Evaluating chemicals of emerging concern in the Ganga River at the two major cities Prayagraj and Varanasi through validated analytical approaches.

Evaluating environmental water quality means to assess and protect the environment against unfriendly impacts from various organic impurities emerging from industrial emissions and those released during harvesting. Potential risks related with release of polycyclic aromatic hydrocarbons (PAHs), pesticides and pharmaceuticals (PhAcs), and personal care products (PCPs) into the environment have turned into an increasingly serious issue in ecological safety. Monitoring helps in control of chemicals and ecological status compliance to safeguard specific water uses, for example, drinking water abstraction. A longitudinal review was carried out for 55 different persistent organic pollutants (POPs) for the Ganga River which passes through the urban areas of Prayagraj and Varanasi, India, through validated analytical approaches and measurement uncertainty (MU) estimation to assess their potential use for routine analysis. Furthermore, environmental risk assessment (ERA) carried out in the present study has revealed risk quotient (RQ) higher than 1 in a portion of the aquatic bodies. Using a conservative RQ strategy, POPs were assessed for having extensive risks under acute and chronic exposure, proposing that there is currently critical ecological risk identified with these compounds present in the Ganga River. In general, these outcomes demonstrate a significant contribution for focusing on measures and feasible techniques to minimize the unfavorable effects of contaminants on the aquatic environment.

Novel ultra-small Pd NPs on SOS spheres: a new catalyst for domino intramolecular Heck and intermolecular Sonogashira couplings.

We report a novel catalyst Pd/SOS that catalyzes the dual C-C bond forming coupling of an iodoarene moiety with an internal alkene and an external alkyne via an intramolecular Heck reaction, followed by an intermolecular Sonogashira reaction, respectively. The catalyst was characterized using XRD, IR, XPS, SEM and TEM analyses. Notably, for the first time, cheap and readily available new silica [nanosilica on microsilica (SOS)] material-supported ultra-small Pd nanoparticles (2.20 nm) are employed for the efficient synthesis of dihydrobenzofuran and oxindole derivatives in a domino one-pot reaction. Significantly, a sub-molar quantity of Pd (0.3 mol%) was found to be sufficient to furnish the products in very good to near quantitative yields. Gratifyingly, the catalyst could be recycled up to five cycles with a marginal loss (∼no loss) of the product.

Bioaccumulation, biotransformation and toxic effect of fipronil in Escherichia coli.

Fipronil is a highly effective, broad-spectrum insecticide used to control pests, globally. The increased usage has led to contamination of soil, water, fruits, and vegetables. The wide and frequent usage of fipronil across the globe calls for attention regarding risk assessment of undesirable effects on non-target microorganisms. In this context, the present study was carried to understand the impact of fipronil on non-pathogenic Escherichia coli. The non-pathogenic E. coli are important commensal of the intestinal tract of humans and animals and are also indicator organisms in the environment. Our study indicates that exposure of E. coli to fipronil (100 µM concentration) leads to significant reactive oxygen species production, loss of membrane potential and viability. Further, we have witnessed the bioaccumulation and biotransformation of fipronil by E. coli at non-lethal concentrations. The bio-transformed products (fipronil sulfone and fipronil sulfide) are also the major metabolites (along with amide) reported in the feces of the mammals when exposed to fipronil. Thus, there is a possibility that the gut E. coli might play a role in the degradation and thereby removal of fipronil. In addition, the bioaccumulation of fipronil in bacteria is of concern and need to be further explored because it can lead to biomagnification in the higher trophic level and can disturb the ecological balance. In our knowledge, this is the first report on the determination of fipronil and its metabolites in bacteria through GC-MS/MS.

Alternariol induced proliferation in primary mouse keratinocytes and inflammation in mouse skin is regulated via PGE2/EP2/cAMP/p-CREB signaling pathway.

Alternariol (AOH) is a mycotoxin that contaminates various food stuffs as well as animal feed and may cause toxicity after consumption. However, a dermal toxic potential of AOH has not been explored so far. In the present study, skin toxicity after topical exposure of AOH and the involved mechanism/s are revealed. Single topical application of different AOH doses (12.5, 25, 50 µg/animal) caused increased bi-fold thickness as well as hyperplasia and higher production of prostaglandin E2 (PGE2) along with cAMP in the skin demonstrating its inflammatory potential. Western blot analysis showed that exposure of AOH lead to phosphorylation of CREB and increased the expression of COX-2, cyclin D1 as well as prostanoid EP2 receptor. Further studies on primary mouse keratinocytes (PMK) revealed that very low concentrations of AOH (50-500 nM) resulted in significant PMK proliferation. Additionally, using specific antagonist or agonist of prostanoid receptors, we delineated that EP2 receptor play a key role in AOH-induced PMKs proliferation. Collectively, our findings show that AOH can lead to dermal toxicity in mice by activating the EP2/cAMP/p-CREB signaling cascade.

