , Humanos , Modelos Lineales , Masculino , Persona de Mediana Edad , Análisis Multivariante , Espasticidad Muscular/etiología , Examen Neurológico/métodos , Paresia/etiología , Paresia/fisiopatología , Medición de Resultados Informados por el Paciente , Examen Físico/métodos , Accidente Cerebrovascular/diagnóstico , Rehabilitación de Accidente Cerebrovascular/métodos , Suecia
7.
Trials ; 19(1): 229, 2018 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-29665842

RESUMEN

BACKGROUND: Many stroke survivors suffer from sensory impairments of their affected upper limb (UL). Although such impairments can affect the ability to use the UL in everyday activities, very little attention is paid to sensory impairments in stroke rehabilitation. The purpose of this trial is to investigate if sensory re-learning in combination with task-specific training may prove to be more effective than task-specific training alone to improve sensory function of the hand, dexterity, the ability to use the hand in daily activities, perceived participation, and life satisfaction. METHODS/DESIGN: This study is a single-blinded pilot randomized controlled trial (RCT) with two treatment arms. The participants will be randomly assigned either to sensory re-learning in combination with task-specific training (sensory group) or to task-specific training only (control group). The training will consist of 2.5 h of group training per session, 2 times per week for 5 weeks. The primary outcome measures to assess sensory function are as follows: Semmes-Weinstein monofilament, Shape/Texture Identification (STI™) test, Fugl-Meyer Assessment-upper extremity (FMA-UE; sensory section), and tactile object identification test. The secondary outcome measures to assess motor function are as follows: Box and Block Test (BBT), mini Sollerman Hand Function Test (mSHFT), Modified Motor Assessment Scale (M-MAS), and Grippit. To assess the ability to use the hand in daily activities, perceived participation, and life satisfaction, the Motor Activity Log (MAL), Canadian Occupational Performance Measure (COPM), Stroke Impact Scale (SIS) participation domain, and Life Satisfaction checklist will be used. Assessments will be performed pre- and post-training and at 3-month follow-up by independent assessors, who are blinded to the participants' group allocation. At the 3-month follow-up, the participants in the sensory group will also be interviewed about their general experience of the training and how effective they perceived the training. DISCUSSION: The results from this study can add new knowledge about the effectiveness of sensory re-learning in combination with task-specific training on UL functioning after stroke. If the new training approach proves efficient, the results can provide information on how to design a larger RCT in the future in persons with sensory impairments of the UL after stroke. TRIAL REGISTRATION: ClinicalTrials.gov, NCT03336749 . Registered on 8 November 2017.


Asunto(s)
Mano/inervación , Umbral Sensorial , Rehabilitación de Accidente Cerebrovascular/métodos , Accidente Cerebrovascular/terapia , Actividades Cotidianas , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Retroalimentación Sensorial , Femenino , Retroalimentación Formativa , Lateralidad Funcional , Humanos , Masculino , Persona de Mediana Edad , Actividad Motora , Satisfacción del Paciente , Proyectos Piloto , Calidad de Vida , Ensayos Clínicos Controlados Aleatorios como Asunto , Recuperación de la Función , Método Simple Ciego , Accidente Cerebrovascular/diagnóstico , Accidente Cerebrovascular/fisiopatología , Accidente Cerebrovascular/psicología , Suecia , Factores de Tiempo , Resultado del Tratamiento , Adulto Joven
8.
J Rehabil Med ; 50(1): 45-51, 2018 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-29068038

RESUMEN

OBJECTIVE: To describe stroke survivors' experiences of sensory impairment in the upper limb, the influence of such impairment on daily life, coping strategies used, and sensory training for the affected hand. DESIGN: A qualitative study with a content analysis approach. SUBJECTS: Fifteen post-stroke patients interviewed individually. RESULTS: Five categories emerged from the data: "Changed and varied perception of the sensation"; "Affected movement control"; "Problems using the hand in daily life"; "Various strategies to cope with upper limb disability"; and "Lack of sensory training". Numbness and tingling, changes in temperature sensitivity, and increased sensitivity to touch and pain were reported. Many subjects had difficulty adjusting their grip force and performing movements with precision. It was problematic and mentally fatiguing managing personal care and carrying out household and leisure activities. Practical adaptations, compensation with vision, increased concentration, and use of the less affected hand were strategies used to overcome difficulties. Despite their problems very few subjects had received any specific sensory training for the hand. CONCLUSION: Stroke survivors perceive that sensory impairment of the upper limb has a highly negative impact on daily life, but specific rehabilitation for the upper limb is lacking. These findings imply that the clinical management of upper limb sensory impairment after stroke requires more attention.


