Rapid Determination and Quantification of Nutritional and Poisonous Metals in Vastly Consumed Ayurvedic Herbal Medicine (Rejuvenator Shilajit) by Humans Using Three Advanced Analytical Techniques.

Shilajit is used commonly as Ayurvedic medicine worldwide which is Rasayana herbo-mineral substance and consumed to restore the energetic balance and to prevent diseases like cognitive disorders and Alzheimer. Locally, Shilajit is applied for patients diagnosed with bone fractures. For safety of the patients, the elemental analysis of Shilajit is imperative to evaluate its nutritional quality as well as contamination from heavy metals. The elemental composition of Shilajit was conducted using three advanced analytical techniques (LIBS, ICP, and EDX). For the comparative studies, the two Shilajit kinds mostly sold globally produced in India and Pakistan were collected. Our main focus is to highlight nutritional eminence and contamination of heavy metals to hinge on Shilajit therapeutic potential. In this work, laser-induced breakdown spectroscopy (LIBS) was applied for qualitative and quantitative analysis of the Shilajit. Our LIBS analysis revealed that Shilajit samples composed of several elements like Ca, S, K, Mg, Al, Na, Sr, Fe, P, Si, Mn, Ba, Zn, Ni, B, Cr, Co, Pb, Cu, As, Hg, Se, and Ti. Indian and Pakistani Shilajits were highly enriched with Ca, S, and K nutrients and contained Al, Sr, Mn, Ba, Zn, Ni, B, Cr, Pb, As, and Hg toxins in amounts that exceeded the standard permissible limit. Even though the content of most elements was comparable among both Shilajits, nutrients, and toxins, in general, were accentuated more in Indian Shilajit with the sole detection of Hg and Ti. The elemental quantification was done using self-developed calibration-free laser-induced breakdown spectroscopy (CF-LIBS) method, and LIBS results are in well agreement with the concentrations determined by standard ICP-OES/MS method. To verify our results by LIBS and ICP-OES/MS techniques, EDX spectroscopy was also conducted which confirmed the presence above mentioned elements. This work is highly significant for creating awareness among people suffering due to overdose of this product and save many human lives.

Behavior of uranium series in groundwater of the Wajid Formation, Wadi AdDawasir, Saudi Arabia.

The inventories and the possible mechanisms behind the relative deficiency of both radium and uranium release processes within an elevated gamma-anomalous rock were investigated. A field survey was performed on the highest radioactive anomalous zone that was recorded at Jabal Al Alam (20° 13' 10.06″ N and 44° 14' 32.13″), with the ferruginous sandstone, iron oxide band, and iron concretions (with uranium content and reaching up to1500 ppm). The chemical analyses and the laboratory's gamma-ray spectrometric measurements demonstrated high uranium levels in the analyzed rock samples of the Wajid Sandstone (up to 1000 ppm). The borehole geophysical logs further confirmed that the radioactive anomalies are attributed to the sandstone sequence of the Wajid Formation that is often found associated with elevated concentrations of uranium. The groundwater samples taken from the wells tapping the Wajid aquifer showed uranium concentrations ranging from 0.01 to 5.5 ppb (µg/L). The average 226Ra in groundwater samples was 0.2 Bq L-1. The majority of the 226Ra and 228Ra activities were below the lower limit of detection (LLD). The radiochemical analyses of water samples from the Wajid aquifer display low concentrations of both uranium and 226Ra, with relation to uranium content in host rocks. This was attributed to the fact that uranium is susceptible to form iron oxide complexes, causing them to precipitate in a more stable form. Furthermore, iron oxides coat the sand grains of the Wajid Formation and accordingly might act as a foundation for re-adsorption for both uranium and radium, resulting in their relative deficiency in the surrounding water. The coating might also act as a physical barrier resulting in hindrance of the recoil nuclei due to its significant thickness (several orders of magnitude) compared with that of the average (120 nm) whole alpha-recoil track (ART). The coating layer thickness was determined via scanning electron microscopy (SEM) and was found to be up to 180 µm.

Spectral analysis of Miracle Moringa tree leaves using X-ray photoelectron, laser induced breakdown and inductively coupled plasma -optical emission spectroscopic techniques.

