Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 26
Filtrar
1.
ACS Omega ; 9(8): 9309-9320, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38434824

RESUMO

Zirconia-alumina-supported Ni (5Ni/10ZrO2+Al2O3) and Sr-promoted 5Ni/10ZrO2+Al2O3 are prepared, tested for carbon dioxide (CO2) methanation at 400 °C, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, surface area and porosity, infrared spectroscopy, and temperature-programmed reduction/desorption techniques. The CO2 methanation is found to depend on the dispersion of Nickel (Ni) sites as well as the extent of stabilization of CO2-interacted species. The Ni active sites are mainly derived from the reduction of 'moderately interacted NiO species'. The dispersion of Ni over 1 wt % Sr-promoted 5Ni/10ZrO2+Al2O3 is 1.38 times that of the unpromoted catalyst, and it attains 72.5% CO2 conversion (against 65% over the unpromoted catalyst). However, increasing strontium (Sr) loading to 2 wt % does not affect the Ni dispersion much, but the concentration of strong basic sites is increased, which achieves 80.6% CO2 conversion. The 5Ni4Sr/10ZrO2+Al2O3 catalyst has the highest density of strong basic sites and the highest concentration of active sites with maximum Ni dispersion. This catalyst displays exceptional performance and achieves approximately 80% CO2 conversion and 70% methane (CH4) yield for up to 25 h on steam. The unique acidic-basic profiles composed of strong basic and moderate acid sites facilitate the sequential hydrogenation of formate species in the COx-free CH4 route.

2.
ChemistryOpen ; 13(4): e202300173, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38085118

RESUMO

The decomposition of methane has been chosen as an alternative method for producing hydrogen. In this study, 20 % Fe was used as the active metal part of the catalyst. To better comprehend the impact of the supporting catalytic properties, alumina and titania-alumina composite were investigated as supports. Iron-based catalysts were prepared by impregnation method and then calcined at different temperatures (300 °C, 500 °C, and 800 °C). The catalysts were examined at 800 °C under atmospheric pressure with a 15 mL/min total flow rate and 2 : 1 CH4 to N2 feed ratio. The textural and morphological characteristics of the fresh calcined and spent catalysts were investigated. The catalytic activity and stability data demonstrated that Fe supported over TiO2-Al2O3 calcined at 500 °C performed the best of all evaluated catalysts with a more than 80 % hydrogen yield. The Raman spectra result showed that graphitic carbon was produced for all used titanium dioxide catalysts. Moreover, according to transmission electron microscopy (TEM) results, the carbon deposited on the catalysts' surface is carbon nanotubes (CNT).

3.
Langmuir ; 39(49): 17723-17732, 2023 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-38029289

RESUMO

This study explores the employment of CO2 methanation for carbon dioxide utilization and global warming mitigation. For the first time, in this work, we combine the interesting properties of the WO3-ZrO2 support and the benefits of Sr to improve the performance of Ni-based catalysts in this reaction. Sr loading on 5Ni/W-Zr samples is increased to 3 wt %, resulting in improved surface basicity through strong basic site formation. After 300 min, the 5Ni + 3Sr/W-Zr catalyst exhibits high activity and stability, achieving 90% CO2 conversion and 82% CH4 yield compared to 62 and 57% on 5Ni/W-Zr. Limited sintering and absence of carbon deposits are confirmed by temperature-programmed oxidation, XRD, Raman, and TEM analyses at 350 °C for 300 min. Sr promotion creates additional CO2 adsorption and conversion sites, enhancing the catalytic performance.

