Ultrasonic energy enhanced the efficiency of advance extraction methodology for enrichment of trace level of copper in serum samples of patients having neurological disorders.

An innovative dual dispersive ionic liquid based on ultrasound assisted microextraction (UDIL-µE), for the enrichment of trace levels of copper ion (Cu2+), in serum (blood) of patients suffering from different neurological disorders. The enriched metal ions were subjected to flame atomic absorption spectrometry (FAAS). In the UDIL-µE method, the extraction solvent, ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], was dispersed into the aqueous samples using an ultrasonic bath. The(PAN) 1-(2-pyridylazo)-2-naphthol was used as ligand for the complexation of Cu ion in IL (as extracting solvent). The various variables such as sonication time, pH, concentration of complexing agent, time and rate of centrifugation, IL volume that affect the extraction process were optimized. The enhancement factor (EF) and detection limit (LOD) was found under favorable condition was 31 and 0.36µgL-1, respectively. Reliability of the proposed method was checked by relative standard deviation (%RSD), which was found to be <5%. The accuracy of developed procedure was assured by using certified reference material (CRM) of blood serum. The developed procedure was applied successfully to the analysis of concentration of Cu ion in blood serum of different neurological disorders subjects and referents of same age group. It was observed that the levels of Cu ion was two folds higher in serum samples of neurological disorders patients as related to normal referents of same age group.

A new dispersive liquid-liquid microextraction using ionic liquid based microemulsion coupled with cloud point extraction for determination of copper in serum and water samples.

A simple and rapid dispersive liquid-liquid microextraction procedure based on ionic liquid assisted microemulsion (IL-µE-DLLME) combined with cloud point extraction has been developed for preconcentration copper (Cu(2+)) in drinking water and serum samples of adolescent female hepatitits C (HCV) patients. In this method a ternary system was developed to form microemulsion (µE) by phase inversion method (PIM), using ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and nonionic surfactant, TX-100 (as a stabilizer in aqueous media). The Ionic liquid microemulsion (IL-µE) was evaluated through visual assessment, optical light microscope and spectrophotometrically. The Cu(2+) in real water and aqueous acid digested serum samples were complexed with 8-hydroxyquinoline (oxine) and extracted into IL-µE medium. The phase separation of stable IL-µE was carried out by the micellar cloud point extraction approach. The influence of of different parameters such as pH, oxine concentration, centrifugation time and rate were investigated. At optimized experimental conditions, the limit of detection and enhancement factor were found to be 0.132 µg/L and 70 respectively, with relative standard deviation <5%. In order to validate the developed method, certified reference materials (SLRS-4 Riverine water) and human serum (Sero-M10181) were analyzed. The resulting data indicated a non-significant difference in obtained and certified values of Cu(2+). The developed procedure was successfully applied for the preconcentration and determination of trace levels of Cu(2+) in environmental and biological samples.

Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry.

An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be <5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L(-1) and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples.

Toxic Risk Assessment of Arsenic in Males Through Drinking Water in Tharparkar Region of Sindh, Pakistan.

Humans are exposed to arsenic (As) through air, drinking water, and food. The arsenic (As) hazardous quotient was calculated on the basis of its concentration in drinking water of different origin and scalp hair of male subjects (n = 313), residents of different exposed and non-exposed areas of Sindh, Pakistan. The total As was determined in water and scalp hair samples, while As species were determined in water samples by advance extraction methodologies. The total As concentrations in drinking water of less-exposed (LE) and high-exposed (HE) areas was found to be 2.63 to 4.46 and 52 to 235, fold higher than the permissible limit, respectively, than recommended by World Health Organization (2004) for drinking water. While the levels of As in drinking water of non-exposed (NE) areas was within the permissible limit. The resulted data indicated that the dominant species was As(+5) in groundwater samples. The levels of As in scalp hair samples of male subjects of two age groups (18-30 and 31-50 years), belonging to NE, LE, and HE areas, ranged from 0.26 to 0.69, 0.58 to 1.34, and 15.6 to 60.9 µg/g, respectively. A significant correlation between As levels in drinking water and scalp hair was observed in HE area (r = 0.86-0.90, p < 0.001) as compared to those subjects belonging to LE area. A toxicity risk assessment was calculated as hazard quotient (HQ), which indicates that the study subjects of HE area have significantly higher values of HQ than LE. The population of As exposed areas is at high risk of non-carcinogenic and carcinogenesis effects.

