Smart Synthesis of Trimethyl Ethoxysilane (TMS) Functionalized Core-Shell Magnetic Nanosorbents Fe3O4@SiO2: Process Optimization and Application for Extraction of Pesticides.

In the current study, a smart approach for synthesizing trimethyl ethoxysilane-decorated magnetic-core silica-nanoparticles (TMS-mcSNPs) and its effectiveness as nanosorbents have been exploited. While the magnetite core was synthesized using the modified Mössbauer method, Stöber method was employed to coat the magnetic particles. The objective of this work is to maximize the magnetic properties and to minimize both particle size (PS) and particle size distribution (PSD). Using a full factorial design (2k-FFD), the influences of four factors on the coating process was assessed by optimizing the three responses (magnetic properties, PS, and PSD). These four factors were: (1) concentration of tetraethyl-orthosilicate (TEOS); (2) concentration of ammonia; (3) dose of magnetite (Fe3O4); and (4) addition mode. Magnetic properties were calculated as the attraction weight. Scanning electron microscopy (SEM) was used to determine PS, and standard deviation (±SD) was calculated to determine the PSD. Composite desirability function (D) was used to consolidate the multiple responses into a single performance characteristic. Pareto chart of standardized effects together with analysis of variance (ANOVA) at 95.0 confidence interval (CI) were used to determine statistically significant variable(s). Trimethyl ethoxysilane-functionalized mcSNPs were further applied as nanosorbents for magnetic solid phase extraction (TMS-MSPE) of organophosphorus and carbamate pesticides.

A Comparison between Different Agro-Wastes and Carbon Nanotubes for Removal of Sarafloxacin from Wastewater: Kinetics and Equilibrium Studies.

In the current study, eco-structured and efficient removal of the veterinary fluoroquinolone antibiotic sarafloxacin (SARA) from wastewater has been explored. The adsorptive power of four agro-wastes (AWs) derived from pistachio nutshells (PNS) and Aloe vera leaves (AV) as well as the multi-walled carbon nanotubes (MWCNTs) has been assessed. Adsorbent derived from raw pistachio nutshells (RPNS) was the most efficient among the four tested AWs (%removal '%R' = 82.39%), while MWCNTs showed the best adsorptive power amongst the five adsorbents (%R = 96.20%). Plackett-Burman design (PBD) was used to optimize the adsorption process. Two responses ('%R' and adsorption capacity 'qe') were optimized as a function of four variables (pH, adsorbent dose 'AD' (dose of RPNS and MWCNTs), adsorbate concentration [SARA] and contact time 'CT'). The effect of pH was similar for both RPNS and MWCNTs. Morphological and textural characterization of the tested adsorbents was carried out using FT-IR spectroscopy, SEM and BET analyses. Conversion of waste-derived materials into carbonaceous material was investigated by Raman spectroscopy. Equilibrium studies showed that Freundlich isotherm is the most suitable isotherm to describe the adsorption of SARA onto RPNS. Kinetics' investigation shows that the adsorption of SARA onto RPNS follows a pseudo-second order (PSO) model.

Mishandling and exposure of farm workers in Qatar to organophosphate pesticides.

We used a combination of subjective (questionnaire) and objective (urinary metabolites) measurements to evaluate factors that can predict the exposure of farm workers in Qatar to organophosphate pesticides and to assess whether the levels of exposure are associated with any self-reported health outcomes. The results show that pesticides were being extensively mishandled in the farms. Very few (<2%) of the farm workers knew the names of the pesticide they were using, and about one-third of the participants did not know the amount of pesticides to be applied to the crops. Nearly all (96%) of the participants had participated in mixing pesticides together before use and few (29%) used protective clothing while engaged in this operation. A significant number of participants (18%) had no knowledge that pesticides are a health hazard. At least one dialkyllphosphate (DAP) metabolite was detected in every worker. The geometric mean (GM) concentration of the dimethylalkylphosphates (DMAP) was 108 nM (range, from below the limit of detection (LOD) to 351 nM), and the GM for the diethylalkylphosphates (DEAP) was 43 nM (range, LOD-180 nM). The GM for total concentration of the metabolites (DAP) of 146 nM (maximum value estimated to be 531 nM) is below the values that have been reported for farmers in some countries, but higher than the levels in the general populations of many countries. We explored the influence of metal exposure and found consistent and negative relationships between the DAP metabolites and the concentrations of most of the trace elements in the urine of the farm workers; the negative associations were statistically significant for Cr, Mn, Fe, Ni, As, and Pb. We suspect that the negative associations are not source-dependent but may be reflective of antagonistic relationships in human metabolism of OPPs and trace metals; hence we recommend that metals should be included as co-factors in assessing the health effects of OPP exposure.

