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1.
Acta Vet Hung ; 72(2): 133-139, 2024 Jul 03.
Article in English | MEDLINE | ID: mdl-38900584

ABSTRACT

This study investigated the sero-epidemiology of bluetongue in ruminants in North-Western Pakistan. A total of 3,173 serum samples were collected from small (n = 1,651) and large (n = 1,522) ruminants being reared by farmers in 14 districts. Antibodies to bluetongue virus (BTV) were detected using competitive ELISA. The overall prevalence of BTV antibodies was 65%. A significant association (P < 0.05) between the prevalence of BTV antibodies and the risk factors including sex, species, age, area, husbandry practices and breed was shown by univariate analysis. In multivariate analysis, the seroprevalence was 6.5 (95% CL = 3.7-11.4), 5.9 (95% CL = 3.8-9.4) and 2.4 (95% CL = 1.5-3.7) times higher in buffaloes, cattle and goats than sheep, respectively. The seroprevalence was 1.4 (95% CL = 1.1-1.7) times higher in local breeds than in cross/exotic breeds. The seroprevalence was 1.6 (95% CL = 1.1 to 2.3) times higher in sedentary animals than in nomadic animals. The seroprevalence was significantly associated with age. Further work is required to determine the BTV serotypes prevalent in the study area for effective control of the disease.


Subject(s)
Bluetongue virus , Bluetongue , Goat Diseases , Animals , Pakistan/epidemiology , Seroepidemiologic Studies , Bluetongue/epidemiology , Bluetongue/virology , Bluetongue virus/immunology , Female , Male , Goat Diseases/epidemiology , Goat Diseases/virology , Sheep , Goats , Cattle , Antibodies, Viral/blood , Ruminants/virology , Risk Factors , Cattle Diseases/epidemiology , Cattle Diseases/virology , Animal Husbandry , Sheep Diseases/epidemiology , Sheep Diseases/virology , Prevalence
2.
Res Vet Sci ; 161: 38-44, 2023 Aug.
Article in English | MEDLINE | ID: mdl-37321009

ABSTRACT

This study reports prevalence of antibodies against bluetongue virus (BTV) in animals kept on Government farms/research stations in North-western Pakistan and its association with different risk factors. In total, 1257 blood samples were collected, at random, from animals on 12 separate Government farms/research stations. The prevalence of antibodies against BTV was evaluated using a competitive ELISA. Mixed effects univariate and multivariate logistic regressions were applied to ascertain different risk factors associated with the prevalence of the infection using farm as random effect variable. The overall weighted seroprevalence was recorded as 52%. In univariate analysis, a significant association between sero-conversion to BTV infection and species (P < 0.0001), sex (P < 0.0001), herd size (P = 0.0295) and age of animal (P < 0.0001) was recorded. In multivariate mixed effects logistic regression analysis, prevalence of the infection was found to be 7 (95% CI =2-28) times higher in goats and buffalo than in sheep. Prevalence of the infection was found to be 2.5 (95% CI =1.7-3.3) times higher in female than male animals. However, no significant association was found between sero-conversion of BTV and herd size in multivariate mixed effects logistic regression. Age was found to be a risk factor for the sero-conversion; odds of sero-conversion to BTV increased by 1.29, 1.4, 1.32 and 1.6 times per year increase in age of sheep, goats, buffalo and cattle, respectively. Prevalence of bluetongue was found higher in animals maintained on Government owned farms than that in individual holdings, as previously reported in Pakistan.


Subject(s)
Bison , Bluetongue virus , Bluetongue , Cattle Diseases , Goat Diseases , Sheep Diseases , Cattle , Sheep , Animals , Female , Male , Bluetongue/epidemiology , Farms , Buffaloes , Prevalence , Pakistan/epidemiology , Seroepidemiologic Studies , Antibodies, Viral , Goats , Risk Factors , Cattle Diseases/epidemiology , Goat Diseases/epidemiology , Sheep Diseases/epidemiology
3.
Materials (Basel) ; 15(19)2022 Sep 24.
Article in English | MEDLINE | ID: mdl-36233969