The antioxidant Moringa oleifera (a medicinal plant) leaves (MOLs) containing diverse nutrients are highly beneficial for the human health. The MOLs upon consumption can lower the blood sugar, cure the heart diseases, and reduce the inflammation. In this perception, the "primary nutrients contents" in the dry MOLs (pellet samples) were evaluated for the first time using the XPS, LIBS and ICP-OES techniques. The XPS analysis of the MOLs showed the presence of vital elements like calcium (Ca), magnesium (Mg), manganese (Mn), copper (Cu), phosphorous (P), sulfur (S) and zinc (Zn). The LIBS analyses of the MOLs revealed the atomic and ionic spectral lines corresponding to the essential nutrients such as the Ca, Na, K, Fe, Mg, Mn, Cu, P, S and Zn. The calibration free LIBS algorithm (CF-LIBSA) was developed to quantify the content of each element in the dry MOLs. In addition, the LIBS results were validated by the analysis using ICP-OES standard analytical technique. The elemental contents in the MOLs obtained from the CF-LIBS analyses were counter verified by the ICP-OES results. Present results are highly valuable for the development of a traditional herbal medicine using the miracle MOLs.

Determination of heavy metals in cancerous and healthy colon tissues using laser induced breakdown spectroscopy and its cross-validation with ICP-AES method.

Certain types of cancer deaths are widespread due to the diagnostic complexities at the early stages. Recent studies revealed that the bio-accumulated heavy metals (act as pro-carcinogens) in the human colon cause strong interactions with the nuclear proteins, leading to the DNA damages and repair processes inhibition, resulting in the cancers. Most of the conventional detection techniques suffer from the insensitiveness, cost-intensiveness, imprecision, slowness, cumbersomeness of sample preparation, and conflicting outcomes. To surmount these shortcomings an accurate, reliable, and rapid detection technique is essential for the early diagnostic and prevention of heavy metals accumulation induced colon cancers. This will enable not only to classify the malignant and non-malignant cells but can differentiate the proteins from abnormal cellular morphology. Using the indigenously developed fast and accurate (calibration-free) laser-induced breakdown spectroscopy (LIBS), we analyzed several cancerous and normal colon tissues collected from the colon cancer infected patients aged 40-60 years. The results showed the presence of carcinogenic heavy metals including lead (Pb), chromium (Cr), and mercury (Hg) in the malignant colon tissues, while the healthy tissues were devoid of these elements. The concentrations of Pb, Cr and Hg in the cancerous samples were discerned to be 3.1, 13.4 and 7.1 µg/L, respectively. Furthermore, the performance accuracy of the LIBS technique was validated by comparing the results obtained from the standard inductively coupled plasma atomic emission spectroscopy (ICP-OES). It was established that the LIBS analysis is useful for the speedy, precise and early detection of the heavy metals amassed malignant colon tissues, thereby saving millions of lives by promoting the chances for cancer cure.

Cardiac magnetic resonance indices reflecting pulmonary regurgitation burden after tetralogy of Fallot repair.

AIM: To investigate cardiac magnetic resonance (CMR)-derived parameters to determine a convenient index reflecting the degree of pulmonary regurgitation (PR) after Tetralogy of Fallot (TOF) repair. MATERIALS AND METHODS: Sixty-three patients (age at CMR study, 23.6 [10.2-34.7] years, 55.6% male) underwent CMR after TOF repair. PR was quantified using ventricular stroke volume difference and phase-contrast mapping of the main pulmonary artery flow. In both approaches, the PRV index (PRVI) and the PR fraction (PRF) were calculated and correlated to the right ventricle end-diastolic volume index (RVEDVI) and the right ventricle end-systolic volume index (RVESVI). RESULTS: No statistically significant difference was observed between the PR volumes and the PRF measured by the stroke volume difference or the phase-contrast method. The PRVI was better correlated to RVEDVI and RVESVI than the PRF. CONCLUSION: The PRVI exhibits more correlation to the RVEDVI than PRF. Thus, it could be a preferable parameter to reflect the PR burden.

Paravalvular leak after transcatheter aortic valve implantation: is it anatomically predictable or procedurally determined? MDCT study.

