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1.
Patient Saf Surg ; 13: 1, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30647774

RESUMO

PURPOSE: Arthrofibrosis after total knee arthroplasty represents a considerable burden for the patient and a therapeutic challenge for the practitioner. One possible cause discussed in the literature is a low-grade infection. This hypothesis should be examined within the scope of this retrospective study. PATIENTS AND METHODS: Nineteen patients with clinical symptoms of arthrofibrosis after primary total knee arthroplasty were examined between January, 1999 and January, 2012. Incorrect positioning was radiologically ruled out. All patients were examined clinically (score of Freeman as well as Blauth and Jäger), radiologically (component and leg alignment, patella height according to Insall and Salvati), microbiologically (culture-based procedures), molecular biologically (PCR) and histologically in the course of an open revision of the prosthesis. RESULTS: According to the score of Freeman et al. (1977), a highly significant improvement in pain (p = 0.007) and in the overall score (p = 0.003) was shown. The knee joint mobility did not change significantly (p = 0.795). PCR was negative in 17 patients. One patient showed a PCR-positive result of the synovial membrane for Corynebacterium spp., while Staphylococcus warneri was detected in the culture. Another patient had a positive result of synovia PCR for Enterococcus cecorum as well as Corynebacterium spp. However, this culture was sterile. In 16 patient samples, no bacterial growth was detectable. Two samples were not evaluable. The main histopathological findings were synovialitis and fibrosis. CONCLUSION: The hypothesis of low-grade-infection-induced arthrofibrosis after total knee arthroplasty could not be confirmed in this study. However, based on this small study population the conclusion needs to be confirmed by new and larger studies, ideally prospectively designed including a control group.

2.
Chem Commun (Camb) ; 52(66): 10133-6, 2016 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-27461079

RESUMO

While the 'breaking and mending of porphyrin strategy' proved versatile in the generation of a range of pyrrole-modified porphyrins containing 4-, 5-, and 6-membered heterocycles, it failed to access systems incorporating larger rings. A reversal of the strategy - first mending, then breaking - now allowed the formation of a pyrrole-modified porphyrin containing an 8-membered 1,3,6-triazocine-2,4,8-trione heterocycle.

3.
Clin Pharmacol Ther ; 99(2): 172-85, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26479518

RESUMO

This article provides nomenclature recommendations developed by an international workgroup to increase transparency and standardization of pharmacogenetic (PGx) result reporting. Presently, sequence variants identified by PGx tests are described using different nomenclature systems. In addition, PGx analysis may detect different sets of variants for each gene, which can affect interpretation of results. This practice has caused confusion and may thereby impede the adoption of clinical PGx testing. Standardization is critical to move PGx forward.


Assuntos
Alelos , Testes Genéticos/normas , Farmacogenética/normas , Terminologia como Assunto , Genes , Testes Genéticos/tendências , Variação Genética , Humanos , Farmacogenética/tendências , Medicina de Precisão
4.
Genet Mol Res ; 13(2): 3237-49, 2014 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-24841656

RESUMO

The objective of this study was to determine the effects of the general and specific combining abilities (GCA and SCA, respectively) of 15 characteristics and to evaluate the most promising crosses and the reciprocal effect between the hybrids of six parents of the Capsicum annuum species. Six parents, belonging to the Horticultural Germplasm Bank of Centro de Ciências Agrárias of Universidade Federal da Paraíba, were crossed in complete diallel manner. The 30 hybrids generated and the parents were then analyzed in a completely randomized design with three replicates. The data were submitted to analysis of variance at 1% probability, and the means were grouped by the Scott-Knott test at 1% probability. The diallel analysis was performed according to the Griffing method, model I and fixed model. Both additive and non-additive effects influenced the hybrids' performance, as indicated by the GCA/SCA ratio. The non-additive effects, epistasis and/or dominance, played a more important role than the additive effects in pedicel length, pericarp thickness, fresh matter, dry matter content, seed yield per fruit, fruit yield per plant, days to fructification, and total soluble solids. The GCA effects were more important than the SCA effects in the fruit weight, fruit length and diameter, placenta length, yield, vitamin C, and titratable acidity characteristics. The results found here clearly show that ornamental pepper varieties can be developed through hybridization in breeding programs with C. annuum.