Biomolecular alterations in acute traumatic brain injury (TBI) using Fourier transform infrared (FTIR) imaging spectroscopy.

Acute injury is one of the substantial stage post-traumatic brain injury (TBI) occurring at the moment of impact. Decreased metabolism, unregulated cerebral blood flow and direct tissue damage are triggered by acute injury. Understating the biochemical alterations associated with acute TBI is critical for brain plasticity and recovery. The objective of this study was to investigate the biochemical and molecular changes in hippocampus, corpus callosum and thalamus brain regions post-acute TBI in rats. Fourier Transform Infrared (FTIR) imaging spectroscopy were used to collect chemical images from control and 3 hrs post-TBI (Marmarou model was used for the TBI induction) rat brains and adjacent sections were treated by hematoxylin and eosin (H&E) staining to correlate with the disruption in tissue morphology and injured brain biochemistry. Our results revealed that the total lipid and total protein content decreased significantly in the hippocampus, corpus callosum and thalamus after brain injury. Reduction in lipid acyl chains (-CH2) associated with an increase in methyl (-CH3) and unsaturated lipids olefin = CH concentrations is observed. Furthermore, there is a decrease in the lipid order (disorder), which leads to an increase in acyl chain fluidity in injured rats. The results suggest acute TBI damages brain tissues mechanically rather than chemical alterations. This will help in assessing successful therapeutic strategy in order to mitigate tissue damage in acute TBI period.

Fourier Transform Infrared Imaging-A Novel Approach to Monitor Bio Molecular Changes in Subacute Mild Traumatic Brain Injury.

Traumatic brain injury (TBI) can be defined as a disorder in the function of the brain after a bump, blow, or jolt to the head, or penetrating head injury. Mild traumatic brain injury (mTBI) can cause devastating effects, such as the initiation of long-term neurodegeneration in brain tissue. In the current study, the effects of mTBI were investigated on rat brain regions; cortex (Co) and corpus callosum (CC) after 24 h (subacute trauma) by Fourier transform infrared (FTIR) imaging and immunohistochemistry (IHC). IHC studies showed the formation of amyloid-ß (Aß) plaques in the cortex brain region of mTBI rats. Moreover, staining of myelin basic protein presented the shearing of axons in CC region in the same group of animals. According to FTIR imaging results, total protein and lipid content significantly decreased in both Co and CC regions in mTBI group compared to the control. Due to this significant decrease in both lipid and protein content, remarkable consistency in lipid/protein band ratio in mTBI and control group, was observed. Significant decrease in methyl content and a significant increase in olefinic content were observed in Co and CC regions of mTBI rat brain tissues. Classification amongst distinguishable groups was performed using principal component analysis (PCA) and hierarchical clustering (HCA). This study established the prospective of FTIR imaging for assessing biochemical changes due to mTBI with high sensitivity, precision and high-resolution.

Remote Corticospinal Tract Degeneration After Cortical Stroke in Rats May Not Preclude Spontaneous Sensorimotor Recovery.

Background. Recovery of motor function after stroke appears to be related to the integrity of axonal connections in the corticospinal tract (CST) and corpus callosum, which may both be affected after cortical stroke. Objective. In the present study, we aimed to elucidate the relationship of changes in measures of the CST and transcallosal tract integrity, with the interhemispheric functional connectivity and sensorimotor performance after experimental cortical stroke. Methods. We conducted in vivo diffusion magnetic resonance imaging (MRI), resting-state functional MRI, and behavior testing in twenty-five male Sprague Dawley rats recovering from unilateral photothrombotic stroke in the sensorimotor cortex. Twenty-three healthy rats served as controls. Results. A reduction in the number of reconstructed fibers, a lower fractional anisotropy, and higher radial diffusivity in the ipsilesional but intact CST, reflected remote white matter degeneration. In contrast, transcallosal tract integrity remained preserved. Functional connectivity between the ipsi- and contralesional forelimb regions of the primary somatosensory cortex significantly reduced at week 8 post-stroke. Comparably, usage of the stroke-affected forelimb was normal at week 28, following significant initial impairment between day 1 and week 8 post-stroke. Conclusions. Our study shows that post-stroke motor recovery is possible despite degeneration in the CST and may be supported by intact neuronal communication between hemispheres.