Asunto(s)
Actividades Cotidianas/psicología , Adaptación Psicológica/fisiología , Rehabilitación de Accidente Cerebrovascular/métodos , Accidente Cerebrovascular/complicaciones , Extremidad Superior/irrigación sanguínea , Adulto , Anciano , Femenino , Humanos , Masculino , Persona de Mediana Edad , Autoinforme
9.
PM R ; 7(10): 1035-1041, 2015 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-25819668

RESUMEN

BACKGROUND: Muscle weakness in the upper limb is common in persons with late effects of polio. To be able to measure muscle strength and follow changes over time, reliable measurements are needed. OBJECTIVE: To evaluate the intra-rater reliability of isometric and isokinetic arm and hand muscle strength measurements in persons with late effects of polio. DESIGN: A test-retest design. SETTINGS: A university hospital outpatient clinic. PARTICIPANTS: Twenty-eight persons (mean age 68 years, SD 11 years) with late effects of polio in their upper limbs. METHODS: Isometric shoulder abduction, isokinetic concentric elbow flexion and extension, isometric elbow flexion, and isometric grip strength were measured twice, 14 days apart. Reliability was evaluated with the intra-class correlation coefficient, the mean difference between the test sessions (d¯), together with the 95% confidence intervals for d¯ , the standard error of measurement (SEM and SEM%), the smallest real difference (SRD and SRD%), and Bland-Altman graphs. MAIN OUTCOME MEASUREMENTS: A fixed dynamometer (Biodex) was used to measure arm strength and an electronic dynamometer (GRIP-it) was used to measure grip strength. RESULTS: Intra-rater reliability was high, with intra-class correlation coefficients between 0.87 and 0.98. The SEM%, representing the smallest change for a group of persons, ranged from 7%-24% for all strength measurements, and the SRD%, representing the smallest change for an individual person, ranged from 20%-67%. CONCLUSION: Muscle strength in the upper limbs can be reliably measured in persons with late effects of polio. However, the measurement errors indicate that the method is more suitable to detect changes in muscle strength for a group of persons than for an individual person.


Asunto(s)
Fuerza Muscular/fisiología , Debilidad Muscular/diagnóstico , Síndrome Pospoliomielitis/complicaciones , Síndrome Pospoliomielitis/fisiopatología , Extremidad Superior , Adulto , Anciano , Anciano de 80 o más Años , Femenino , Humanos , Masculino , Persona de Mediana Edad , Dinamómetro de Fuerza Muscular , Debilidad Muscular/etiología , Variaciones Dependientes del Observador , Rango del Movimiento Articular/fisiología , Reproducibilidad de los Resultados
10.
Artículo en Inglés | MEDLINE | ID: mdl-20886006

RESUMEN

In order to elucidate aspects of the mechanism of the hydrolytic enzyme urease, theoretical calculations were undertaken on a model of the active site, using density functional theory. The bridging oxygen donor that has been found in the crystal structures was determined to be a hydroxide ion. The initial coordination of urea at the active site occurs most likely through the urea oxygen to the nickel ion with the lowest coordination number. This coordination can be made without much gain in energy. The calculations also showed that weak coordination of one of the urea amine nitrogen atoms to the second nickel atom is energetically feasible. Furthermore, a proposed mechanism including a tetrahedral intermediate generated by hydrolytic attack on the urea carbon by the bridging hydroxide was modeled, and the tetrahedral intermediate was found to be energetically unfavorable relative to terminal coordination of the substrate (urea).