ABSTRACT

Alkali-silica reaction (ASR) is one of the major durability issues that affect the material degradation and structural performance, compromising the service life of concrete structures. Therefore, this study was planned to investigate the potential of ASR for locally available unexplored and vastly used aggregates, as per ASTM C1260. Aggregates from five different sources (Shalozan, Abbotabad, Orakzai, Swabi and Sada) were procured from their respective crusher sites. Mineralogical components of these aggregates were studied using the petrographic analysis. Cube, prism and mortar bar specimens were cast using mixture design in accordance with ASTM C1260 and placed in sodium hydroxide solution at 80 °C for 90 days. Identical specimens were also cured in water for the purpose of comparison. It was observed that mortar bar expansion of Orakzai aggregate was higher among the other tested aggregates and greater than 0.20% at 28 days, indicating the reactive nature according to ASTM C1260. Petrographic analysis also revealed the presence of reactive silica (quartzite) in the tested Orakzai source. It was observed that the compressive and flexural strengths of specimens exposed to ASR conducive environment was lower than the identical specimens placed in water. For instance, an approximately 9% decrease in compressive strength was observed for Orakzai aggregates exposed to ASR environment at 90 days compared to similar specimens placed in water curing. Moreover, microstructural analysis showed the development of micro-cracks for specimens incorporating Orakzai source aggregates. This study assists the construction stakeholders for the potential of unexplored local aggregates with regard to ASR before its utilization in mega construction projects.

4.
Materials (Basel) ; 15(11)2022 May 30.
Article in English | MEDLINE | ID: mdl-35683184

ABSTRACT

In this study, the durability of cement-based repairs was observed, especially at the interface of debonding initiation and propagation between the substrate-overlay of thin-bonded cement-based material, using monotonic tests experimentally and numerically. Overlay or repair material (OM) is a cement-based mortar with the addition of metallic fibres (30 kg/m3) and rubber particles (30% as a replacement for sand), while the substrate is a plain mortar without any addition, known as control. Direct tension tests were conducted on OM in order to obtain the relationship between residual stress-crack openings (σ-w law). Similarly, tensile tests were conducted on the substrate-overlay interface to draw the relationship between residual stress and opening of the substrate-overlay interface. Three-point monotonic bending tests were performed on the composite beam of the substrate-overlay in order to observe the structural response of the repaired beam. The digital image correlation (DIC) method was utilized to examine the debonding propagation along the interface. Based on the different parameters obtained through the above-mentioned experiments, a three-point bending monotonic test was modelled through finite elements using a software package developed in France called CAST3M. Structural behaviour of repaired beams observed by experimental results and that analysed by numerical simulation are in coherence. It is concluded from the results that the hybrid use of fibres and rubber particles in repaired material provides a synergetic effect by improving its strain capacity, restricting crack openings by the transfer of stress from the crack. This enhances the durability of repair by controlling propagation of the interface debonding.

5.
Transbound Emerg Dis ; 68(6): 3126-3135, 2021 Nov.
Article in English | MEDLINE | ID: mdl-33915027

ABSTRACT

The presence of foot-and-mouth disease virus (FMDV) of the O/ME-SA/Ind-2001e sublineage within Pakistan was initially detected in two samples collected during 2019. Analysis of further serotype O FMDVs responsible for disease outbreaks in 2019-2020 in the country has now identified the spread of this sublineage to 10 districts within two separate provinces in North-Eastern and North-Western Pakistan. Phylogenetic analysis indicates that these viruses are closely related to those circulating in Bhutan, Nepal and India. The VP1 coding sequences of these viruses from Pakistan belong to three distinct clusters, which may indicate multiple introductions of this virus sublineage, although the routes of introduction are unknown. Vaccine matching studies against O1 Manisa, O 3039 and O TUR/5/2009 support the suitability of existing vaccine strains to control current field outbreaks, but further studies are warranted to monitor the spread and evolution of the O/ME-SA/Ind-2001e sublineage in the region. (145 words).