Eco-structured Adsorptive Removal of Tigecycline from Wastewater: Date Pits' Biochar versus the Magnetic Biochar.

Non-magnetic and magnetic low-cost biochar (BC) from date pits (DP) were applied to remove tigecycline (TIGC) from TIGC-artificially contaminated water samples. Pristine biochar from DP (BCDP) and magnetite-decorated biochar (MBC-DP) were therefore prepared. Morphologies and surface chemistries of BCDP and MBC-DP were explored using FT-IR, Raman, SEM, EDX, TEM, and BET analyses. The obtained IR and Raman spectra confirmed the presence of magnetite on the surface of the MBC-DP. SEM results showed mesoporous surface for both adsorbents. BET analysis indicated higher amount of mesopores in MBC-DP. Box-Behnken (BB) design was utilized to optimize the treatment variables (pH, dose of the adsorbent (AD), concentration of TIGC [TIGC], and the contact time (CT)) and maximize the adsorptive power of both adsorbents. Higher % removal (%R), hitting 99.91%, was observed using MBC-DP compared to BCDP (77.31%). Maximum removal of TIGC (99.91%) was obtained using 120 mg/15 mL of MBC-DP for 10 min at pH 10. Equilibrium studies showed that Langmuir and Freundlich isotherms could best describe the adsorption of TIGC onto BCDP and MBC-DP, respectively, with a maximum adsorption capacity (qmax) of 57.14 mg/g using MBC-DP. Kinetics investigation showed that adsorption of TIGC onto both adsorbents could be best-fitted to a pseudo-second-order (PSO) model.

Application of geopolymers synthesized from incinerated municipal solid waste ashes for the removal of cationic dye from water.

In this study, municipal solid waste bottom ash (MSW-BA) and fly ash (MSW-FA) were used as a source of aluminosilicate to prepare geopolymer (GEO) adsorbents (GEO-MSWBA and GEO-MSWFA) for the removal of methylene blue (MB) from water. The effects of temperature, pH, and initial concentration on the MB adsorption onto GEO-MSWBA and GEO-MSWFA were evaluated. The adsorption isotherms parameters and thermodynamics were also determined. Detailed physical and chemical characterizations of the prepared adsorbents were carried out to further understand their impact on MB adsorption. The results from the scanning electron microscopy revealed a uniform granule-sphere like structure on both prepared geopolymers, which would facilitate the MB adsorption onto the adsorbents. The X-ray diffraction allowed observation of the microstructural transformations that occur after the alkaline activation. The surface areas of the GEO-MSWBA and the GEO-MSWFA were recorded as 32.78 m2/g and 4.5 m2/g, respectively. From the Fourier transform infrared, a stretching vibration of the aluminosilicate tetrahedral was observed, which indicated the success of geopolymerization. The prepared geopolymers showed a high capability of MB adsorption from an aqueous solution. The adsorption process was best suited and explained using the Langmuir isotherm model with a maximum adsorption capacity of 666.7 mg/g for the GEO-MSWBA (at 25°C) and 769.2 mg/g for the GEO-MSWFA (at 35°C). The positive value of the enthalpy (ΔHo) for the GEO-MSWBA suggested the reaction favored endothermic reaction while the negative value of entropy (ΔSo) indicated a solid/liquid random interaction. On the other hand, the negative ΔHo value for the GEO-MSWFA indicated the reaction followed an exothermic reaction causing energy to be released, the positive ΔSo value indicated a good affinity at the solid-liquid surface. The overall negative value for Gibbs free energy (ΔGo) for both adsorbents suggested the adsorption was spontaneous and feasible. It was also inferred that n- π interaction, direct and indirect hydrogen bond, and electrostatic interaction between the MB and the prepared geopolymers facilitated the adsorption process. The current study shows that the GEO-MSWBA and the GEO-MSWFA have a great potential of removing MB as a cationic dye from water without performing any sort of laborious pretreatments.

Physiochemical characterization and systematic investigation of metals extraction from fly and bottom ashes produced from municipal solid waste.