11.
J Chromatogr A ; 1129(1): 1-8, 2006 Sep 29.
Artículo en Inglés | MEDLINE | ID: mdl-16934277

RESUMEN

A method for determining organophosphate esters in air samples using C8 Empore solid phase extraction (SPE) membranes has been developed. After the sampling the analytes trapped in the membrane are completely desorbed with methanol, using an extraction cell connected online to the organic modifier channel of a HPLC gradient pump. The addition of water to the mobile phase prior to analytical chromatography ensures that the analytes are refocused and efficiently separated. Sampling with Empore SPE membranes enables the collection of analytes in both the vapour phase and particulate matter. During the air sampling procedure no losses were observed after 24 h of sampling, yielding a total volume of 14.4 m3, even for the most volatile compound used in this investigation (trimethylphosphate). Complete desorption was observed for all the organophosphate esters and recoveries were greater than 95%, with a relative standard deviation of less than 8%. The limits of detection ranged between 0.4 and 19 pg/m3. The effect of particulate matter on the extraction efficiency was investigated in detail by spiking the membranes with reference standard material. It was also found that the SPE membranes could be stored for at least 5 days at room temperature without any evidence of loss. The efficacy of the method was verified using real samples from different common indoor environments. Interestingly, significant quantities of several phosphate esters were found in a NIST standard reference material (urban dust, SRM 1649a).


Asunto(s)
Contaminantes Atmosféricos/análisis , Cromatografía Liquida/métodos , Espectrometría de Masas/métodos , Compuestos Organofosforados/análisis , Contaminación del Aire/análisis , Monitoreo del Ambiente/métodos , Ésteres/análisis , Ésteres/química , Compuestos Organofosforados/química , Reproducibilidad de los Resultados
12.
J Chromatogr A ; 1099(1-2): 127-35, 2005 Dec 16.
Artículo en Inglés | MEDLINE | ID: mdl-16213509

RESUMEN

A new LC-MS method for the determination and characterization of three groups of commonly used organic explosives (nitroaromatic compounds, cyclic nitroamines and nitrate esters) was developed using a porous graphitic carbon (PGC) (Hypercarb) column. Twenty-one different explosive-related compounds--including 2,4,6-trinitrotoluene, its by-products and its degradation products--were chromatographically separated in a single analysis. This efficient separation facilitates the identification of the manufacturer of the explosive using the identified analytes as a fingerprint. A final, conclusive identification of the analytes can be obtained using LC-MS equipped with an atmospheric pressure chemical ionization (APCI) interface. Solvent effects on chromatographic behaviour were investigated, as were the effects of solvent mixtures and mobile phase additives. The number and the relative positions of the nitro groups within analyte molecules influence their order of elution; these effects were investigated. The data thus generated can be interpreted to support a hypothesis concerning the retention mechanism of nitro-containing compounds when using PGC. Limits of detection ranged from 0.5 to 41.2 ng. The new methodology described herein improves the sensitivity and selectivity of explosive detection. The effectiveness of the method is demonstrated by the analysis of soil samples containing explosives residue from test fields in Sweden and Afghanistan.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Explosiones , Grafito/química , Espectrometría de Masas/métodos , Compuestos Orgánicos/análisis , Presión Atmosférica , Sensibilidad y Especificidad , Espectrofotometría Ultravioleta
13.
Inorg Chem ; 43(26): 8252-62, 2004 Dec 27.
Artículo en Inglés | MEDLINE | ID: mdl-15606171

RESUMEN

Two new carboxylate-containing polydentate ligands have been synthesized, the symmetric ligand 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-aminomethyl)-4-methylphenol (ICIMP). The ligands have been used to prepare model complexes for the active site of the dinuclear nickel enzyme urease, viz. [Ni(2)(BCIMP)Ac(2)](-) (6), [Ni(2)(BCIMP)(Ph(2)Ac)(2)](-) (7), [Ni(2)(ICIMP)(Ph(2)Ac)(2)] (14), [Ni(4)(ICIMP)(2)(Ph(2)Ac)(2)][ClO(4)](2) (15), [Ni(4)(ICIMP)(2)(Ph(2)Ac)(2)(DMF)(2)][ClO(4)](2) (16), and [Ni(4)(ICIMP)(2)(Ph(2)Ac)(2)(urea)(H(2)O)][ClO(4)](2) (17), where the latter complex contains urea coordinated in a unidentate fashion through the carbonyl oxygen. The N(2)O-N(2)O(2) donor set of ICIMP provides a good framework for the preparation of urease models, but in some cases tetranuclear nickel complexes are formed due to coordination of the carboxylate moiety of one dinickel-ICIMP unit to one or both of the nickels of a second Ni(2) unit. Reactivity and kinetics studies of 7 and 15 show that these model complexes catalyze hydrolysis of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) at basic pH. In this assay, complexes based on the asymmetric ligand ICIMP exhibit a significantly faster rate of hydrolysis than the corresponding BCIMP complexes. Magnetic measurements indicate that there are weak antiferromagnetic interactions between the nickel ions in complex 16.