4.
Pak J Pharm Sci ; 35(3): 859-864, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35791488

RESUMO

SARS-CoV-2 pandemic, drawn attention to the need of virus culture. In vitro SARS-COV-2 culture was performed to carry out therapeutic, environmental and virus genome studies. Isolation of virus from nasopharyngeal swab was performed by inoculating virus positive samples in available cell lines. SARS-CoV-2 topography was observed by using Scanning Electron Microscopy (SEM). Virus specificity was defined by serological confirmation through neutralization assay with COVID 19 convalescent sera. The SARS-COV-2 virus replicated successfully in Vero cell lines (both in E6 and CCL-81). The TCID50 and PFUs of isolated virus were defined as 107 TCID50/mL and 1.4 Х 106 pfu/mL respectively. The virus particles with the SARS-CoV morphology was <150ɳM size. Virus inhibition in presence of convalescent sera of COVID-19 patients was observed. Sisybrium irio (Khaksi) was found cytotoxic on Vero E6 cell line and its antiviral activity could not be established against SARS-COV-2 virus in vitro. Successful isolated and archived native SARS-COV-2 may be utilized further for therapeutic, environmental and virus genome sequencing studies.


Assuntos
COVID-19 , SARS-CoV-2 , Animais , Antivirais/farmacologia , COVID-19/terapia , Chlorocebus aethiops , Humanos , Imunização Passiva , Células Vero , Soroterapia para COVID-19
5.
Gen Thorac Cardiovasc Surg ; 66(5): 247-256, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29322433

RESUMO

Controversy still surrounds the optimal biological valve substitute for aortic valve replacement. In light of the current literature, we review advantages and optimal indications of stentless compared to stented aortic bio-prostheses. Recent meta-analyses, prospective randomized controlled trials and retrospective studies comparing the most frequently used stentless and stented aortic bio-prostheses were analyzed. In the present review, the types and implantation techniques of the bio-prosthesis that are seldom taken into account by most studies and reviews were integrated in the interpretation of the relevant reports. For stentless aortic root bio-prostheses, full-root vs. sub-coronary implantation offered better early transvalvular gradients, effective orifice area and left ventricular mass regression as well as late freedom from structural valve deterioration in retrospective studies. Early mortality and morbidity did not differ between the stentless and stented aortic bio-prostheses. Early transvalvular gradients, effective orifice area and regression of left ventricular hypertrophy were significantly better for stentless, especially as full-root, compared to stented bio-prostheses. The long-term valve-related survival for stentless aortic root and Toronto SPV bio-prosthesis was as good as that for stented pericardial aortic bio-prostheses. For full-root configuration this survival advantage was statistically significant. There seems to be not one but different ideal biological valve substitutes for different subgroups of patients. In patients with small aortic root or exposed to prosthesis-patient mismatch full-root implantation of stentless bio-prostheses may better meet functional needs of individual patients. Longer follow-ups on newer generation of stented bio-prostheses are needed for comparison of their hemodynamic performance with stentless counterparts especially in full-root configuration.


Assuntos
Valva Aórtica/cirurgia , Bioprótese , Doenças das Valvas Cardíacas/cirurgia , Implante de Prótese de Valva Cardíaca/instrumentação , Próteses Valvulares Cardíacas , Idoso , Aorta/cirurgia , Estenose da Valva Aórtica/cirurgia , Feminino , Doenças das Valvas Cardíacas/fisiopatologia , Implante de Prótese de Valva Cardíaca/métodos , Hemodinâmica/fisiologia , Humanos , Hipertrofia Ventricular Esquerda/etiologia , Hipertrofia Ventricular Esquerda/fisiopatologia , Masculino , Pericárdio/cirurgia , Complicações Pós-Operatórias/etiologia , Complicações Pós-Operatórias/fisiopatologia , Estudos Prospectivos , Desenho de Prótese , Ensaios Clínicos Controlados Aleatórios como Assunto , Estudos Retrospectivos , Stents
6.
J Neurosci Rural Pract ; 5(2): 139-43, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24966551