Incineration has emerged as one of the acceptable ways to treat municipal solid waste (MSW) due to its potential in reducing the mass and volume of the waste. However, it produces two major by-product residues, namely MSW-bottom ash (MSW-BA) and MSW-fly ash (MSW-FA). These residues have gained great attention to their hazardous nature and potential to be reused and recycled. In this paper, the physicochemical characterizations of the MSW-BA and the MSW-FA were performed, followed by a systematic investigation of metals extraction from MSW-BA and MSW-FA. Various extracting agents were used to investigate the possibility to extract 21 metals including cadmium (Cd), vanadium (V), chromium (Cr), and lead (Pb). It was revealed that some metals were present in a high amount in the MSW-BA while other metals were higher in the MSW-FA. Moreover, the energy-dispersive X-ray spectroscopy results revealed that the MSW-BA was dominated by oxygen (O) 55.4 ±0.6 wt%, silicon (Si) 22.5 ±0.3 wt%, and calcium (Ca) 18.5 ±0.2 wt%. On the other hand, the MSW-FA was enriched with Ca 45.2 ±0.5 wt%, and O 40.3 ±0.4 wt%. From the scanning electron microscopy, the MSW-BA was observed as flaky with an irregular surface that consisted of large pores, while, the MSW-FA was present as agglomerated particles and had a bimodal distribution. Moreover, Fourier transform infrared spectroscopy revealed that Al-Fe-OH, Al-Al-OH, Si-O, C-O, and C-H were some of the major functional groups present in the ashes. The F-tests concluded that the metal extraction from the MSW-BA and MSW-FA were significantly affected by the acid type. it is concluded that nitric acid and phosphoric acid were the best-suited acid for the MSW-BA while sulfuric acid and phosphoric acid for the MSW-FA. More than 11 wt% of Cd and 9 wt% of Cu were extracted from MSW-BA while 6 wt% of Pb and 4.5 wt% of V were extracted from the MSW-FA. The present methodology is an interesting development in metal extraction from the MSW-BA and the MSW-FA, which can develop in a cost-effective and sustainable option to utilize MSW.

An Innovative Platform Merging Elemental Analysis and Ftir Imaging for Breast Tissue Analysis.

Histopathology and immunohistology remain the gold standard for breast cancer diagnostic. Yet, these approaches do not usually provide a sufficiently detailed characterization of the pathology. The purpose of this work is to demonstrate for the first time that elemental analysis and Fourier transform infrared spectroscopy microscopic examination of breast tissue sections can be merged into one dataset to provide a single set of markers based on both organic molecules and inorganic trace elements. For illustrating the method, 6 mammary tissue sections were used. Fourier transform infrared (FTIR) spectroscopy images reported a fingerprint of the organic molecules present in the tissue section and laser ablation elemental analysis (LA-ICP-MS) images brought inorganic element profiles. The 6 tissue sections provided 31 106 and 150,000 spectra for FTIR and LA-ICP-MS spectra respectively. The results bring the proof of concept that breast tissue can be analyzed simultaneously by FTIR spectroscopy and laser ablation elemental analysis (LA-ICP-MS) to provide in both case reasonably high resolution images. We show how to bring the images obtained by the two methods to a same spatial resolution and how to use image registration to analyze the data originating from both techniques as one block of data. We finally demonstrates the elemental analysis is orthogonal to all FTIR markers as no significant correlation is found between FTIR and LA-ICP-MS data. Combining FTIR and LA-ICP-MS imaging becomes possible, providing two orthogonal methods which can bring an unprecedented diversity of information on the tissue. This opens a new avenue of tissue section analyses providing unprecedented diagnostic potential.

Investigation of Biochemical Alterations in Ischemic Stroke Using Fourier Transform Infrared Imaging Spectroscopy-A Preliminary Study.