Asunto(s)
Bacillus/enzimología , Níquel/química , Compuestos Organometálicos/síntesis química , Ureasa/química , Sitios de Unión , Catálisis , Cristalografía por Rayos X , Ligandos , Modelos Moleculares , Conformación Molecular , Estructura Molecular , Estereoisomerismo , Ureasa/metabolismo
14.
Inorg Chem ; 43(18): 5681-7, 2004 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-15332820

RESUMEN

In an attempt to prepare structural and functional models for the active site of the hydrolytic enzyme zinc phosphotriesterase, five new zinc complexes of the ligands 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-methylimidazolyl)methyl)aminomethyl)-6-(N-carboxylmethyl-N-((1-methylimidazolyl)methyl)aminomethyl)-4-methylphenol (ICIMP) have been synthesized, viz. Na[Zn(2)(BCIMP)Ac(2)] (1), [Zn(2)(BCIMP)(Ph(2)Ac)] (2), [Zn(2)(ICIMP)Ac(2)] (3), [Zn(4)(ICIMP)(2)(Me(3)Ac)(2)][ClO(4)](2) (4), and [Zn(4)(ICIMP)(2)(Ph(2)Ac)(2)][ClO(4)](2) (5). The X-ray structure of complex 5 has been determined and reveals that the complex is a dimer of dimers in the solid state, which in solution dissociates to potent structural models. Studies using NMR show that only one carboxylate coligand bridges the dizinc units in the case of diphenyl acetate and pivalate, while the steric bulk of acetate is sufficiently small to permit the coordination of two acetates/dizinc unit. Functional studies involving the hydrolysis/transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) show that the complex with ICIMP (compound 5) has a significantly higher rate of catalysis than the BCIMP complex (compound 2). This is attributed to the vacant/labile coordination site that is available in the ICIMP complex but not the BCIMP complex.


Asunto(s)
Modelos Moleculares , Compuestos Organometálicos , Hidrolasas de Triéster Fosfórico/química , Zinc/química , Sitios de Unión , Catálisis , Cristalografía por Rayos X , ADN/química , ADN/metabolismo , Concentración de Iones de Hidrógeno , Hidrólisis , Cinética , Ligandos , Modelos Químicos , Estructura Molecular , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/química , Compuestos Organometálicos/metabolismo , Hidrolasas de Triéster Fosfórico/síntesis química , Hidrolasas de Triéster Fosfórico/metabolismo , Relación Estructura-Actividad
15.
Anal Chem ; 75(13): 3137-44, 2003 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-12964762

RESUMEN

A complete method for sampling and analyzing of energetic compounds in the atmosphere is described. The method consists of the hyphenation of several techniques: active air sampling using a solid-phase extraction cartridge to collect the analytes, extraction of the sorbed analytes by toluene/methyl tert-butyl ether modified supercritical fluid extraction (SFE), and analysis of the extract by large-volume injection GC-nitrogen/phosphorus detection. The GC system is equipped with a loop-type injection interface with an early solvent vapor exit, a utilizing concurrent solvent evaporation technique. Chemometric approaches, based on a Plackett-Burman screening design and a central composite design for response surface modeling, were used to determine the optimum SFE conditions. The relative standard deviations of the optimized method were determined to be 4.3 to 7.7%, giving raise to method detection limits ranging from 0.06 to 0.36 ng in the sampling cartridge, equivalent to 6.2-36.4 pg/L in the atmosphere, standard sampling volume 10 L. The analytical method was applied to characterize headspace composition above military grade trinitrotoluene (TNT). Results confirm that 2,4-dinitrotoluene (DNT) and 1,3-dinitrobenzene (DNB) constitute the largest vapor flux, but TNT, 2,6-DNT, and trinitrobenzene TNB were also consistently detected in all the samples.