Correlation of cadmium and aluminum in blood samples of kidney disorder patients with drinking water and tobacco smoking: related health risk.

The combined exposure to aluminum (Al) and cadmium (Cd) causes more pronounced adverse health effects on humans. The kidneys are the main organs affected by internal exposure to Cd and Al via food and non-food items. The objective of present study was to measure the Al and Cd concentrations in cigarettes tobacco (branded and non-branded) and drinking water (domestic treated, ground and lake water) samples in southern part of Pakistan, to assess the risk due to ingestion of water and inhalation of cigarettes smoke containing high concentrations of both elements. The study population (kidney disorder and healthy) divided into two group based on consuming lake and ground water, while smoking non-branded cigarette as exposed, while drinking domestic treated water and smoking branded cigarette as non-exposed. Electrothermal atomic absorption spectrometry was used to determined Cd and Al concentrations in tobacco, drinking water and blood samples. The resulted data indicated that the levels of Al and Cd in lake and underground water were higher than the permissible limit in drinking water recommended by the World Health Organization. The biochemical parameters of exposed and referent patients, especially urinary N-acetyl-h-glucosaminidase, were used as a biomarkers of kidney disorder. Exposed kidney disorder patients have higher levels of Cd and Al than the exposed referents subjects, while difference was significant when compared to resulted data of non-exposed patients and referents (p = 0.01-0.001). The pearson correlation showed positive correlation between both toxic element concentrations in water, cigarettes versus blood samples of exposed subjects (r = 0.20-0.67 and 0.71-0.82), while lower values were observed for non-exposed subjects (r = 0.123-0.423 and 0.331-0.425), respectively.

Estimation of Nickel in Different Smokeless Tobacco Products and Their Impact on Human Health of Oral Cancer Patients.

It has been extensively investigated that the chewing of smokeless tobacco (SLT) products may enhance the inflammation of the oral cavity. The aim of the present study is to evaluate the relationship between nickel (Ni) exposure via different SLT products with oral cancer (different sites) incidence in the population of Sindh, Pakistan. The different brands of SLT products (mainpuri, gutkha, and moist snuff) commonly consumed by the studied population were analyzed for Ni contents. The biological samples of oral cancer patients and noncancerous control subjects of both genders, who have or have not consumed SLT products, were collected. The concentration of Ni in biological samples and SLT products were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by using certified reference materials. The results of this study showed that the Ni level was significantly higher in scalp hair and blood samples of oral cancer patients compared to controls (P < 0.01). The study suggested that exposure of Ni as a result of chewing different SLT products may be synergistic with risk factors associated with oral cancer.

Evaluation of the fate of arsenic-contaminated groundwater at different aquifers of Thar coalfield Pakistan.

In present study, the ground water at different aquifers was evaluated for physicochemical parameters, iron, total arsenic, total inorganic arsenic and arsenic species (arsenite and arsenate). The samples of groundwater were collected at different depths, first aquifer (AQ1) 50-60 m, second aquifer (AQ2) 100-120 m, and third aquifer (AQ3) 200-250 m of Thar coalfield, Pakistan. Total inorganic arsenic was determined by solid phase extraction using titanium dioxide as an adsorbent. The arsenite was determined by cloud point extraction using ammonium pyrrolidinedithiocarbamate as a chelating reagent, and resulted complex was extracted by Triton X-114. The resulted data of groundwater were reported in terms of basic statistical parameters, principal component, and cluster analysis. The resulted data indicated that physicochemical parameters of groundwater of different aquifers were exceeded the World Health Organization provisional guideline for drinking water except pH and SO4(2-). The positive correlation was observed between arsenic species and physicochemical parameters of groundwater except F(-) and K(+), which might be caused by geochemical minerals. Results of cluster analysis indicated that groundwater samples of AQ1 was highly contaminated with arsenic species as compared to AQ2 and AQ3 (p > 0.05).

Variation in the Levels of Aluminum and Manganese in Scalp Hair Samples of the Patients Having Different Psychiatric Disorders with Related to Healthy Subjects.