RESUMO

BACKGROUND: Abnormal brain development due to neurodevelopmental disorders in children has always been an important concern, but yet has to be considered as a significant public health problem, especially in the low- and middle-income countries including Nigeria. AIMS: The aim of this study is to determine whether abnormal brain development in the form of neurodevelopmental disorders causes any deviation in the cranial index of affected children. MATERIALS AND METHODS: This is a comparative study on the head length, head width, and cranial index of 112 children (72 males and 40 females) diagnosed with at least one abnormal problem in brain development, in the form of a neurodevelopmental disorder (NDD), in comparison with that of 218 normal growing children without any form of NDD (121 males and 97 females), aged 0-18 years old seen at the Usmanu Danfodiyo University Teaching Hospital, Sokoto, over a period of six months, June to December, 2012. The head length and head width of the children was measured using standard anatomical landmarks and cranial index calculated. The data obtained was entered into the Microsoft excel worksheet and analyzed using SPSS version 17. RESULTS: The mean Cephalic Index for normal growing children with normal brain development was 79.82 ± 3.35 and that of the children with abnormal brain development was 77.78 ± 2.95 and the difference between the two groups was not statistically significant (P > 0.05). CONCLUSION: It can be deduced from this present study that the cranial index does not change in children with neurodevelopmental disorders.

7.
Talanta ; 99: 441-9, 2012 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-22967577

RESUMO

Poly (sodium 10-undecenyl sulfate) (poly SUS), poly (sodium 10-undecenyl leucinate) (poly SUL), and their five molecular binary mixed micelles with varied SUS:SUL composition were prepared. The purity of these molecular micelles was confirmed by elemental analysis. Their partial specific volume, aggregation number, methylene selectivity, polarity, phase ratio, mobility, and elution window values were determined using a variety of analytical techniques. These molecular micelles were then evaluated as pseudostationary phases in micellar electrokinetic chromatography (MEKC) for separation of benzene derivatives with a wide range of chemical properties. Elemental analysis results reveal that the ratio of the two surfactants in the binary mixture does not change significantly during the polymerization process. Poly SUS was found to have the lowest partial specific volume and it increases gradually with an increase of SUL mole fraction. Poly SUL was found to provide the most hydrophobic environment for test solutes. Based on the retention results, the strength of interaction between the molecular micelles and the analytes was found to follow the following order: NHB>HBA>HBD. This order indicates that the hydrophobic interaction plays a major role in retention of benzene derivatives.

8.
Mem Inst Oswaldo Cruz ; 107(4): 470-5, 2012 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-22666856

RESUMO

Visceral leishmaniasis (VL) has been known to occur since the 1980s on the western bank of the White Nile River (Central Sudan), 150 km south of Khartoum, and has resulted in high mortality. The most recent outbreak of the disease in this area began in 2006. Entomological surveys were carried out during May 2008, June 2010 and May and July 2011 in the White Nile area. Sandflies were collected using Centers for Disease Control light traps and sticky oil traps in the village of Kadaba and the nearby woodland. Phlebotomus females were dissected for the presence of Leishmania promastigotes. A total of 17,387 sandflies, including six species of Phlebotomus and 10 species of Sergentomyia, were identified. The Phlebotomus species recorded were Phlebotomus orientalis, Phlebotomus papatasi, Phlebotomus bergeroti, Phlebotomus duboscqi, Phlebotomus rodhaini and Phlebotomus saevus. P. orientalis was collected in both habitats. The relative abundance of P. orientalis in the woodland habitat was higher than that recorded in the village habitat. In the woodland habitat, there was a notable increase in the relative abundance of P. orientalis during the surveys conducted in 2008 and 2010 compared to 2011. None of the 311 P. orientalis females dissected were infected with Leishmania promastigotes, although relatively high parous rates were recorded in both habitats. Based on the distribution of P. orientalis recorded in this study, this species is the most likely vector of VL in the endemic focus in the White Nile area. Further investigation is required to elucidate the seasonal abundance and distribution of the vector, as well as the transmission season of VL in both habitats so that appropriate control strategies for the vector can be designed.