AIM: To investigate the determinants of paravalvular leak (PVL) occurring after transcatheter aortic valve implantation (TAVI). MATERIALS AND METHODS: One hundred and eight patients with severe symptomatic aortic stenosis (mean age 75.5±11.8 years, 72.2% male) underwent contrast-enhanced electrocardiogram (ECG)-gated multidetector computed tomography (MDCT) then successful TAVI. The following parameters were determined in the late systolic phase: annular and left ventricular outflow tract (LVOT) diameters, annular perimeter, ellipticity index, annular area, indexed annular area, LVOT perimeter, annulus/LVOT perimeter difference ratio, the LVOT to ascending aorta angle (< LVOT-AO). In the diastolic phase, the extent of calcification of the aortic valve (AVC) was assessed visually and graded semi-quantitatively as grade I, II, and III at the annulus, LVOT, and aortic cusps levels. Pre-discharge transthoracic echocardiography (TTE) was performed, and the PVL was graded as grade I, II, and III. The area-dependent device-annulus sizing ratio was calculated. RESULTS: Absence of PVL was observed in 44.44% of the patients, 30.56% had grade I PVL, 25% of the patients had grade II or above, and any PVL was observed in 55.56%. There was no statistically significant association between the degree of PVL and the extent or the distribution of AVC, aortic annulus diameters, ellipticity index, annulus/LVOT perimeter difference ratio or < LVOT-AO. The frequency of PVL was not significantly different with the use of balloon-expandable or self-expandable valves. A larger transcatheter heart valve (THV)/annulus sizing ratio was associated with a lower incidence and degree of PVL (p<0.001); there was no detectable PVL with a mean sizing ratio of 14.89±7.29, and grade I PVL occurred with a mean sizing ratio 12.43±0.84, while PVL of grade II or above occurred using the mean sizing ratio -0.42±5.57. CONCLUSION: The procedure-related THV/annulus sizing ratio was an important determinant of the degree of PVL after TAVI, whereas the MDCT-derived anatomical measurements of the aortic root and AVC were not predictors of PVL.

Detection of hazardous pollutants in chrome-tanned leather using locally developed laser-induced breakdown spectrometer.

Highly toxic contaminants like Cr, As, and Pb were detected in chrome-tanning process of animal skin to produce leather by applying locally developed laser-induced breakdown spectrometer. An Nd-YAG laser with 1,064 nm wavelength was focused on the surface of leather samples (natural and manufactured) to generate a plasma spark and spectrally resolved spectra were used for identification and quantification of contaminants. The leather samples were collected from a tannery located in industrial cities of Riyadh and Jeddah, Saudi Arabia. The study was carried out on fully, half manufactured (wet blue leather), and natural hide (skin). To the best of our knowledge, this is the first attempt where laser-induced breakdown spectroscopy (LIBS) technique has been applied for the analysis of leather before and after tanning process. The maximum concentration of different elements of environmental significance like chromium, lead, arsenic, sulfur, magnesium were 199, 289, 31, 38, and 39 ppm, respectively, in one of the manufactured leather samples. The limit of detection (LOD) of our LIBS system for chromium, lead, arsenic, sulfur, and magnesium were 2, 3, 1.5,7, and 3 ppm, respectively. The safe permissible limit for tanned leather for highly toxic elements like chromium, lead, and arsenic are 1, 0.5, 0.01 ppm, respectively, as prescribed in Environmental Regulation Standards for Saudi Industries set by Royal Commission Jubail, Saudi Arabia. The LIBS technique is superior to other conventional techniques like ICP or atomic absorption that a little or no sample preparation is required, no chemicals are needed, multi-elemental analysis is possible for all kinds of samples (natural and anthropogenic materials), microgram of sample is essential, and LIBS could be applied for remote analysis. It is highly selective and sensitivity higher than ICP, and as no sample and chemicals are required, it is cost effective for multi-sample analysis per unit time as compared with other conventional techniques. The concentration of some toxic elements (Cr, Pb, As) is much higher than the safe permissible limits set by Occupational Safety and Health Administration in USA or Saudi environmental regulatory agencies. Results obtained with our LIBS systems were in close agreement with the results obtained using other standard analytical technique such as the inductively coupled plasma atomic emission spectroscopy.