Subject(s)
Foot-and-Mouth Disease Virus , Foot-and-Mouth Disease , Animals , Disease Outbreaks/veterinary , Foot-and-Mouth Disease/epidemiology , Foot-and-Mouth Disease Virus/genetics , Pakistan/epidemiology , Phylogeny , Serogroup
6.
Article in English | WPRIM (Western Pacific) | ID: wpr-895291

ABSTRACT

Objectives@#Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has caused devastation in over 200 countries. Italy, Spain, and the United States (US) were most severely affected by the first wave of the pandemic. The reasons why some countries were more strongly affected than others remain unknown. We identified the most-affected and lessaffected countries and states and explored environmental, host, and infrastructure risk factors that may explain differences in the SARS-CoV-2 mortality burden. @*Methods@#We identified the top 10 countries/US states with the highest deaths per population until May 2020. For each of these 10 case countries/states, we identified 6 control countries/ states with a similar population size and at least 3 times fewer deaths per population. We extracted data for 30 risk factors from publicly available, trusted sources. We compared case and control countries/states using the non-parametric Wilcoxon rank-sum test, and conducted a secondary cluster analysis to explore the relationship between the number of cases per population and the number of deaths per population using a scalable EM (expectation– maximization) clustering algorithm. @*Results@#Statistically significant differences were found in 16 of 30 investigated risk factors, the most important of which were temperature, neonatal and under-5 mortality rates, the percentage of under-5 deaths due to acute respiratory infections (ARIs) and diarrhea, and tuberculosis incidence (p < 0.05) @*Conclusion@#Countries with a higher burden of baseline pediatric mortality rates, higher pediatric mortality from preventable diseases like diarrhea and ARI, and higher tuberculosis incidence had lower rates of coronavirus disease 2019-associated mortality, supporting the hygiene hypothesis.

7.
Article in English | WPRIM (Western Pacific) | ID: wpr-902995

ABSTRACT

Objectives@#Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has caused devastation in over 200 countries. Italy, Spain, and the United States (US) were most severely affected by the first wave of the pandemic. The reasons why some countries were more strongly affected than others remain unknown. We identified the most-affected and lessaffected countries and states and explored environmental, host, and infrastructure risk factors that may explain differences in the SARS-CoV-2 mortality burden. @*Methods@#We identified the top 10 countries/US states with the highest deaths per population until May 2020. For each of these 10 case countries/states, we identified 6 control countries/ states with a similar population size and at least 3 times fewer deaths per population. We extracted data for 30 risk factors from publicly available, trusted sources. We compared case and control countries/states using the non-parametric Wilcoxon rank-sum test, and conducted a secondary cluster analysis to explore the relationship between the number of cases per population and the number of deaths per population using a scalable EM (expectation– maximization) clustering algorithm. @*Results@#Statistically significant differences were found in 16 of 30 investigated risk factors, the most important of which were temperature, neonatal and under-5 mortality rates, the percentage of under-5 deaths due to acute respiratory infections (ARIs) and diarrhea, and tuberculosis incidence (p < 0.05) @*Conclusion@#Countries with a higher burden of baseline pediatric mortality rates, higher pediatric mortality from preventable diseases like diarrhea and ARI, and higher tuberculosis incidence had lower rates of coronavirus disease 2019-associated mortality, supporting the hygiene hypothesis.

8.
Int J Occup Saf Ergon ; 26(3): 562-572, 2020 Sep.
Article in English | MEDLINE | ID: mdl-29882723

ABSTRACT

This study demonstrates how field employees' perceived threat of terrorism (PTT) is magnified by the incompatibility between role demand (travel and work outdoors) and resources (terrorism-endangered environment). With a foundation in the conservation of resources perspective and transactional theory of stress, a theoretical framework was proposed to test the mediating effect of role ambiguity (RA) and role conflict (RC) in the relationship between PTT and emotional exhaustion (EE). An approach involving confirmatory factor analysis and the structural equation was used for analysis. Data from 432 pharmaceutical sales representatives indicate a significant positive relationship between PTT and EE, while RA and RC significantly mediated the relationship. The findings are potentially useful for employers in charge of field employees in high-risk regions by explaining how such groups can be provided with support to reduce their role stress and exhaustion, leading ultimately to increased satisfaction.