16.
J Chromatogr A ; 993(1-2): 103-10, 2003 Apr 18.
Artículo en Inglés | MEDLINE | ID: mdl-12735442

RESUMEN

An on-line method for the determination of airborne organophosphate esters based on dynamic sonication-assisted solvent extraction and large-volume injection (LVI) gas chromatography with nitrogen-phosphorous detection is introduced. The LVI is performed with a programmed-temperature vaporizer. The entire extracted fraction of 800 microl (hexane-methyl-tert.-butyl ether, 7:3, v/v) is introduced directly into the GC system without any clean-up step following extraction. The extraction and analysis step were completed in less than 15 min. The limit of detection of the investigated organophosphate esters was established to be in the range of 5-32 pg/filter. The correlation coefficients (r2) were investigated in the linear range study of the entire system and established to be approximately 0.9900 for all the investigated organophosphates esters. Applications of the method was demonstrated with the extraction of air samples collected onto glass fiber filters from different indoor environments. Six organophosphate esters were found at the levels 0.4-138 ng/m3.


Asunto(s)
Aire/análisis , Cromatografía de Gases/métodos , Compuestos Organofosforados/análisis , Ésteres/análisis , Sensibilidad y Especificidad , Solventes , Temperatura
17.
Inorg Chem ; 41(20): 4981-3, 2002 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-12354025

RESUMEN

Reaction of the new asymmetric ligand 2-(N-isopropyl-N-((1-methylimidazolyl)methyl)aminomethyl)-6-(N-carboxylmethyl-N-((1-methylimidazolyl)methyl) aminomethyl)-4-methylphenol (ICIMP) with nickel perchlorate and diphenylacetic acid leads to the formation of tetranuclear nickel complexes, whose crystal structures reveal that they consist of dimers of dimers in which each Ni(2) unit has a coordination environment that is similar to the active site of urease. One complex has been shown to coordinate urea and catalyze the hydrolysis of an organophosphate monoester.


Asunto(s)
Bacillus/enzimología , Imidazoles/química , Níquel/química , Compuestos Organometálicos/química , Ureasa/química , Sitios de Unión , Catálisis , Cristalografía por Rayos X , Ligandos , Modelos Moleculares , Conformación Molecular , Estructura Molecular , Ureasa/metabolismo
18.
J Chromatogr A ; 963(1-2): 73-82, 2002 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-12188003

RESUMEN

An analytical method for determining nitroaromatic explosives in vapour phases is presented. Samples were collected by pumping air through glass fibre filters and polyurethane foam adsorbents, and an on-line extraction system combining supercritical fluid extraction (SFE) and high-performance liquid chromatography (HPLC) was developed. This allows analytes to be transferred from the adsorbent to the HPLC system via a porous graphitic carbon trap. When using gradient elution with a suitable mobile phase, most of the nitroaromatic isomers tested were separated. The proposed method is fully automated, allows a complete analysis to be processed in less than 30 min, and it is compatible with most of the organic solvents commonly used as SFE modifiers or additives. The method has been applied to the analysis of real samples obtained from headspace sampling of military-grade 2,4,6-trinitrotoluene and has been shown to constitute a promising alternative for assessing whether areas are mined in landmine-clearing operations.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Cromatografía con Fluido Supercrítico/métodos
19.
J Chromatogr A ; 957(2): 227-34, 2002 May 31.
Artículo en Inglés | MEDLINE | ID: mdl-12113345

RESUMEN

A new system for extracting solid samples based on dynamic sonication-assisted solvent extraction (DSASE) is described. The technique is highly efficient with respect to both time and solvent consumption. In tests reported here, organophosphate esters were extracted from air sampling filters in 3 min with an extraction volume of 600 microL of solvent. Furthermore, it was possible to replace a previously used chlorinated solvent with a halogen-free solvent mixture. The sample was placed in a cartridge through which fresh solvent was pumped continuously. A restrictor connected to the outlet of the cartridge allowed the system to be used at a temperature of 70 degrees C without reaching the boiling point of the solvent. Both spiked and non-spiked native samples were used for the evaluation, which clearly revealed a stronger analyte-matrix interaction in native samples. The DSASE technique was shown to recover larger amounts of organophosphate esters from native samples, compared to a static method. DSASE was applied to air samples collected in a lecture hall and from above a computer monitor.


Asunto(s)
Aire/análisis , Cromatografía de Gases/métodos , Compuestos Organofosforados/aislamiento & purificación , Solventes/química , Ésteres , Reproducibilidad de los Resultados
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