There is very limited information available on the role of trace elements in psychiatric disorders (PSD). Immense pieces of evidence support the idea that exposure to trace and toxic metals, such as aluminum (Al) and manganese (Mn), may be factors or cofactors in the etiopathogenesis of a variety of psychiatric disorders. The aim of our study was to assess the Al and Mn in scalp hair samples of 102 patients having different types of psychiatric disorder PSD diseases together with 120 referent subjects of male patients in the age group of 45-60 years. The understudy elements in scalp hair samples were assessed by the flame atomic absorption spectrophotometry after microwave-assisted acid digestion method .The validity of methodology was checked by the certified human hair reference material (NCS ZC81002). The recovery of studied elements was found in the range of 98.1-99.2 % of certified reference material. The results of this study showed that the mean values of Al and Mn were significantly higher in scalp hair samples of all types of PSD as compared to referents subjects. The resulted data indicated a significant increase in the contents of Mn and Al in scalp hair samples of psychiatric patients than that of its control counterpart, which may provide prognostic tool for the diagnosis of the mental disorders. However, further work is suggested to examine the exact correlation between trace elements level and the degree of disorder.

Estimation of lead in biological samples of oral cancer patients chewing smokeless tobacco products by ionic liquid-based microextraction in a single syringe system.

Several studies have reported that the chewing habit of smokeless tobacco (SLT) has been associated with oral cancer. The aim of the present study was to evaluate the trace levels of lead (Pb) in biological samples (blood, scalp hair) of oral cancer patients and referents of the same age group (range 30-60 years). As the concentrations of Pb are very low in biological samples, so a simple and efficient ionic liquid-based microextraction in a single syringe system has been developed, as a prior step to determination by flame atomic absorption spectrometry. In this procedure, the hydrophobic chelates of Pb with ammonium pyrrolidinedithiocarbamate (APDC) were extracted into fine droplets of 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] within a syringe while using Triton X-114 as a dispersant. Factors influencing the microextraction efficiency and determination, such as pH of the sample, volume of [C4MIM][PF6] and Triton X-114, ligand concentration, and incubation time, were studied. To validate the proposed method, certified reference materials were analyzed and the results of Pb(2+) were in good agreement with certified values. At optimum experimental values of significant variables, detection limit and enhancement factor were found to be 0.412 µg/L and 80, respectively. The coexisting ions showed no obvious negative outcome on Pb preconcentration. The proposed method was applied satisfactorily for the preconcentration of Pb(2+) in acid-digested SLT and biological samples of the study population. It was observed that oral cancer patients who consumed different SLT products have 2-3-fold higher levels of Pb in scalp hair and blood samples as compared to healthy referents (p < 0.001). While 31.4-50.8% higher levels of Pb were observed in referents chewing different SLT products as compared to nonconsumers (p < 0.01).

Assessment of selenium and mercury in biological samples of normal and night blindness children of age groups (3-7) and (8-12) years.

The causes of night blindness in children are multifactorial and particular consideration has been given to childhood nutritional deficiency, which is the most common problem found in underdeveloped countries. Such deficiency can result in physiological and pathological processes that in turn influence biological sample composition. This study was designed to compare the levels of selenium (Se) and mercury (Hg) in scalp hair, blood, and urine of night blindness children age ranged (3-7) and (8-12) years of both genders, comparing them to sex- and age-matched controls. A microwave-assisted wet acid digestion procedure was developed as a sample pretreatment for the determination of Se and Hg in biological samples of night blindness children. The proposed method was validated by using conventional wet digestion and certified reference samples of hair, blood, and urine. The Se and Hg in biological samples were measured by electrothermal atomic absorption spectrometry and cold vapor atomic absorption spectrometry, prior to microwave acid digestion, respectively. The concentration of Se was decreased in scalp hair and blood samples of male and female night blindness children while Hg was higher in all biological samples as compared to referent subjects. The Se concentration was inversely associated with the risk of night blindness in both genders. These results add to an increasing body of evidence that Se is a protecting element for night blindness. These data present guidance to clinicians and other professional investigating deficiency of essential micronutrients in biological samples (scalp hair and blood) of night blindness children.

Arsenic in coal of the Thar coalfield, Pakistan, and its behavior during combustion.

The aim of the current study is to evaluate the occurrence of arsenic in coal collected from Thar coalfield, Pakistan, and its behavior during the combustion. Fractionation of arsenic (As) in coal samples was carried out by Community Bureau of Reference sequential extraction scheme (BCR-SES) and single-step-based BCR method (BCR-SS). These methods are validated using the certified reference material of sediment BCR 701 and standard addition method. The stepwise fractions of As in laboratory-made ash (LMA) have been also investigated. The extractable As content associated with different phases in coal and LMA samples were analyzed by electrothermal atomic absorption spectrophotometer. The extraction efficiency of As by BCR-SS was slightly higher than BCR-SES, while the difference was not significant (p < 0.05). The BCR-SS method is a time-saving method because it can reduce the extraction time from 51 to 22 h. The As contents in LMA revealed that during combustion of the coal, >85 % of As may be released into atmosphere. The relative mobility of As in the coal samples was found in increasing order as follows: oxidizable fraction < reducible fraction < acid soluble fraction. The total and extractable As obtained by BCR-SES and BCR-SS were higher in coal samples of block III as compared to block V (p > 0.05).