Assuntos
Cruzamento , Capsicum/genética , Cruzamentos Genéticos , Frutas/genética , Ácido Ascórbico/metabolismo , Capsicum/crescimento & desenvolvimento , Frutas/crescimento & desenvolvimento , Variação Genética , Genótipo , Humanos
5.
Eur J Med Res ; 16(9): 420-4, 2011 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-22024444

RESUMO

OBJECTIVE: For transbronchial biopsy of peripheral pulmonary lesions manouevering the biopsy instrument into acutely angulated subsegmental ostia is frequently problematic. The aim of the present study was to compare the stiffness of various biopsy instruments with regard to their use in the clinical setting. - METHODS: The maximal anterograde and retrograde bending angles, were measured for various bronchoscopes and biopsy instruments. Measurement was made with the distal tip of the biopsy instrument either flush with the distal end of the bronchoscope, or extending 1.5 cm beyond it. The following scopes and biopsy instruments were investigated: 1. the 6.2 mm outside diameter (OD) bronchoscope, with the 2.4 mm OD forceps, 0.7 mm needle, 2.3 mm catheter, and the 1.9 mm cryoprobe. 2. the 5.1 mm OD bronchoscope, with the 1.8 mm forceps, 0.7 mm needle, and the 1.8 mm catheter. 3. the 3.7 mm bronchoscope, with the 1.0 mm forceps and the 0.8 mm forceps. - RESULTS: Maximum angulation was greater by 35.4° with the needle extended, vis-a-vis the needle "flush". Both needle and catheter were associated with a greater angulation of up to 20.5° in comparison with the forceps. With an instrument in the working channel the largest anterograde angles were measured for the 5.1 mm bronchoscope, and the largest retrograde angles for the 6.2 mm bronchoscope. - CONCLUSION: When selecting the optimal instrument for transbronchial biopsy specimen collection, account must be taken of the fact that the degree of angulation will depend on the type and diameter of the instrument employed.


Assuntos
Biópsia por Agulha/instrumentação , Brônquios/patologia , Broncoscópios , Broncoscopia/métodos , Pulmão/patologia , Humanos
7.
Br J Dermatol ; 160(4): 835-43, 2009 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-19183180

RESUMO

BACKGROUND: Digital ulcers (DU) are a major complication in the course of systemic sclerosis (SSc). In recent years, efficacious, but expensive therapies (e.g. iloprost, sildenafil, bosentan) have been shown to improve healing or to reduce the recurrence of DU. For optimal management it would be useful to identify the risk factors for DU. Such statistical analyses have been rare because they require a high number of patients. OBJECTIVES: To identify potential risk factors for DU in patients with SSc. METHODS: We used the registry of the German Network for Systemic Scleroderma and evaluated the data of 1881 patients included by August 2007. We assessed potential risk factors for DU by comparing patients with (24.1%) and without active DU at time of entry (75.9%). RESULTS: Multivariate analysis revealed that male sex, presence of pulmonary arterial hypertension (PAH), involvement of the oesophagus, diffuse skin sclerosis (only when PAH was present), anti-Scl70 antibodies, young age at onset of Raynaud's phenomenon (RP), and elevated erythrocyte sedimentation rate (ESR) significantly impacted on the appearance of DU. Certain combinations increased the patients' probability of presenting with DU, with the highest probability (88%) for male patients with early onset of RP, ESR>30 mm h(-1), anti-Scl70 antibodies and PAH. Patients with DU developed RP, skin sclerosis and organ involvement approximately 2-3 years earlier than patients without DU. CONCLUSIONS: The results reveal possible risk factors for the occurrence of DU in SSc. As DU are prone to local complications, prophylactic vasoactive treatment for patients presenting with these factors may be justified.