Effect of splenectomy on liver regeneration and function following partial hepatectomy: experimental study.

The presence of enough remaining functioning liver parenchyma to avoid life-threatening post-operative liver failure is a major prerequisite for hepatic resection in patients with hepato-biliary carcinoma. There are clinical reports which confirm the beneficial clinical effects of splenectomy on integrity of the residual liver following liver resection for hepatocellular carcinoma in cirrhotic patients with hypersplenism and portal hypertension. This experimental study was designed on hamsters to evaluate the proliferative capacity and function of the remaining liver lobes; in which splenectomy was done simultaneously with partial hepatectomy compared with those in which splenectomy was not done. Forty hamsters were divided into two groups: GI; in which partial hepatectomy was performed without splenectomy and the GII; in which animals were subjected to partial hepatectomy with prior splenectomy. Animals from each group were subjected to liver biopsy from the remaining lobes 48, 72 hours and one week after surgery. Also, serum alanine aminotransferase (ALT) and total bilirubin were tested before, 48, 72 hours and one week after hepatectomy. Hepatic regeneration in the remaining lobes was assessed through histo-pathological study, DNA ploidy of the hepatic nuclei using computerized image analysis system and determining of the labeling index of the nuclear factor NF Kappa B (P105), a novel monoclonal antibody specific for P105 protein by immunohistochemistry. In GII: induction of NK kappa B (P105) labeling index showed maximum expression depending on the regenerative capacity of the remaining liver lobes. In contrast, in GI; liver regeneration was slow. Also, changes in liver function of GII indicated that splenectomy prior hepatecotomy may minimize dysfunction in the remaining hypertrophied liver lobes.

Spectroscopic detection of health hazardous contaminants in lipstick using Laser Induced Breakdown Spectroscopy.

Laser Induced Breakdown Spectroscopy (LIBS) technique was applied to determine the concentrations of different toxic elements like lead, chromium, cadmium and zinc in four different lipstick brands sold at local markets in Saudi Arabia. These samples contain toxic elements like lead, cadmium and chromium which are carcinogen dermatitis, allergic and eczematous. Their extraction from human body takes over 40 years and accumulation in the body cause problems like disruption of nervous systems and kidney damage. They could trigger to systemic lupus erythematosus (SLE). In order to test the validity of our LIBS results, standard technique like (ICP-AES) was also applied. To the best of our knowledge, this is the first study where LIBS technique was applied for the measurement of toxic substances in lipsticks. The maximum concentration detected in four lipstick brands was much higher than the permissible safe limits for human use and could lead to serious health problems. It is worth mentioning that the lipstick is not a solid rather is in fluid state which is not trivial to analyze using LIBS technique. For this purpose, special treatment of the lipstick samples was necessary to analyze with our LIBS method.

A new acylated flavonol triglycoside from Carrichtera annua.

A new acylated flavonol triglycoside, quercetin 3-O-[(6-feruloyl-beta-glucopyranosyl)-(1-->2)-beta-arabinopyran oside] -7-O-beta-glucopyranoside (1), as well as the known flavonoid quercetin, were isolated from the whole plants of Carrichtera annua. The structure of 1 was established by UV, MS, and 1D and 2D NMR spectroscopy, including DEPT, DQF-COSY, TOCSY, HSQC, HSQC-TOCSY, and HMBC experiments.

Stimulation of anthraquinone production in suspension cultures of Cassia acutifolia by salt stress.

Suspension cultures of Cassia acutifolia were established by transferring callus tissues derived from root, hypocotyl and cotyledon explants onto liquid MS-medium supplemented with 1.0 mg/l 2.4-D and 0.1 mg/l kinetin and containing increasing levels of NaCl. The stress induced by salt NaCl raised anthraquinone content and reduced growth of cultures. The levels of anthraquinones and their glycosides as sennosides showed distinct changes in cells and media as well as in the different cultures initiated from various explants. Furthermore, the salt stress tended to affect more drastically the productivity of anthraquinones in hypocotyl and cotyledon cell cultures than in root cultures.