OBJECTIVE: Brain damage, long-term disability and death are the dreadful consequences of ischemic stroke. It causes imbalance in the biochemical constituents that distorts the brain dynamics. Understanding the sub-cellular alterations associated with the stroke will contribute to deeper molecular understanding of brain plasticity and recovery. Current routine approaches examining lipid and protein biochemical changes post stoke can be difficult. Fourier Transform Infrared (FTIR) imaging spectroscopy can play a vital role in detecting these molecular alterations on a sub-cellular level due to its high spatial resolution, accuracy and sensitivity. This study investigates the biochemical and molecular changes in peri-infract zone (PIZ) (contiguous area not completely damaged by stroke) and ipsi-lesional white matter (WM) (right below the stroke and PIZ regions) nine weeks post photothrombotic ischemic stroke in rats. MATERIALS AND METHODS: FTIR imaging spectroscopy and transmission electron microscopy (TEM) techniques were applied to investigate brain tissue samples while hematoxylin and eosin (H&E) stained images of adjacent sections were prepared for comparison and examination the morphological changes post stroke. RESULTS: TEM results revealed shearing of myelin sheaths and loss of cell membrane, structure and integrity after ischemic stroke. FTIR results showed that ipsi-lesional PIZ and WM experienced reduction in total protein and total lipid content compared to contra-lesional hemisphere. The lipid/protein ratio reduced in PIZ and adjacent WM indicated lipid peroxidation, which results in lipid chain fragmentation and an increase in olefinic content. Protein structural change is observed in PIZ due to the shift from random coli and α-helical structures to ß-sheet conformation. CONCLUSION: FTIR imaging bio-spectroscopy provide novel biochemical information at sub-cellular levels that be difficult to be obtained by routine approaches. The results suggest that successful therapeutic strategy that is based on administration of anti-oxidant therapy, which could reduce and prevent neurotoxicity by scavenging the lipid peroxidation products. This approach will mitigate tissue damage in chronic ischemic period. FTIR imaging bio-spectroscopy can be used as a powerful tool and offer new approach in stroke and neurodegenerative diseases research.

Investigation of the Effect of PD-L1 Blockade on Triple Negative Breast Cancer Cells Using Fourier Transform Infrared Spectroscopy.

Interactions between programmed death-1 (PD-1) with its ligand PD-L1 on tumor cells can antagonize T cell responses. Inhibiting these interactions using immune checkpoint inhibitors has shown promise in cancer immunotherapy. MDA-MB-231 is a triple negative breast cancer cell line that expresses PD-L1. In this study, we investigated the biochemical changes in MDA-MB-231 cells following treatment with atezolizumab, a specific PD-L1 blocker. Our readouts were Fourier Transform Infrared (FTIR) spectroscopy and flow cytometric analyses. Chemometrical analysis, such as principal component analysis (PCA), was applied to delineate the spectral differences. We were able to identify the chemical alterations in both protein and lipid structure of the treated cells. We found that there was a shift from random coil and α-helical structure to ß-sheet conformation of PD-L1 on tumor cells due to atezolizumab treatment, which could hinder binding with its receptors on immune cells, ensuring sustained T cell activation for potent immune responses. This work provides novel information about the effects of atezolizumab at molecular and cellular levels. FTIR bio-spectroscopy, in combination with chemometric analyses, may expedite research and offer new approaches for cancer immunology.

Correction: Discrimination of breast cancer from benign tumours using Raman spectroscopy.

[This corrects the article DOI: 10.1371/journal.pone.0212376.].

Recycling of Date Pits Into a Green Adsorbent for Removal of Heavy Metals: A Fractional Factorial Design-Based Approach.

Date pits (DPs) have been recycled into a low-cost adsorbent for removing of selected heavy metals (HMs) from artificially contaminated aqueous solutions. Adsorption of targeted HMs, both by raw date pits (RDP) and burnt date pits (BDP) was tested. Results showed that BDP is more efficient as an adsorbent and mostly adsorbing Cu(II). A novel approach; fractional factorial design (2 k-p - FrFD) was used to build the experimental pattern of this study. The effects of four factors on the maximum percentage (%) of removal (Y) were considered; pH, adsorbent dose (AD), heavy metal concentration (HMC), and contact time (CT). Statistically significant variables were detected using Pareto chart of standardized effects, normal and half-normal plots together with analysis of variance (ANOVA) at 95.0 confidence intervals (CI). Optimizing (maximizing) the percentage (%) removal of Cu(II) by BDP, was performed using optimization plots. Results showed that the factors: pH and adsorbent dose (AD) affect the response positively. Scanning electron microscopy (SEM) was used to study the surface morphology of both adsorbents while fourier-transform infrared spectroscopy (FTIR) was employed to get an idea on the functional groups on the surface and hence the adsorption mechanism. Raman spectroscopy was used to characterize the prepared adsorbents before and after adsorption of Cu(II). Equilibrium studies show that the adsorption behavior differs according to the equilibrium concentration. In general, it follows Langmuir isotherm up to 155 ppm, then Freundlich isotherm. Free energy of adsorption (ΔG ad) is -28.07 kJ/mole, when equilibrium concentration is below 155 ppm, so the adsorption process is spontaneous, while (ΔG ad) equals +17.89 kJ/mole above 155 ppm, implying that the process is non-spontaneous. Furthermore, the adsorption process is a mixture of physisorption and chemisorption processes, which could be endothermic or exothermic reactions. The adsorption kinetics were described using a second order model.