Subject(s)
Drug Industry , Role , Terrorism/psychology , Adult , Age Factors , Female , Humans , Male , Occupational Stress , Pakistan , Psychological Distress , Surveys and Questionnaires
9.
J Biomed Inform ; 98: 103272, 2019 10.
Article in English | MEDLINE | ID: mdl-31479747

ABSTRACT

INTRODUCTION: With the growth in Internet technology, online rating websites encourage patients to contribute actively in rating their physicians. These rating sites provide more information for patients, such as electronic word of mouth (eWOM) and physician trustworthiness. Although several studies in e-commerce have investigated the role of eWOM and seller trustworthiness in the consumer purchase decision-making process and the price premium for products or services, studies on the role of different information sources that reflect the service quality and delivery process in choosing a competent physician remain scarce. This research develops a two-equation model to examine the effect of different signals, i.e., patient-generated signals (PGSs) and system-generated signals (SGSs), on patient choice, which is an important predictor of physicians' economic returns. METHODS: A secondary data econometric analysis and structural modeling using 2896 physicians' real data from a publicly available online physician rating site, i.e., Healthgrades.com, were conducted using a mixed-methods approach. A hybrid text mining approach was adopted to calculate the sentiment of each review. RESULTS: We find that both PGSs and SGSs have a significant impact on patient choice at different stages of health consultation. Furthermore, disease risk negatively moderates the association between PGSs and information search, while the impact of both signals on patient willingness to pay a price premium is positively moderated by the disease risk. CONCLUSION: Our study contributes to the unified framework of signaling theory and Maslow's hierarchy of needs theory by making a clear distinction between PGSs or SGSs and their influence on patient decision-making across different disease risks. Moreover, PGSs and SGSs are two essential factors for physicians to increase their income.


Subject(s)
Patient Satisfaction , Physicians/economics , Professional Practice/economics , Algorithms , Commerce , Data Mining , Decision Making , Economics, Medical , Humans , Income , Internet , Models, Econometric , Physician-Patient Relations , Physicians/statistics & numerical data , Social Media , Surveys and Questionnaires , United States
10.
Electrophoresis ; 28(11): 1762-78, 2007 Jun.
Article in English | MEDLINE | ID: mdl-17480038

ABSTRACT

In this work, six amino acid derived (L-leucinol, L-leucine, L-isoleucinol, L-isoleucine, L-valinol, and L-valine) polymeric chiral surfactants with carboxylate and sulfate head groups that were recently synthesized in our laboratory [30, 33, 35] are compared for the simultaneous enantioseparation of several groups of structurally similar analytes under neutral and basic pH conditions. The physicochemical properties of the monomers and polymers of both classes of sulfated and carboxylated surfactants are compared. In addition, cryogenic high-resolution electron microscopy showed tubular structures with distinct order of the tubes of 50-100 nm width. A Plackett-Burmann experimental design is used to study the factors that influence the chiral resolution and analysis time of ten structurally related phenylethylamines (PEAs). It is observed that increasing the number of hydroxy groups on the benzene ring of the PEAs resulted in deterioration of enantioseparation using any of the six polymeric surfactants. For all three classes of PEAs, polysodium N-undecenoxycarbonyl-L-amino acidate (poly-L-SUCAA)-type surfactants provided enhanced resolution compared to that of polysodium N-undecenoxycarbonyl-L-amino acid sulfates (poly-L-SUCAASS). Several classes of basic and neutral chiral compounds (e.g., beta-blockers benzoin derivatives, PTH-amino acids, and benzodiazepines) also provided improved chiral separations with poly-L-SUCAA. Among the poly-L-SUCAAs, polysodium N-undecenoxycarbonyl-L-isoleucine sulfate (poly--SUCL) exhibited overall the best enantioseparation capability for the investigated basic and neutral compounds, while among the poly-L-SUCAASs, polysodium N-undecenoxycarbonyl-L-isoleucine sulfate (poly-L-SUCILS), and polysodium N-undecenoxycarbonyl-L-valine sulfate (poly-L-SUCVS) proved to be equally effective for enantioseparation. This work clearly demonstrates that variation in the head group of polymeric alkenoxy amino acid surfactants has a significant effect on chiral separations.