Assuntos
Doença de Raynaud/etiologia , Escleroderma Sistêmico/etiologia , Úlcera/complicações , Adulto , Feminino , Dedos , Alemanha , Humanos , Masculino , Pessoa de Meia-Idade , Análise Multivariada , Razão de Chances , Doença de Raynaud/psicologia , Doença de Raynaud/terapia , Medição de Risco , Escleroderma Sistêmico/psicologia , Escleroderma Sistêmico/terapia , Fatores Socioeconômicos , Úlcera/psicologia , Úlcera/terapia
8.
Opt Express ; 15(26): 17652-60, 2007 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-19551061

RESUMO

We present THz imaging with 1D electro-optic sampling of ultrashort THz pulses by multichannel balanced detection. Using a lock-in technique, it combines the advantage of a high signal to noise ratio along with the fast acquisition time of multichannel detection. The object is probed by a line focus and the resolution can be adjusted. The performance of the system is demonstrated exemplarily by imaging two objects.


Assuntos
Eletrônica/instrumentação , Interpretação de Imagem Assistida por Computador/instrumentação , Lasers , Lentes , Espectroscopia Terahertz/instrumentação , Desenho Assistido por Computador , Desenho de Equipamento , Análise de Falha de Equipamento , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Radiação Terahertz
10.
J Am Chem Soc ; 123(37): 8923-38, 2001 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-11552799

RESUMO

The rigid tris- and bis(catecholamide) ligands H(6)A, H(4)B and H(4)C form tetrahedral clusters of the type M(4)L(4) and M(4)L(6) through self-assembly reactions with tri- and tetravalent metal ions such as Ga(III), Fe(III), Ti(IV) and Sn(IV). General design principles for the synthesis of such clusters are presented with an emphasis on geometric requirements and kinetic and thermodynamic considerations. The solution and solid-state characterization of these complexes is presented, and their dynamic solution behavior is described. The tris-catecholamide H(6)A forms M(4)L(4) tetrahedra with Ga(III), Ti(IV), and Sn(IV); (Et(3)N)(8)[Ti(4)A(4)] crystallizes in R3(-)c (No. 167), with a = 22.6143(5) A, c = 106.038(2) A. The cluster is a racemic mixture of homoconfigurational tetrahedra (all Delta or all Lambda at the metal centers within a given cluster). Though the synthetic procedure for synthesis of the cluster is markedly metal-dependent, extensive electrospray mass spectrometry investigations show that the M(4)A(4) (M = Ga(III), Ti(IV), and Sn(IV)) clusters are remarkably stable once formed. Two approaches are presented for the formation of M(4)L(6) tetrahedral clusters. Of the bis(catecholamide) ligands, H(4)B forms an M(4)L(6) tetrahedron (M = Ga(III)) based on an "edge-on" design, while H(4)C forms an M(4)L(6) tetrahedron (M = Ga(III), Fe(III)) based on a "face-on" strategy. K(5)[Et(4)N](7)[Fe(4)C(6)] crystallizes in I43(-)d (No. 220) with a = 43.706(8) A. This M(4)L(6) tetrahedral cluster is also a racemic mixture of homoconfigurational tetrahedra and has a cavity large enough to encapsulate a molecule of Et(4)N(+). This host-guest interaction is maintained in solution as revealed by NMR investigations of the Ga(III) complex.


Assuntos
Catecóis/química , Modelos Químicos , Algoritmos , Amidas/síntese química , Amidas/química , Catecóis/síntese química , Cristalografia por Raios X , Enterobactina/química , Cinética , Ligantes , Substâncias Macromoleculares , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Mimetismo Molecular , Espectrometria de Massas por Ionização por Electrospray , Termodinâmica
11.
Anal Chem ; 73(3): 675-83, 2001 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-11217781