Discrimination of breast cancer from benign tumours using Raman spectroscopy.

Breast cancer is the most common cancer among women worldwide, with an estimated 1.7 million cases and 522,000 deaths in 2012. Breast cancer is diagnosed by histopathological examination of breast biopsy material but this is subjective and relies on morphological changes in the tissue. Raman spectroscopy uses incident radiation to induce vibrations in the molecules of a sample and the scattered radiation can be used to characterise the sample. This technique is rapid and non-destructive and is sensitive to subtle biochemical changes occurring at the molecular level. This allows spectral variations corresponding to disease onset to be detected. The aim of this work was to use Raman spectroscopy to discriminate between benign lesions (fibrocystic, fibroadenoma, intraductal papilloma) and cancer (invasive ductal carcinoma and lobular carcinoma) using formalin fixed paraffin preserved (FFPP) tissue. Haematoxylin and Eosin stained sections from the patient biopsies were marked by a pathologist. Raman maps were recorded from parallel unstained tissue sections. Immunohistochemical staining for estrogen receptor (ER) and human epidermal growth factor receptor 2 (HER2/neu) was performed on a further set of parallel sections. Both benign and cancer cases were positive for ER while only the cancer cases were positive for HER2. Significant spectral differences were observed between the benign and cancer cases and the benign cases could be differentiated from the cancer cases with good sensitivity and specificity. This study has shown the potential of Raman spectroscopy as an aid to histopathological diagnosis of breast cancer, in particular in the discrimination between benign and malignant tumours.

Fourier Transform Infrared (FT-IR) and Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) Imaging of Cerebral Ischemia: Combined Analysis of Rat Brain Thin Cuts Toward Improved Tissue Classification.

Microspectroscopic techniques are widely used to complement histological studies. Due to recent developments in the field of chemical imaging, combined chemical analysis has become attractive. This technique facilitates a deepened analysis compared to single techniques or side-by-side analysis. In this study, rat brains harvested one week after induction of photothrombotic stroke were investigated. Adjacent thin cuts from rats' brains were imaged using Fourier transform infrared (FT-IR) microspectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The LA-ICP-MS data were normalized using an internal standard (a thin gold layer). The acquired hyperspectral data cubes were fused and subjected to multivariate analysis. Brain regions affected by stroke as well as unaffected gray and white matter were identified and classified using a model based on either partial least squares discriminant analysis (PLS-DA) or random decision forest (RDF) algorithms. The RDF algorithm demonstrated the best results for classification. Improved classification was observed in the case of fused data in comparison to individual data sets (either FT-IR or LA-ICP-MS). Variable importance analysis demonstrated that both molecular and elemental content contribute to the improved RDF classification. Univariate spectral analysis identified biochemical properties of the assigned tissue types. Classification of multisensor hyperspectral data sets using an RDF algorithm allows access to a novel and in-depth understanding of biochemical processes and solid chemical allocation of different brain regions.

Fourier-Transform Infrared Imaging Spectroscopy and Laser Ablation -ICPMS New Vistas for Biochemical Analyses of Ischemic Stroke in Rat Brain.

Objective: Stroke is the main cause of adult disability in the world, leaving more than half of the patients dependent on daily assistance. Understanding the post-stroke biochemical and molecular changes are critical for patient survival and stroke management. The aim of this work was to investigate the photo-thrombotic ischemic stroke in male rats with particular focus on biochemical and elemental changes in the primary stroke lesion in the somatosensory cortex and surrounding areas, including the corpus callosum. Materials and Methods: FT-IR imaging spectroscopy and LA-ICPMS techniques examined stroke brain samples, which were compared with standard immunohistochemistry studies. Results: The FTIR results revealed that in the lesioned gray matter the relative distribution of lipid, lipid acyl and protein contents decreased significantly. Also at this locus, there was a significant increase in aggregated protein as detected by high-levels Aß1-42. Areas close to the stroke focus experienced decrease in the lipid and lipid acyl contents associated with an increase in lipid ester, olefin, and methyl bio-contents with a novel finding of Aß1-42 in the PL-GM and L-WM. Elemental analyses realized major changes in the different brain structures that may underscore functionality. Conclusion: In conclusion, FTIR bio-spectroscopy is a non-destructive, rapid, and a refined technique to characterize oxidative stress markers associated with lipid degradation and protein denaturation not characterized by routine approaches. This technique may expedite research into stroke and offer new approaches for neurodegenerative disorders. The results suggest that a good therapeutic strategy should include a mechanism that provides protective effect from brain swelling (edema) and neurotoxicity by scavenging the lipid peroxidation end products.