Algorithms for validating chiral properties of insulins.

The combination of chiral ligand exchange on Cu(II) complexes in aqueous base with circular dichroism spectropolarimetric detection provides excellent avenues to validate the chirality properties of oligopeptides and proteins. The method is quick and simple and has the potential for development into an automated, routine procedure for quality control applications. Target analytes used for this first study of a protein system are human, porcine, and bovine insulins prepared by different procedures and obtained from different sources, production lots, and manufacturers. The analytical specificity of the test makes the method a potentially useful technique for validating the chirality properties of many peptide and protein forms.

In vitro study of nicotine release from smokeless tobacco.

Four brands (Copenhagen Snuff, Skoal Bandit Classic, Skoal Wintergreen Long Cut, and Skoal Wintergreen Fine Cut) of smokeless tobacco products were tested for their rate of nicotine release into artificial saliva via direct contact or through a dialysis bag. Nicotine was determined by reversed-phase liquid chromatography. When samples were in direct contact with artificial saliva, most of the nicotine was released from the tobacco in the first minute. Nicotine release from Skoal Bandit Classic, marketed as smokeless tobacco in a sachet, was slower with the sachet intact than without the sachet. When smokeless tobacco and artificial saliva were placed inside a dialysis bag, nicotine release was much slower and primarily depended upon the permeability of the dialysis membrane. Although total nicotine was lowest for Skoal Bandit Classic, little difference was seen in nicotine release rates among the brands tested. When smokeless tobacco was placed in dialysis bags with artificial saliva outside, a significant difference was seen in rates of nicotine migration through the membrane. In this model, nicotine release from Copenhagen Snuff was much faster than from Skoal Bandit Classic with or without the sachet. This difference may be related to the pH of the smokeless tobacco products.

Effect of drug load and plate coating on the particle size distribution of a commercial albuterol metered dose inhaler (MDI) determined using the Andersen and Marple-Miller cascade impactors.

PURPOSE: The purpose of this study is to investigate the effect of drug load, the coating of impactor stages, and the design of cascade impactors on albuterol MDIs particle size distribution measurements. The results of the investigation will be used to explain the "loading effect" recently reported. METHODS: Particle size distribution parameters of a commercial albuterol MDI were measured using both Andersen (AI) and Marple-Miller (MMI) Cascade Impactors, where plates were either left uncoated or coated with silicone or glycerin. A previously validated HPLC-EC method was used for the assay of albuterol collected by the impactor and in single spray content determinations. RESULTS: Coating impactor collection plates had an impact on measured MMAD and GSD values for single puff measurements but very little or no effect for the multi puff measurements. Due to particle bounce, the percent of albuterol fine particles deposited in the filter and impactor finer stages (< 1.10 microns in AI and < 1.25 microns in MMI) in uncoated single puff experiments was much higher in comparison to either coated single puff or multi-puff (coated and uncoated) measurements. CONCLUSIONS: Evaluation of drug load and plate coating are necessary to determine whether observed particle size distributions are representative of the generated aerosol or are the result of particle bounce and reentrainment. In order to minimize particle bounce, especially for single puff determinations, it may be useful to apply a thin layer of a sticky coating agent to the surfaces of impactor plates.

Loading effect on particle size measurements by inertial sampling of albuterol metered dose inhalers.

PURPOSE: The purpose of this study is to investigate the albuterol loading effect on particle size measurements by studying the effect of the amount of albuterol delivered, the number of puffs used, and the sampling techniques used in particle size measurement. METHODS: Particle size distribution profiles for different albuterol loadings were evaluated using an 8-stage cascade impactor and a sensitive HPLC electrochemical assay method. A commercial albuterol MDI (Proventil) and other specially prepared albuterol MDIs were used in the study. RESULTS: As the amount of albuterol was increased, either by increasing the number of puffs or the amount delivered per puff, the measured MMAD increased. This increase was more prominent in some formulations (Proventil) than others. Further, albuterol particles previously deposited on the valve and/or actuator didn't play a role in the observed multi-puff/loading effect. CONCLUSIONS: The collection of the least amount of aerosol in a cascade impactor provides a better estimate of MMAD, as it minimizes modifications of the collection surfaces.