Correlation of aluminum and manganese concentration in scalp hair samples of patients having neurological disorders.

Neurodegenerative diseases are thought to be multifactorial, while metals (aluminum and manganese) can be involved as cofactors in abnormalities or suspected of being risk factors for this disorder. The aim of our study was to assess the aluminum (Al) and manganese (Mn) concentrations in scalp hair samples of 397 patients having different types of neurological disorder diseases. For comparative purpose, scalp hair samples of 201 control subjects does not have any neuro-disorders of same age group (30-60 years) and were selected as referents. The Al and Mn in scalp hair samples were assessed by the electrothermal atomic absorption spectrophotometry after microwave-assisted acid digestion. The validity of methodology was checked by the certified human hair reference material (NCS ZC81002). The results of this study showed that the mean values of Al and Mn were significantly higher in scalp hair samples of all types of neurological disorder patients as compared to controls (p = 0.01-0.001). The high levels of Al and Mn may play a role in the development of neurological disorders. However, further work is suggested to examine the precise correlation between trace elemental level and the degree of disorders in neurological patients.

Comparative evaluation of essential and toxic elements in the blood of kidney failure patients and healthy referents.

The aim of the present study was to evaluate the comparative distribution, correlation, and apportionment of selected elements-aluminum (Al), calcium (Ca), cadmium (Cd), potassium (K), magnesium (Mg), sodium (Na), and lead (Pb)-in the blood samples of male kidney failure patients (KFP) and healthy subjects of age ranged 30-60 years. The blood samples were digested with nitric acid and perchloric acid mixture (2:1), followed by the quantification of elements by atomic absorption spectrometry. The concentration of essential elements in blood samples of KFP were found in the range of Ca (97-125), Mg (18-36), Na (2971-3685), and K (177-270) mg/L while, the levels of Al, Cd, and Pb were found in the range of (475-1275), (0.9-9.9), and (211-623) µg/L, respectively. In the healthy referents, concentration of electrolytes in blood samples was lower than KFP, but difference was not significant (p > 0.05). While the levels of toxic elements in blood samples of referents were three- to sixfold lower than KFP (p < 0.01). Principal component analysis (PCA) and cluster analysis (CA) of the element data manifested diverse apportionment of the selected elements in the blood sample of the KFP compared with the healthy counterparts.

Temperature controlled ionic liquid-based dispersive micro-extraction using two ligands, for determination of aluminium in scalp hair samples of Alzheimer's patients: a multivariate study.

A green and sensitive temperature controlled dispersive liquid-liquid microextraction (TIL-DLLME) methodology based on the application of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], as an extractant solvent was proposed for the preconcentration of trace levels of aluminium (Al(3+)) in scalp hair samples of Alzheimer's (AD) patients, prior to analyzing by flame atomic absorption spectrometry (FAAS). The Al(3+) was complexed with 8-hydrooxyquinoline (oxine) (L1) and 3,5,7,2'-4' pentahydroxy flavone (morin) (L2) separately and then extracted by IL at temperature (50±2.0°C). Some effective factors that influence the TIL-DLLME efficiency such as pH, ligands concentrations, volume of IL, ionic strength, and incubation time were investigated and optimized by multivariate analysis. In the optimum experimental conditions, the limit of detection (3s) and enhancement factor were 0.56 µg L(-1), 0.64 µg L(-1) and 85, 73 for both ligands, respectively. The relative standard deviation (RSD) for six replicate determinations of 100 µg L(-1) Al(3+) complexed with oxine and morin were found to be 3.88% and 4.74%, respectively. The developed method was validated by the analysis of certified reference material of human hair (NCSZC81002).and applied satisfactorily to the determination of Al(3+) in acid digested scalp hair samples of AD patients and healthy controls. The resulted data shows significant higher level in scalp hair samples of AD male patients with related to referents of same age and socioeconomic status.

Scalp hair and blood cadmium levels in association with chewing gutkha, mainpuri, and snuff, among patients with oral cancer in Pakistan.