Subject(s)
Amino Acids/chemistry , Carboxylic Acids/chemistry , Chromatography, Micellar Electrokinetic Capillary/methods , Sulfuric Acid Esters/chemistry , Surface-Active Agents/chemistry , Adrenergic beta-Antagonists/isolation & purification , Benzodiazepines/isolation & purification , Chemical Phenomena , Chemistry, Physical , Leucine/analogs & derivatives , Leucine/chemistry , Micelles , Microscopy, Electron, Scanning , Optical Rotation , Phenethylamines/isolation & purification , Phenylthiohydantoin/analogs & derivatives , Phenylthiohydantoin/isolation & purification , Polymers/chemistry , Stereoisomerism
11.
Anal Chem ; 79(3): 879-98, 2007 Feb 01.
Article in English | MEDLINE | ID: mdl-17263313

ABSTRACT

In this work, three amino acid-derived (l-leucinol, l-isoleucinol, l-valinol) sulfated chiral surfactants are synthesized and polymerized. These chiral sulfated surfactants are thoroughly characterized to determine critical micelle concentration, aggregation number, polarity, optical rotation, and partial specific volume. For the first time the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The polysodium N-undecenoyl-l-leucine sulfate shows distinct tubular structure, while polysodium N-undecenoyl-l-valine sulfate also shows tubular morphology but without any distinct order of the tubes. On the other hand, polysodium N-undecenoyl-l-isoleucine sulfate (poly-l-SUCILS) displays random distribution of coiled/curved filaments with heavy association of tightly and loosely bound water. All three polymeric sulfated surfactants are compared for enantioseparation of a broad range of structurally diverse racemic compounds at very acidic, neutral, and basic pH conditions in micellar electrokinetic chromatography (MEKC). A small combinatorial library of 10 structurally related phenylethylamines (PEAs) is investigated for chiral separation under acidic and moderately acidic to neutral pH conditions using an experimental design. In contrast to neutral pH conditions, at acidic pH, significantly enhanced chiral resolution is obtained for class I and class II PEAs due to the compact structure of polymeric sulfated surfactants. It is observed that the presence of a hydroxy group on the benzene ring of PEAs resulted in deterioration of enantioseparation. A sensitive MEKC-mass spectrometry (MS) method is developed for one of the PEAs (e.g., (+/-)-pseudoephedrine) in human urine. Very low limit of detection (LOD) is obtained at pH 2.0 (LOD 325 ng/mL), which is approximately 16 times better compared to pH 8.0 (LOD 5.2 microg/mL). Another broad range of chiral analytes (beta-blockers, phenoxypropionic acid, benzoin derivatives, PTH-amino acids, benzodiazepinones) studied also provided improved chiral separation at low pH compared to high-pH conditions. Among the three polymeric sulfated surfactants, poly-l-SUCILS with two chiral centers on the polymer head group provided overall higher enantioresolution for the investigated acidic, basic, and neutral compounds. This work clearly demonstrates for the first time the superiority of chiral separation and sensitive MS detection at low pH over conventional high-pH chiral separation and detection employing anionic chiral polymeric surfactants in MEKC and MEKC-MS.


Subject(s)
Chromatography, Micellar Electrokinetic Capillary/methods , Surface-Active Agents/chemistry , Amino Acids , Hydrogen-Ion Concentration , Mass Spectrometry , Micelles , Phenethylamines , Polymers , Stereoisomerism
12.
Electrophoresis ; 27(21): 4273-87, 2006 Nov.
Article in English | MEDLINE | ID: mdl-17075924

ABSTRACT

The CEC-MS of alkyltrimethylammonium (ATMA+) ions with chain lengths ranging from C1-C18 is optimized using an internally tapered column packed with mixed mode reversed phase/strong cation exchange stationary phase. A systematic study of the CEC separation parameters is conducted followed by evaluation of the ESI-MS sheath liquid and spray chamber settings. First, the optimization of CEC separation parameters are performed including the ACN concentration, triethylamine (TEA) content, buffer pH and ammonium acetate concentration. Using 90% v/v ACN with 0.04% v/v TEA as mobile phase, the separation of longer chain C6-C18-TMA+ surfactants could be achieved in 15 min. Lowering the ACN concentration to 70% v/v provided resolution of shorter chain C1, C2-TMA+ from C6-TMA+ although the total analysis time increased to 40 min. Furthermore, variation of both the ACN and TEA content as well as ionic strength has found to significantly influence the retention of longer chain surfactants as compared to shorter chains. The optimum CEC conditions are 70% v/v ACN, 0.04% v/v TEA, pH 3.0 and 15 mM ammonium acetate. Next, the optimization of the ESI-MS sheath liquid composition is conducted comparing methanol to isopropanol followed by the use of experimental design for analysis of spray chamber parameters. Overall, the developed CEC-ESI-MS method allows quantitative and sensitive monitoring of ATMA+ from < or =10 microg/mL down to 10 ng/mL. Utilizing the optimized CEC-ESI-MS protocol, the challenging analysis of commercial sample Arquad S-50 ATMA+ containing cis-trans unsaturated and saturated soyabean fatty acid derivatives is demonstrated.