RESUMO

Comprehensive two-dimensional (2-D) separations are emerging as powerful tools for the analysis of complex samples. The substantially larger peak capacity for a given length of time relative to 1-D separations is a well-known benefit of comprehensive 2-D separation methods. Unfortunately, with complex samples, the probability of peak overlap in 2-D separations is still quite high. This is especially true if one desires to speed up the analysis by reducing the run time and, thus, by reducing the resolving power along the first dimension separation. Chemometric methods hold considerable promise to overcome the limitations brought upon by the likelihood of peak overlap. Thus, chemometric methods should be able to effectively extend the resolving power of 2-D separation methods. In this paper, the theoretical enhancement provided by application of the generalized rank annihilation method (GRAM) for the analysis of unresolved peaks in comprehensive 2-D separations is carefully modeled and critically evaluated. First, Monte Carlo simulations are used to determine the conditions where the use of GRAM results in the successful analysis of unresolved peaks. A wide range of experimental conditions and performance criteria are modeled, typical to many available 2-D separation methods, including analyte/interference peak height ratio, first- and second-dimension resolutions, signal-to noise ratio, injection volume reproducibility, and run-to-run retention time reproducibility. Essentially, a wide range of experimental conditions and performance criteria are found to provide reliable data amenable to GRAM analysis. The information gleaned from this first set of simulations is then used in conjunction with Monte Carlo simulations of comprehensive 2-D separations. For these simulated 2-D separations, the total number of analyzable peaks when using GRAM was determined and found to be substantially better than using only traditional quantitative methods such as peak integration or height. For example, it was determined that the use of GRAM increases the average number of analyzable peaks by a factor of 2 for 2-D separations in which the peak capacity is 67% occupied by randomly distributed peaks. The results of the studies are general, and the use of GRAM should increase the number of analyzable peaks for all forms of comprehensive 2-D separations.

12.
Brain Res ; 859(1): 15-20, 2000 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-10720610

RESUMO

Application of 4-aminopyridine (4-AP) has previously been reported to produce different patterns of epileptiform discharges in entorhinal cortex (EC)-hippocampal slices: recurrent short discharges (RSDs) in hippocampal area CA1, seizure-like events (SLEs) and negative-going potentials (NGPs) in the medial entorhinal cortex (mEC). Using recordings of field potentials, we investigated the pharmacological effects of the clinically employed standard anticonvulsant drugs phenytoin (PHT), carbamazepine (CBZ), valproic acid (VPA) and phenobarbital (PHB) and those of pentobarbital (PB) on 4-AP-induced epileptiform activity. The anticonvulsant drugs showed different effects: SLEs were completely blocked by all tested drugs. Valproic acid, which suppressed all epileptiform activities, seemed to have the most fundamental effect of all drugs on 4-AP induced activity, because under phenytoin and carbamazepine, some epileptiform activity was still observable. The RSDs in hippocampal area CA1 of the hippocampus did not respond to the different anticonvulsants. In contrast, PB decreased the frequency of the RSDs in CA1 and enhanced the frequency of the NGPs in the EC. We propose that the activities induced by 4-AP in the combined entorhinal cortex-hippocampal slices may provide an in vitro model for the development of new drugs against difficult-to-treat focal epilepsy.


Assuntos
Anticonvulsivantes/farmacologia , Córtex Entorrinal/efeitos dos fármacos , Córtex Entorrinal/fisiopatologia , Epilepsias Parciais/tratamento farmacológico , Epilepsias Parciais/fisiopatologia , Hipocampo/efeitos dos fármacos , Hipocampo/fisiopatologia , 4-Aminopiridina , Animais , Carbamazepina/farmacologia , Epilepsias Parciais/induzido quimicamente , Feminino , Hipnóticos e Sedativos/farmacologia , Masculino , Pentobarbital/farmacologia , Fenobarbital/farmacologia , Fenitoína/farmacologia , Proibitinas , Ratos , Ratos Wistar , Ácido Valproico/farmacologia , Ácido gama-Aminobutírico/metabolismo
13.
Naunyn Schmiedebergs Arch Pharmacol ; 361(1): 25-32, 2000 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-10651143