BACKGROUND: It has been reported that smokeless tobacco (SLT) chewing can lead to caners of oral cavity. In this study, the relationship between cadmium exposure via consumption of different SLT products by patients with oral cancer with related to referents belongs to different cities of Pakistan are investigated. METHODS: The cadmium in different types of SLT products (gutkha, mainpuri and snuff) consumed by studied population and biological samples (scalp hair and blood) of cancerous and healthy subjects were analyzed. Both referents and patients with cancer have same age group (ranged 30-60 years), socioeconomic status, localities, and dietary habits. The concentrations of cadmium in SLT products and biological samples were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials. RESULTS: It was estimated that 10 g intake of different types of gutkha, mainpuri, and snuff could contribute, 18-40%, 15.7-33.6%, and 14-68% of the provisional maximum tolerable daily intake of cadmium, respectively for adults (60 kg). The results of present study showed that the mean value of cadmium was significantly higher in scalp hair and blood samples of patients with oral cancer as compared to those results obtained for referents (P < 0.001). CONCLUSIONS: The high exposure of cadmium due to consuming different SLT products may have synergistic effects with other risk factors associated for oral cancer.

A new solid phase microextraction method using organic ligand in micropipette tip syringe system packed with modified carbon cloth for preconcentration of cadmium in drinking water and blood samples of kidney failure patients.

A simple and efficient miniaturized solid phase microextraction (M-SPµE) in a syringe system was developed for preconcentration of cadmium (Cd) in environmental and biological samples, followed by flame atomic absorption technique. The syringe system contains the micropipette tip packed with activated carbon cloth, coated with modified magnetic nanoparticles of iron oxide Triton X114 (ACC-NPs). Scanning electron microscopy and energy dispersive spectroscopy used for characterization of the size, morphology and elemental composition of ACC-NPs. The sample solution treated with a complexing reagent 8-hydroxyqunilone (8-HQ), and drawn into the syringe, filled with ACC-MNPs and dispensed manually for 2-10 drawing/discharging cycles. The analyte retained on ACC-NPs in micropipette tip-syringe system were then eluted with different volume of 1.5molL(-1) HCl by 1-5 drawing/discharging cycles. The syringe system directly couple with FAAS for analysis. The influence of different variables on the extraction efficiency of Cd, including adsorbent dosage, pH, sample volume, eluent volume and drawing/discharging cycles of syringe system were optimized. At optimized extraction conditions, the method showed good linearity in the range of 5-250µgL(-1), with a limit of detection 0.15µgL(-1). Repeatability of the extraction (%RSD) was <5%, n=5. The validity and accuracy of the method was checked by the certified reference materials. The proposed method was successfully applied for the determination of Cd in different drinking water and biological samples of kidney failure patients and healthy controls.

Maturation of the adolescent brain.

Adolescence is the developmental epoch during which children become adults - intellectually, physically, hormonally, and socially. Adolescence is a tumultuous time, full of changes and transformations. The pubertal transition to adulthood involves both gonadal and behavioral maturation. Magnetic resonance imaging studies have discovered that myelinogenesis, required for proper insulation and efficient neurocybernetics, continues from childhood and the brain's region-specific neurocircuitry remains structurally and functionally vulnerable to impulsive sex, food, and sleep habits. The maturation of the adolescent brain is also influenced by heredity, environment, and sex hormones (estrogen, progesterone, and testosterone), which play a crucial role in myelination. Furthermore, glutamatergic neurotransmission predominates, whereas gamma-aminobutyric acid neurotransmission remains under construction, and this might be responsible for immature and impulsive behavior and neurobehavioral excitement during adolescent life. The adolescent population is highly vulnerable to driving under the influence of alcohol and social maladjustments due to an immature limbic system and prefrontal cortex. Synaptic plasticity and the release of neurotransmitters may also be influenced by environmental neurotoxins and drugs of abuse including cigarettes, caffeine, and alcohol during adolescence. Adolescents may become involved with offensive crimes, irresponsible behavior, unprotected sex, juvenile courts, or even prison. According to a report by the Centers for Disease Control and Prevention, the major cause of death among the teenage population is due to injury and violence related to sex and substance abuse. Prenatal neglect, cigarette smoking, and alcohol consumption may also significantly impact maturation of the adolescent brain. Pharmacological interventions to regulate adolescent behavior have been attempted with limited success. Since several factors, including age, sex, disease, nutritional status, and substance abuse have a significant impact on the maturation of the adolescent brain, we have highlighted the influence of these clinically significant and socially important aspects in this report.