Subject(s)
Capillary Electrochromatography/methods , Quaternary Ammonium Compounds/analysis , Spectrometry, Mass, Electrospray Ionization/methods , Surface-Active Agents/analysis , Acetates/chemistry , Buffers , Cations/analysis , Ethylamines/chemistry , Hydrogen-Ion Concentration
13.
Anal Chem ; 78(19): 7061-9, 2006 Oct 01.
Article in English | MEDLINE | ID: mdl-17007537

ABSTRACT

Two amino acid-derived (leucinol and N-methylpyrrolidinol) chiral ionic liquids are synthesized and characterized in both monomeric and polymeric forms. Leucinol-based chiral cationic surfactant is a room-temperature ionic liquid, and pyrrolidinol-based chiral cationic surfactant melts at 30-35 degrees C to form an ionic liquid (IL). The monomeric and polymeric ILs are thoroughly characterized to determine critical micelle concentration, aggregation number, polarity, optical rotation, and partial specific volume. Herein, we present the first enantioseparation using chiral IL as a pseudostationary phase in capillary electrophoresis. Chiral separation of two acidic analytes, (+/-)-alpha-bromophenylacetic acid and (+/-)-2-(2-chlorophenoxy)propanoic acid (+/-)-(2-PPA) can be achieved with both monomers and polymers of undecenoxycarbonyl-L-pryrrolidinol bromide (L-UCPB) and undecenoxycarbonyl-L-leucinol bromide (L-UCLB) at 25 mM surfactant concentration using phosphate buffer at pH 7.50. The chiral recognition seems to be facilitated by the extent of interaction of the acidic analytes with the cationic headgroup of chiral selectors. Polysodium N-undecenoxycarbonyl-L-leucine sulfate (poly-L-SUCLS) and polysodium N-undecenoxycarbonyl-L-leucinate (poly-L-SUCL) were compared at high and low pH for the enantioseparation of (+/-)-(2-PPA). At pH 7.5, poly-L-SUCLS, poly-L-SUCL, and (+/-)-(2-PPA) are negatively charged resulting in no enantioseparation. However, chiral separation was observed for (+/-)-(2-PPA) using poly-L-SUCLS at low pH (pH 2.00) at which the analyte is neutral. The comparison of chiral separation of anionic and cationic surfactants demonstrates that the electrostatic interaction between the acidic analyte and cationic micelle plays a profound role in enantioseparation.


Subject(s)
Chromatography, Micellar Electrokinetic Capillary/methods , Polymers/chemistry , Ions , Stereoisomerism
14.
Electrophoresis ; 26(21): 4127-37, 2005 Nov.
Article in English | MEDLINE | ID: mdl-16211542

ABSTRACT

The monomers and polymers of four anionic amide type sodium undecenoxy carbonyl glycinate (SUCG) surfactants and four anionic carbamate type sodium undecenoyl glycinate (SUG) surfactants with 1-, 2-, 3-, and 4-glycine unit as head group were synthesized and characterized. The CMC and aggregation number (A) for all eight surfactants were determined using fluorescence spectroscopy. In addition, the CMC values of these surfactants were also projected by surface tension and CE. The CMC of the monomers decreases with increases in the size of glycine head groups and correlates well when the fluorescence method was compared to CE. The A number increases and partial specific volume (V) decreases with increase in size of the head group of both monomers and polymers. However, A and V are always lower for the polymers than the corresponding monomers. The electrophoretic and chromatographic parameters of micelle polymers of SUG and SUCG were also examined. The coefficient of EOF increases with the increase in size of the head group but the electrophoretic mobility decreases which results in a decrease in the elution range. The retention data suggest that the selectivity differences among the mono-, di-, and tripeptide derivatives of poly-SUCG surfactants are relatively higher compared to the derivatives of poly-SUG series.