Assuntos
Surtos de Doenças , Insetos Vetores/parasitologia , Leishmania/isolamento & purificação , Leishmaniose Visceral/epidemiologia , Psychodidae/parasitologia , Animais , Ecossistema , Feminino , Humanos , Insetos Vetores/classificação , Leishmaniose Visceral/transmissão , Densidade Demográfica , Vigilância da População , Psychodidae/classificação , Estações do Ano , Sudão/epidemiologia
9.
Mem. Inst. Oswaldo Cruz ; 107(4): 470-475, June 2012. mapas, tab
Artigo em Inglês | LILACS | ID: lil-626439

RESUMO

Visceral leishmaniasis (VL) has been known to occur since the 1980s on the western bank of the White Nile River (Central Sudan), 150 km south of Khartoum, and has resulted in high mortality. The most recent outbreak of the disease in this area began in 2006. Entomological surveys were carried out during May 2008, June 2010 and May and July 2011 in the White Nile area. Sandflies were collected using Centers for Disease Control light traps and sticky oil traps in the village of Kadaba and the nearby woodland. Phlebotomus females were dissected for the presence of Leishmania promastigotes. A total of 17,387 sandflies, including six species of Phlebotomus and 10 species of Sergentomyia, were identified. The Phlebotomus species recorded were Phlebotomus orientalis, Phlebotomus papatasi, Phlebotomus bergeroti, Phlebotomus duboscqi, Phlebotomus rodhaini and Phlebotomus saevus. P. orientalis was collected in both habitats. The relative abundance of P. orientalis in the woodland habitat was higher than that recorded in the village habitat. In the woodland habitat, there was a notable increase in the relative abundance of P. orientalis during the surveys conducted in 2008 and 2010 compared to 2011. None of the 311 P. orientalis females dissected were infected with Leishmania promastigotes, although relatively high parous rates were recorded in both habitats. Based on the distribution of P. orientalis recorded in this study, this species is the most likely vector of VL in the endemic focus in the White Nile area. Further investigation is required to elucidate the seasonal abundance and distribution of the vector, as well as the transmission season of VL in both habitats so that appropriate control strategies for the vector can be designed.


Assuntos
Animais , Feminino , Humanos , Surtos de Doenças , Insetos Vetores/parasitologia , Leishmania/isolamento & purificação , Leishmaniose Visceral/epidemiologia , Psychodidae/parasitologia , Ecossistema , Insetos Vetores/classificação , Leishmaniose Visceral/transmissão , Densidade Demográfica , Vigilância da População , Psychodidae/classificação , Estações do Ano , Sudão/epidemiologia
10.
J Chromatogr A ; 1236: 207-14, 2012 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-22446078

RESUMO

Poly(sodium 10-undecenyl sulfate) (poly-SUS), poly(sodium N-undecenyl leucinate) (poly-SUL) and their five molecular binary mixed micelles with varied SUS:SUL composition were prepared and used as pseudostationary phases in micellar electrokinetic chromatography (MEKC). Linear solvation energy relationships (LSERs) model and free energy of transfer studies were used to characterize the retention behavior and the selectivity differences among the seven surfactant systems. System constant differences and regression models for varied benzene derivative compounds are used to establish the selectivity differences of the seven pseudostationary phases. The cavity formation and dispersion interaction (the v system constant) and the hydrogen-bonding acidity (the b system constant) of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention. The molecular micelle with sulfate head group, poly-SUS, was found to be more hydrogen-bond acidic than the molecular micelle with leucinate head group, poly-SUL. The other system constants (a, s and e) have modest effect on the retention and selectivity of the benzene derivatives. The model intercept coefficients (c system constants), which are negative for all surfactant systems have unusually large values. The free energy changes of transfer for the functional groups studied have all negative values except phenol and benzyl alcohol. Selectivity differences between pseudostationary phases were also compared by plotting the log k values against each other and were found to agree well with LSER results.


Assuntos
Leucina/análogos & derivados , Micelas , Modelos Químicos , Polímeros/química , Ácidos Undecilênicos/química , Cromatografia Capilar Eletrocinética Micelar , Ligação de Hidrogênio , Leucina/química , Modelos Lineares , Compostos Orgânicos/química , Termodinâmica
11.
Inorg Chem ; 50(13): 5861-3, 2011 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-21627089

RESUMO

Circular dichroism (CD) spectroelectrochemistry is used to determine the extent of singly occupied molecular orbital delocalization in mixed-valence multinuclear complexes, specifically the mixed-valence Ru(II)Ru(III) states of the four diastereoisomers of [(Ru(bpy)(2))(2)(bpt)](3+) [1; bpy = 2,2'-bipyridyl and bpt = 3,5-bis(pyrid-2'-yl)-1,2,4-triazolato anion]. The complex was found to be stable to thermal racemization in the three oxidation states, but photoracemization in the Ru(II)Ru(II) state was observed.