RESUMO

Results regarding the anticonvulsant potency of bromide have been questioned, and the mechanisms of its action are unclear. Using combined rat hippocampus-entorhinal cortex slices we analyzed the effects of NaBr on four types of epileptiform discharges in two different models of epilepsy, the low-Ca2+ and the low-Mg2+ model. NaBr concentration-dependently reduced the frequency and finally blocked the low Ca2+-induced discharges. Low Mg2+-induced short recurrent discharges were also reduced in a concentration-dependent manner. In the entorhinal cortex the frequency of seizure-like events was reduced by 3 and 5 mM and the discharges were blocked by 7 mM NaBr. Also, the late recurrent discharges in the entorhinal cortex which do not respond to most clinically employed anticonvulsants were reduced by concentrations of 10 and 15 mM and completely blocked by 30 mM NaBr. Using pH-sensitive microelectrodes different effects of NaBr were seen than those of acetazolamide on extracellular pH under control conditions and after stimulation. Acetazolamide at 1 mM caused a reversible acidification of delta pH: 0.2+/-0.14 at rest whereas no change on extracellular pH was seen with 5 mM NaBr. Acetazolamide increased the transient alkalosis induced by repetitive stimulation of the stratum radiatum in area CA1 and reduced the subsequent acidosis. NaBr also increased the alkalosis but had no effect on the subsequent acidosis. A significant increase in paired-pulse inhibition was seen in a paired-pulse stimulation protocol used to monitor the efficacy of GABAergic inhibition at concentrations of 5 mM NaBr. This finding was confirmed in whole-cell patch clamp recordings from cultured hippocampal neurons showing an increase in inhibitory postsynaptic current amplitude. In summary, our results suggest a broad-spectrum anticonvulsant activity which is likely to be caused by its effects on membrane excitability, by an increase in GABAergic inhibition and is less likely caused by its effects on extracellular pH.


Assuntos
Anticonvulsivantes/farmacologia , Brometos/farmacologia , Epilepsia/fisiopatologia , Espaço Extracelular/metabolismo , Compostos de Sódio/farmacologia , Ácido gama-Aminobutírico/fisiologia , Acetazolamida/farmacologia , Algoritmos , Animais , Cálcio/fisiologia , Inibidores da Anidrase Carbônica/farmacologia , Estimulação Elétrica , Eletrofisiologia , Potenciais Pós-Sinápticos Excitadores/efeitos dos fármacos , Espaço Extracelular/efeitos dos fármacos , Feminino , Concentração de Íons de Hidrogênio , Técnicas In Vitro , Magnésio/fisiologia , Masculino , Potenciais da Membrana/efeitos dos fármacos , Microeletrodos , Técnicas de Patch-Clamp , Ratos , Ratos Wistar , Fatores de Tempo
14.
Inorg Chem ; 39(26): 6100-6, 2000 Dec 25.
Artigo em Inglês | MEDLINE | ID: mdl-11151510

RESUMO

The metal-chelating ability of 2-pyrrolylthiones is described. The readily available ligands di-2-pyrrolyl thione (6), 2-thioacetylpyrrole (10), and 2-thiobenzoylpyrrole (11) constitute examples of monoanionic ligands with N,S-donor atom sets, although di-2-pyrrolyl thione (6) could theoretically also achieve chelation through an N,N-donor set. A square planar Ni(II) complex, 14, an octahedral Co(III) complex, 18, and a tetrahedral Hg(II) complex, 17, with the di-2-pyrrolyl thionato chelate have been prepared, and their structures have been characterized by 1H NMR, UV-vis, MS, IR, elemental analysis, and single-crystal X-ray diffraction. Crystal data for 14: C18H14N4NiS2.0.28H2O, trigonal, R3, a = 18.467(1) A, b = 18.467(1) A, c = 26.404(2) A, V = 7797(1) A3; Z = 18, R = 3.2%. Crystal data for 18-mer: C27H21CoN6S3.C3H6O (acetone), monoclinic, P21/n, a = 9.569(1) A, b = 23.152(1) A, c = 13.659(1) A, beta = 100.882(8) degrees, V = 2971.6(5) A3, Z = 4, R = 4.3%. Crystal data for 17: C18H14HgN4S2, triclinic, P1, a = 8.443(2), b = 14.278(1) A, c = 7.445(1) A, alpha = 90.561(9) degrees, beta = 97.64(1) degrees, gamma = 104.250(9) degrees, V = 861.3(2) A3, Z = 2, R = 4.2%. The bond lengths and angles of these metal complexes are comparable to those of known N,S-chelates. A comparison of the structural parameters of the ligand in the metal complexes with those for the free ligand 6 demonstrates the preorganization of the free ligand for complexation and demonstrates the spectator role of the noncoordinating pyrrolic unit. Chelation of Ni(II) by 2-thioacetylpyrrole (10) and 2-thiobenzoylpyrrole (11) to provide complexes 12 and 13 with structures analogous to complex 14 is also described.