Structural analysis of phosphatidylcholines by post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

The utility of post-source decay (PSD) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was investigated for the structural analysis of phosphatidylcholine (PC). PC did not produce detectable negative molecular ion from MALDI, but positive ions were observed as both [PC+H](+) and [PC+Na](+). The PSD spectra of the protonated PC species contained only one fragment corresponding to the head group (m/z 184), while the sodiated precursors produced many fragment ions, including those derived from the loss of fatty acids. The loss of fatty acid from the C-1 position (sn-1) of the glycerol backbone was favored over the loss of fatty acid from the C-2 position (sn-2). Ions emanating from the fragmentation of the head group (phosphocholine) included [PC+Na-59](+), [PC+Na-183](+) and [PC+Na-205](+), which corresponded to the loss of trimethylamine (TMA), non-sodiated choline phosphate and sodiated choline phosphate, respectively. Other fragments reflecting the structure of the head group were observed at m/z 183, 146 and 86. The difference in the fragmentation patterns for the PSD of [PC+Na](+) compared to [PC+H](+) is attributed to difference in the binding of Na(+) and H(+). While the proton binds to a negatively charged oxygen of the phosphate group, the sodium ion can be associated with several regions of the PC molecule. Hence, in the sodiated PC, intermolecular interaction of the negatively charged oxygen of the phosphate group, along with sodium association at multiple sites, can lead to a complex and characteristic ion fragmentation pattern. The preferential loss of sn-1 fatty acid group could be explained by the formation of an energetically favorable six-member ring intermediate, as apposed to the five-member ring intermediate formed prior to the loss of sn-2 fatty acid group.

Biophysical studies of the effect of high power ultrasound on the DNA solution.

Stability and molecular size of the DNA double helical structure were studied on an aqueous solution of DNA after exposure to high power doses of continuous wave ultrasound at frequency of 20 kHz. Thermal transition spectrophotometry (UV-melting), constant-field gel electrophoresis (CFGE), differential scanning calorimetry (DSC) and dielectric properties measurements were used to evaluate the ultrasound-induced changes in the DNA double helical structure. The thermal transition spectrophotometry (UV-melting) and differential scanning calorimetry (DSC) results showed that ultrasound power caused loss of DNA double helical structure and the DNA double strands melting temperature decreased as the ultrasound power increased, indicating a decrease in the stability of the double helical structure of DNA. The constant-field gel electrophoresis (CFGE) results showed that the molecular size of the DNA fragments decreased as the ultrasound power increased. The dielectric data in the frequency range from 20 Hz to 100 kHz for the native DNA showed that dispersion at frequency of about 500 Hz resulted from polarization induced by counterions. The decrease in the dielectric increment indicated a decrease in length of DNA molecule after exposure to ultrasound power.

A market basket survey of As, Zn and Se in rice imports in Qatar: health implications.

Qatar is dependent on importation of rice, its staple dish, and is therefore susceptible to compromises of food quality in the global market. This market basket study assesses potential health risks of As exposure from rice consumption in Qatar and examines its contribution to the recommended nutritional intakes (RNI) for Zn and Se. Fifty-six rice types and 12 products sold in Qatar were analyzed by ICP/MS. Mean concentrations and ranges were 96.2±54.1µg/kg (9.76-258µg/kg) for As; 12.5±5.35mg/kg (2.79-29.9mg/kg) for Zn and 103±113µg/kg (<5.94-422µg/kg) for Se. Calculated risk quotient shows rice consumption in Qatar is not a significant route of As exposure but can contribute up to 100% and 50% of the RNI for Se and Zn, respectively. Results indicate that children in Qatar may be at elevated risk of arsenic exposure from rice-based infant cereals but more data is needed to obtain a definitive assessment.