Assuntos
Compostos Organometálicos/química , Piridinas/química , Rutênio/química , Dicroísmo Circular , Conformação Molecular , Compostos Organometálicos/síntese química , Oxirredução
13.
Photochem Photobiol Sci ; 9(7): 985-90, 2010 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-20473431

RESUMO

Photochemically-induced ligand rearrangements for the N2 and N4 coordination isomers of the complex [Ru(bpy)(2)(Hpztr)](2+) and its deprotonated analogue [Ru(bpy)(2)(pztr)](+), where bpy is 2,2'-bipyridyl and Hpztr is pyrazine-1,2,4-triazole ligand, are reported. (1)H NMR spectroscopic and HPLC studies indicate that in acetone and acetonitrile the complexes are photostable when the triazole ring is deprotonated. Irradiation of the protonated N2 isomer in acetone results in formation of the N4 isomer, with the N4 isomer being photostable. In acetonitrile both isomers show photolability of the triazole-based ligand and full dissociation to form [Ru(bpy)(2)(CH(3)CN)(2)](2+) is observed. The activation parameters for the population of the (3)MC state from the lowest (3)MLCT manifold, as obtained from temperature-dependent emission lifetime studies, are reported and their relevance to the observed photochemical behaviour is considered. The results obtained are discussed in relation the analogous pyridine-triazole complexes.

14.
Inorg Chem ; 49(6): 2799-807, 2010 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-20141180

RESUMO

The synthesis of two asymmetric dinuclear complexes with the formula [M(bpy)(2)(bpt)Ru(tpy)Cl](2+), where M = Ru (1a), Os(2a); bpy = 2,2'-bipyridyl; Hbpt = 3,5-bis(pyridin-2-yl)1,2,4-triazole and tpy = 2,2',6',2''-terpyridine, is reported. The compounds obtained are characterized by mass spectrometry, (1)H NMR, UV/vis/NIR absorption, luminescence, and resonance Raman spectroscopy. Deuterium isotope labeling facilitates assignment of the (1)H NMR and resonance Raman spectra. The interaction between the two metal centers, mediated by the bridging 1,2,4-triazolato moiety in the mixed valent state, is assigned as type II based on the observation of metal to metal charge transfer absorption bands at 7090 and 5990 cm(-1) for 1a and 2a, respectively. The extent of localization of the emissive excited state was determined by transient resonance Raman and emission spectroscopy. Both 1a and 2a show phosphorescence at the same wavelengths; however, whereas for compound 1a the emission is based on the Ru(tpy)Cl- center, for 2a the emissive state is localized on the Os(bpy)(2)- unit. This indicates that also in the excited state there is efficient interaction between the two metal centers.

15.
J Egypt Soc Parasitol ; 39(2): 599-605, 2009 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-19795766

RESUMO

Cryptosporidiosis has a worldwide geographical and zoological distribution. Cryptosporidium baileyi oocysts were isolated from the bursa of Fabricius (BF) of 4 weeks-old of 100 broilers. Twenty five broiler chicks of 2 day old free from cryptosporidial infection were inoculated intratracheally at a dose of 1 x 10(6) chicks. Five chicks were sacrificed at 4th, 8th, 12th, 16th, and 20th day postinoculation. Selected tissues from bursa of Fabricius, cloaca, colon, caeci and tracheas were taken and examined directly by scraping technique for endogenous stages. The distribution of C. baileyi in different tissues in the case of intratracheal inoculation; trachea 23 (92 %) chicks infected, bursa of Fabricius 21 (84%) chicks, Cloaca 5 (16 %) chicks, Colon 1 (4%) chick and the caeci showing no infection. Daily examination of the intratracheal droppings inoculation was done at the 5th day and lasted for 18-20 days, the patent period.