Assuntos
Quelantes/química , Cobalto , Mercúrio , Níquel , Pirróis/química , Tionas/química , Quelantes/síntese química , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Conformação Molecular , Estrutura Molecular , Pirróis/síntese química , Relação Estrutura-Atividade , Tionas/síntese química
15.
Neurosci Lett ; 268(3): 163-5, 1999 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-10406030

RESUMO

Application of 4-aminopyridine (4AP) has previously been reported to produce different patterns of epileptiform discharges in entorhinal cortex-hippocampal-slices. Here we describe that 4-AP induced epileptiform activity in the EC becomes insensitive to anticonvulsant drugs (phenytoin, carbamazepine, valproic acid, phenobarbital) when GABAergic transmission is blocked by bicuculline. We propose that the activities induced by 4-aminopyridine and bicuculline may provide an in vitro model for the development of new drugs against difficult-to-treat focal epilepsy.


Assuntos
4-Aminopiridina , Anticonvulsivantes/farmacologia , Bicuculina , Convulsivantes , Epilepsia/tratamento farmacológico , Potenciais Evocados/efeitos dos fármacos , Animais , Córtex Entorrinal/efeitos dos fármacos , Córtex Entorrinal/fisiologia , Epilepsia/induzido quimicamente , Epilepsia/fisiopatologia , Hipocampo/efeitos dos fármacos , Hipocampo/fisiologia , Ratos
16.
Chirurg ; 68(5): 525-9; discussion 530, 1997 May.
Artigo em Alemão | MEDLINE | ID: mdl-9303844

RESUMO

The endoscopic release of the carpal ligament gives the opportunity to treat the carpal tunnel syndrome in a comfortable and minimal invasive way. Between 1 October 1994 and 7 May 1995, 46 patients who underwent endoscopic surgery on 55 hands were documented in a prospective study. The following results were taken from a questionnaire. There were not any complaints, or the complaints were so much diminished that complete division of the carpal ligament could be viewed as accomplished in 51 of 55 cases. There were continuing complaints in four cases, and after an additional check two patients were operated on again. The advantage of the endoscopic method is the inconspicuous scar and the reduced postoperative disablement. No complications have occurred.


Assuntos
Artroscópios , Síndrome do Túnel Carpal/cirurgia , Endoscópios , Adulto , Idoso , Idoso de 80 Anos ou mais , Documentação/métodos , Desenho de Equipamento , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Satisfação do Paciente , Complicações Pós-Operatórias/etiologia , Estudos Prospectivos
17.
Anal Chem ; 69(17): 3465-70, 1997 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-21639269

RESUMO

A flame ionization detector (FID) is used to detect volatile organic compounds that have been separated by water-only reversed-phase liquid chromatography (WRP-LC). The mobile phase is 100% water at room temperature, without use of organic solvent modifiers. An interface between the LC and detector is presented, whereby a helium stream samples the vapor of volatile components from individual drops of the LC eluent, and the vapor-enriched gas stream is sent to the FID. The design of the drop headspace cell is simple because the water-only nature of the LC separation obviates the need to do any organic solvent removal prior to gas phase detection. Despite the absence of organic modifier, hydrophobic compounds can be separated in a reasonable time due to the low phase volume ratio of the WRP-LC columns. The drop headspace interface easily handles LC flows of 1 mL/min, and, in fact, compound detection limits are improved at faster liquid flow rates. The transfer efficiency of the headspace interface was estimated at 10% for toluene in water at 1 mL/min but varies depending on the volatility of each analyte. The detection system is linear over more than 5 orders of 1-butanol concentration in water and is able to detect sub-ppb amounts of o-xylene and other aromatic compounds in water. In order to analyze volatile and nonvolatile analytes simultaneously, the FID is coupled in series to a WRP-LC system with UV absorbance detection. WRP-LC improves UV absorbance detection limits because the absence of organic modifier allows the detector to be operated in the short-wavelength UV region, where analytes generally have significantly larger molar absorptivities. The selectivity the headspace interface provides for flame ionization detection of volatiles is demonstrated with a separation of 1-butanol, 1,1,2-trichloroethane (TCE), and chlorobenzene in a mixture of benzoic acid in water. Despite coelution of butanol and TCE with the benzoate anion, the nonvolatile benzoate anion does not appear in the FID signal, allowing the analytes of interest to be readily detected. The complementary selectivity of UV-visible absorbance detection and this implementation of flame ionization detection allows for the analysis of volatile and nonvolatile components of complex samples using WRP-LC without the requirement that all the components of interest be fully resolved, thus simplifying the sample preparation and chromatographic requirements. This instrument should be applicable to routine automated water monitoring, in which repetitive injection of water samples onto a gas chromatograph is not recommended.