Subject(s)
Chromatography, Micellar Electrokinetic Capillary/methods , Surface-Active Agents/chemistry , Glycine , Micelles , Polymers , Surface-Active Agents/chemical synthesis
15.
Electrophoresis ; 26(21): 4172-86, 2005 Nov.
Article in English | MEDLINE | ID: mdl-16217829

ABSTRACT

Four alkenoxy leucine-based surfactants with C8-C11 chains containing a terminal double bond, and one C11 chain surfactant with a terminal triple bond are synthesized and characterized in monomeric and polymeric forms. These polymeric pseudophases are then utilized to study the influence of chain length and DP for the enantioseparations of seven beta-blockers in MEKC. Variations in chain length and concentration of polymeric surfactants showed significant effects on the chiral resolution (Rs) and efficiency (N). A relatively large elution range combined with the highest polarity and aggregation number (A) but the lowest retention time, partial specific volume, and optical rotation generated with C8-polymeric surfactant results in simultaneous enantioseparation of all seven beta-blockers with higher N and R(s). In particular, highly hydrophobic beta-blockers are better resolved with shorter hydrocarbon chain even at higher surfactant concentration, which is unachievable with longer chain surfactant. On the other hand, polymer derived from C11-triple bond provided smaller A value compared to C11-double bond surfactant. However, chiral Rs of hydrophobic beta-blockers are still achievable with the C11-triple bond surfactant with enhanced N and shorter analysis time. In addition, effect of polymerization concentration is evaluated by polymerizing all five surfactants at five times their respective CMCs and 100 mM equivalent monomer concentrations. Polymerization of shorter chain (C8 and C9) double-bonded surfactants at five times their respective CMCs results in higher A values with better chiral Rs and N compared to the same two surfactants polymerized at 100 mM.


Subject(s)
Adrenergic beta-Antagonists/isolation & purification , Chromatography, Micellar Electrokinetic Capillary/methods , Surface-Active Agents/chemistry , Amino Acids , Hydrophobic and Hydrophilic Interactions , Micelles , Stereoisomerism
16.
J Chromatogr A ; 1043(2): 291-302, 2004 Jul 23.
Article in English | MEDLINE | ID: mdl-15330104

ABSTRACT

In this study, microemulsions of the chiral surfactant polysodium N-undecenoyl-D-valinate (poly-D-SUV) was utilized for enantiomeric separation by investigating two approaches using polymeric chiral surfactant in microemulsion electrokinetic chromatography (MEEKC). In the first approach, poly-D-SUV was used as an emulsifier surfactant along with 1-butanol and n-heptane. Enantioseparation of anionic or partially anionic binaphthyl derivatives, anionic barbiturates, and cationic paveroline derivatives were achieved by varying the mass fraction of 1-butanol, n-heptane and poly-D-SUV. For anionic or partially anionic analytes, relatively lower mass fractions of n-heptane, and poly-D-SUV were found to give optimum chiral separations as compared to that for cationic solutes. In the second approach, the chiral microemulsion polymer was prepared by polymerizing mixtures of 3.50% (w/w) of sodium N-undecenoyl-D-valinate (D-SUV) and 0.82% (w/w) of n-heptane (core phase) at varying concentration of 1-butanol. After polymerization, the n-heptane and 1-butanol were removed to yield solvent free microemulsion polymers (MPs) which were then utilized for the separation of anionic binaphthyl derivatives and anionic barbiturates. When MPs of D-SUV were utilized for chiral separation, 1.00% (w/w) 1-butanol and 3.50% (w/w) 1-butanol was optimum for enantioseparation of (+/-)-BNP and (+/-)-BOH, respectively. On the other hand, for anionic (+/-)-barbiturates very low concentration of butanol (0.25%, w/w) provided optimum resolution. Compared with micellar electrokinetic chromatography (MEKC), the use of micelle polymers or microemulsion polymers in MEEKC showed dramatic enhancement for resolution of (+/-)-BNP, while this enhancement was less dramatic for other binaphthyls [(+/-)-BOH, (+/-)-BNA] as well as for (+/-)-barbiturates and (+/-)-paveroline derivatives. However, higher separation efficiency of the enantiomers was always observed with MEEKC than in MEKC.