Assuntos
Galinhas , Criptosporidiose/veterinária , Cryptosporidium/patogenicidade , Doenças das Aves Domésticas/parasitologia , Animais , Bolsa de Fabricius/parasitologia , Ceco/parasitologia , Cloaca/parasitologia , Colo/parasitologia , Criptosporidiose/parasitologia , Oocistos , Especificidade de Órgãos , Distribuição Aleatória , Traqueia/parasitologia
16.
J Chromatogr A ; 1169(1-2): 179-92, 2007 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-17888932

RESUMO

Measurements of retention factors by gas chromatography on up to 10 complementary stationary phases at up to 5 temperatures for each stationary phase and liquid-liquid partition coefficients in three biphasic organic solvent systems (n-hexane-acetonitrile, n-heptane-N,N-dimethylformamide and n-heptane-2,2,2-trifluoroethanol) were used to estimate solute descriptors for 54 organosilicon compounds for use in the solvation parameter model. Many of the E descriptor values (electron lone pair interactions) are negative for simple siloxanes and silanes indicating that these compound bind electron lone pairs more tightly than n-alkanes. Silanes and siloxanes with alkyl groups have near zero dipolarity/polarizability (S descriptor). The S descriptor is only modest for simple phenylsilanes, silazanes, silanols, orthosilicates, and alkoxides. All organosilicon compounds with silicon-oxygen bonds are reasonably strong hydrogen-bond bases (B descriptor) but only the silanol group is a reasonably strong hydrogen-bond acid (A descriptor). Silanes (SiH) and silazanes (SiNHSi) are weak hydrogen-bond acids. Cavity formation and dispersion interactions (V or L descriptor) are often the main component of solvation models for siloxanes and silanes that have simple alkyl and aromatic substituents. A number of physicochemical properties (vapor pressure, aqueous solubility, biphasic partition coefficients, sorption coefficients, etc.) for linear and cyclic dimethylsiloxanes can be reliably predicted from their descriptors in established models for organic compounds.


Assuntos
Cromatografia Gasosa/métodos , Modelos Químicos , Compostos Orgânicos/química , Compostos de Organossilício/análise , Compostos de Organossilício/química , Solventes/química , Adsorção , Calibragem , Fracionamento Químico/instrumentação , Fracionamento Químico/métodos , Físico-Química/métodos , Cromatografia Líquida/métodos , Ligação de Hidrogênio , Concentração de Íons de Hidrogênio , Compostos Orgânicos/classificação , Software , Solubilidade , Solventes/classificação
17.
J Sep Sci ; 29(14): 2158-65, 2006 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-17069245

RESUMO

Partition coefficients for a number of varied compounds were determined for the n-heptane-methanol and n-heptane-DMF partition systems and used to derive a general model for the distribution of neutral compounds in the biphasic systems. The partition coefficient, log Kp, was correlated through the solvation parameter model giving log Kp = -0.056 + 0.164E-0.620S-1.337A-0.957B + 0.507V for the n-heptane-methanol system with a multiple correlation coefficient of 0.986, standard error of the estimate 0.086, and Fischer statistic 413 for 65 compounds. For n-heptane-DMF, the model is log Kp = 0.065 + 0.030E-1.405S-2.039A-0.806B + 0.721V with a multiple correlation coefficient of 0.991, standard error of the estimate 0.080, and Fischer statistic 560 for 59 compounds. In the models the solute descriptors are excess molar refraction E, dipolarity/polarizability S, overall hydrogen bond acidity, and basicity A and B, respectively, and McGowan's characteristic volume V. Either model is expected to be able to estimate further values of the partition coefficient to about 0.08 log units and is applicable to a wide range of compounds. Applications include the choice of partitioning systems for sample clean-up, countercurrent chromatography, and estimation of solute descriptors for water insoluble or unstable compounds.