18.
Clin Chem ; 43(12): 2345-52, 1997 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-9439453

RESUMO

Ring core-biotinylated testosterone tracers were synthesized with bridges of three different lengths connecting the biotin moiety to the steroid core (7 alpha-Cn-Bio-T, n = 3, 6, or 11). Together with a position 7-specific polyclonal anti-testosterone antibody, we used the 7 alpha-C11-Bio-T tracer to develop a novel, labeled-hapten competitive immunoassay for total testosterone in serum. (The C3 and C6 tracers proved to be not suitable for analogous immunoassays.) Enhanced chemiluminescence signal was generated by use of a second immobilized antibody and a streptavidin-horseradish peroxidase conjugate. The measuring range of the assay is 0.2-20.0 nmol/L, linearity of serial dilutions can be demonstrated, the lower detection limit is 0.125 nmol/L, and the interassay imprecisions are 13-16%. Accuracy determinations in mass spectrometry-controlled reference specimens showed a mean recovery of 95%. In addition, the assay shows low cross-reactivities, demonstrating the favorable specificity of the combination of a "nearly native" tracer with a position analog antibody. The optimized steric structure and the long spacer arm of the biotinylated testosterone tracer make this chemiluminescence assay well-suited for measuring total testosterone concentration in serum.


Assuntos
Testosterona/sangue , Adolescente , Adulto , Feminino , Humanos , Imunoensaio , Medições Luminescentes , Masculino , Pessoa de Meia-Idade , Radioimunoensaio , Sensibilidade e Especificidade , Testosterona/análogos & derivados
19.
Talanta ; 43(6): 901-7, 1996 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-18966560

RESUMO

A chemical sensor for gas phase measurements is reported which combines the principles of chemical separation and fiber optic detection. The analyzer incorporates an annular column Chromatographic sensor, constructed by inserting a polymer-clad optical fiber into a silica capillary. Light from a helium-neon laser is launched down the fiber, producing a steady intensity distribution within the fiber, but a low background of scattered light. When sample vapor is introduced to the sensor, and an analyte-rich volume interacts with the polymer cladding, Chromatographic retention is observed simultaneously with a change in the local refractive index of the cladding. An increase in cladding refractive index (RI) causes light to be coupled out of the fiber, with detection at a right-angle to the annular column length to provide optimum S/N ratio. This detection mechanism is called mode-filtered light detection. We report a gas Chromatographic separation on a 3.1 m annular column (320 microm i.d. silica tube, 228 microm o.d. fiber with a 12 microm fluorinated silicone clad) of methane, benzene, butanone and chlorobenzene in 6 min. The annular column length was reduced to 22 cm to function as a sensor, with selected organic vapors exhibiting unique retention times and detection selectivity. The detection selectivity is determined by the analyte RI and the partition coefficient into the cladding. The calculated limit of detection (LOD) for benzene vapor is 0.03% by volume in nitrogen, and several chlorinated species had LOD values less than 1%. For binary mixtures of organic vapors, the detected response appears to be the linear combination of the two organic standards, suggesting that the annular column may be useful as a general approach for designing chemical sensors that incorporate separation and optical detection principles simultaneously.

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