Subject(s)
Chromatography, Micellar Electrokinetic Capillary/methods , Micelles , Polymers/chemistry , Stereoisomerism
17.
Electrophoresis ; 25(4-5): 712-22, 2004 Feb.
Article in English | MEDLINE | ID: mdl-14981700

ABSTRACT

Micellar electrokinetic chromatography (MEKC) was investigated for the enantiomeric separations of three binaphthyl derivatives ((+/-)-1,1'-bi-(2-naphthol) (BOH), (+/-)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BNP), and (+/-)-1,1'-binaphthyl-2,2'-diamine (BNA)) using two recently synthesized chiral polymeric surfactants (polysodium N-undecenoxy carbonyl-L-leucinate (poly-L-SUCL) and polysodium N-undecenoxy carbonyl-L-isoleucinate (poly-L-SUCIL)) in our laboratory. Enantiomeric separation (resolution and selectivity) of the binaphthyl derivatives was influenced by polymerization concentration of the monomeric surfactant, pH, type and concentration of the background electrolyte (BGE) as well as concentration of the polymeric surfactant. Two BGEs (dibasic phosphate and Tris-borate) were compared for this study. The use of dibasic phosphate as BGE in poly-L-SUCL provides baseline resolution of (+/-) BOH and (+/-) BNP, however, no resolution and selectivity at all was observed for (+/-) BNA. A similar approach was adopted with Tris-borate-poly-L-SUCL system at fixed pH 10.1, which resulted in baseline resolution of all three binaphthyl derivatives. Although R(s) of binaphthyl derivatives was always higher and electroosmotic flow (EOF) was always lower using Tris-borate than with dibasic phosphate, the selectivity values for the two buffer systems did not differ significantly. In addition, it was found that poly-L-SUCL provided better enantiomeric resolution and selectivity for (+/-) BOH and (+/-) BNA, while poly-L-SUCIL provided enhanced enantiomeric resolution but similar enantioselectivity for (+/-) BNP. This indicates that the depth of analyte penetration into the palisade layer and the micellar core are responsible for chiral recognition of hydrophobic analyte (e.g., (+/-) BOH, and (+/-) BNA) whereas for moderately hydrophobic analyte (e.g., (+/-) BNP) interaction with the polar head group seems to dictate chiral recognition. Simultaneous enantioresolution of all three binaphthyl derivatives was possible in a single electrophoretic run using either poly-L-SUCL or poly-L-SUCIL. Further comparison of the two polymeric surfactants showed that poly-L-SUCL provided slightly longer analysis time than poly-L-SUCIL but the use of the former polymeric surfactant should be preferred due to its ability to provide complete baseline resolution and higher selectivity of all the three atropisomers with a wider chiral window.


Subject(s)
Alkenes/chemistry , Amino Acids/chemistry , Chromatography, Micellar Electrokinetic Capillary/methods , Naphthalenes/isolation & purification , Polymers/chemistry , Buffers , Electrolytes , Hydrogen-Ion Concentration , Hydrophobic and Hydrophilic Interactions , Micelles , Stereoisomerism , Surface-Active Agents/chemistry
18.
J Orthop Trauma ; 17(1): 70-4, 2003 Jan.
Article in English | MEDLINE | ID: mdl-12499973

ABSTRACT

Gluteal artery aneurysms are rare, and the majority of them are pseudoaneurysms secondary to blunt or penetrating trauma. The superior gluteal artery is normally affected. Inferior gluteal artery pseudoaneurysms are uncommon, and review of the literature revealed only 10 cases in the last 30 years. The mainstay of diagnosis is angiography, but these aneurysms may not be visible on an aortic flush angiogram, and super selective angiography may be required to delineate the anatomy. Treatment is either by surgical therapy or minimally invasive techniques, such as embolization, during angiography. We report two cases of pseudoaneurysms of the inferior gluteal artery following pelvic and acetabular trauma, presenting very differently in time and clinical picture. A review of the relevant literature is also presented.


Subject(s)
Aneurysm, False/etiology , Fractures, Bone/surgery , Multiple Trauma/complications , Pelvis/injuries , Adult , Aneurysm, False/complications , Aneurysm, False/diagnostic imaging , Humans , Injury Severity Score , Male , Multiple Trauma/classification , Radiography
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