18.
J Sep Sci ; 29(2): 211-7, 2006 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-16524094

RESUMO

The solvation parameter model is used to characterize the retention properties of five open-tubular column stationary phases (ZB-5 ms, DB-5 ms, DB-XLB, DB-17 ms, and DB-35 ms) based on silarylene-siloxane copolymer chemistries at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and regression models for varied compounds are used to establish the selectivity equivalence of the silarylene-siloxane copolymer stationary phases and to compare their separation characteristics with poly(dimethyldiphenylsiloxane) stationary phases containing a nominally similar concentration of phenyl groups. These studies demonstrate that ZB-5 ms and DB-5 ms are selectivity equivalent. DB-XLB is significantly more dipolar and polarizable than DB-5 ms. In general terms, the silarylenesiloxane copolymer stationary phases are slightly less cohesive and more dipolar and polarizable with similar hydrogen-bond basicity to the poly(dimethyldiphenylsiloxane) stationary phases they were designed to replace. None of the silarylenesiloxane copolymer or poly(dimethyldiphenylsiloxane) stationary phases are hydrogen-bond acidic. Selectivity differences between the two types of stationary phase are temperature dependent and tend to be smaller at higher temperatures within the temperature range studied. Consequently, selectivity differences cannot be globalized without reference to the temperature for the comparison.

19.
J Chromatogr A ; 1104(1-2): 299-312, 2006 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-16343516

RESUMO

An iteration procedure is used to calculate revised solute descriptors for 103 varied compounds suitable for characterizing the retention properties of stationary phases for gas chromatography using the solvation parameter model. The iteration procedure utilizes a database of retention factors obtained on up to 39 open-tubular columns and up to five temperatures in the range 60-140 degrees C for the 103 solutes. The average of the standard deviation [Sigma(logk(exp)-logk(calc))(2)/(n(c)-1)](0.5) where logk(exp) is the experimental retention factor, logk(calc) the model predicted retention factor, and n(c) the total number of retention factors) on all columns is 0.018 for the revised solute descriptors compared with 0.045 for the original values. When used to characterize the retention properties of six open-tubular columns selected to represent different selectivity groups the revised solute descriptors afford improved values for the multiple correlation coefficient and standard deviations of the system constants, and about a three-fold improvement in the standard error of the estimate compared with the original solute descriptors. The revised solute descriptors were used to model retention on the carborane-siloxane copolymer stationary phase Stx-500. This phase has low cohesion, is weakly electron lone pair repulsive, weakly dipolar/polarizable, and weakly hydrogen-bond basic. It has no hydrogen-bond acidity. Its separation properties are similar to those of the poly(diphenyldimethylsiloxane) stationary phases containing 5% diphenylsiloxane monomer, but it is not selectivity equivalent to these phases, being more dipolar/polarizable and a weaker hydrogen-bond base.


Assuntos
Cromatografia Gasosa/instrumentação , Polímeros/química , Siloxanas/química , Desenho de Equipamento
20.
J Chromatogr A ; 1104(1-2): 82-90, 2006 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-16337209

RESUMO

Partition coefficients for 69 varied compounds were determined for the n-hexane-acetonitrile partition system and combined with 74 partition coefficients for (largely) terpenes, esters and alkylaromatic compounds determined by Isidorov and coworkers and 27 extraction p-values determined by Bowman and Beroza to derive a general model for the distribution of neutral compounds in the biphasic system. The partition coefficients, logK(p), were correlated through the solvation parameter model giving logK(p) = 0.097(+/- 0.049) + 0.189(+/-0.041)E - 1.332(+/-0.056)S - 1.649(+/-0.055)A - 0.966(+/-0.074)B + 0.773(+/-0.040)V with a multiple correlation coefficient of 0.985, standard error of the estimate 0.114, and Fischer statistic 1087. The solute descriptor E is the excess molar refraction, S is the dipolarity/polarizability, A and B are the overall hydrogen-bond acidity and basicity, respectively, and V is McGowan's characteristic volume. The model is expected to be able to estimate further values of the partition coefficient to about 0.1 log units and is applicable to a wide range of compounds except for n-alkylcarboxylic acids, which have higher partition coefficients than predicted, most likely due to the formation of oligomers (e.g. dimers) in the n-hexane layer.


Assuntos
Acetonitrilas/química , Hexanos/química , Compostos Orgânicos/química , Cromatografia Gasosa
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...