Association between PAHs biomarkers and kidney injury biomarkers among kitchen workers with microalbuminuria: A cross-sectional pilot study.

BACKGROUND: To study the association between kidney injury biomarkers and urinary OH-PAH metabolites in kitchen workers, with microalbuminuria. METHODS: A cross-sectional pilot study was conducted among 120 male kitchen workers in a mega kitchen located at Coimbatore, India. Personal and sub-clinical details of study subjects were collected using a questionnaire. Albumin, creatinine, and albumin-creatinine ratio (ACR) were measured using urine dipstick test for the determination of microalbuminuria. Urinary hydroxylated PAHs metabolites (1-NAP, 9-HF, 3-HF, 2-HF, 9-PHN, and 1-OHP) were measured using GC-MS/MS and urinary kidney biomarkers (uNGAL, uCyst-C, uKIM-1, uOPN, and uTIMP-1) were measured using Multiplex Reader. RESULTS: Concentrations of urinary PAHs metabolites (1-NAP, 3-HF, 2-HF, 9-PHN, and 1-OHP) and kidney biomarkers (uKIM-1, uTIMP-1, uCyst-C and uNGAL) were significantly higher among kitchen workers with MAU compared to non-kitchen workers with MAU. Urinary kidney biomarkers viz., uKIM-1, uTIMP-1, uCyst-C, uNGAL, and uOPN showed higher median concentration among the kitchen workers with MAU compared to kitchen workers without MAU. Significant positive correlation was observed for 9-HF with uKIM-1 and uTIMP-1 and 1-OHP with uKIM-1. ACR was also well correlated with urinary kidney biomarkers. ROC analysis showed higher sensitivity and specificity for uKIM-1, uCyst-C, and uNGAL as biomarkers for early prediction of acute kidney injury among kitchen workers. CONCLUSIONS: The PAHs exposure among kitchen workers can lead to kidney injury. This was evident from the association of OH-PAHs and kidney injury biomarkers in kitchen workers with microalbuminuria.

Determination of organochlorine compounds in fish liver by ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of organic droplet coupled with gas chromatography-electron capture detection.

A simple and rapid method for the extraction of organochlorine compounds (OCs) including poly-chlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in fish liver using ultrasound assisted dispersive liquid-liquid microextraction based on the solidification of floating organic droplet (US-DLLME-SFO) was developed. For reducing the complexity of the matrix, the sample was pre-treated prior to microextraction. Factors affecting US-DLLME-SFO were optimized by using statistical design of experiment (DoE). The analysis was carried out by Gas Chromatography (GC) equipped with micro electron capture detector (µ-ECD). The optimized parameters were 4.8 min of ultrasound, 3.0 mL of Milli-Q and 24 µL of 1-undecanol as an extraction solvent as determined by DoE. US-DLLME-SFO was validated in terms of limit of detection, limit of quantification, dynamic linearity range, coefficient of determination (linearity) and extraction recovery in fish liver for OCs, and the respective values were (1.06-3.84 ng g-1), (3.50-12.67 ng g-1), (1.0-500 ng g-1), (R2 = 0.994-0.999), (88.5-108.4%). Interday and intraday precisions were evaluated as relative standard deviation (% RSD) and the values were ≤10%.

Foiling fungal disease post hematopoietic cell transplant: review of prophylactic strategies.

Hematopoietic cell transplantation (HCT) offers definitive management for a wide variety of malignant and nonmalignant diseases. Conditioning regimens and therapies used to prevent and treat GvHD are immune suppressive, often increasing the risk of developing fungal disease due to yeasts or molds. Antifungal prophylaxis may be useful in preventing morbidity and mortality during and after HCT. In this article, we review the epidemiology and current literature regarding strategies for prevention of invasive fungal disease (IFD) in the pre-engraftment and post-engraftment settings, and propose future direction for scientific discovery.

Recyclable Pd/CuFe2O4 nanowires: a highly active catalyst for C-C couplings and synthesis of benzofuran derivatives.

Pd/CuFe2O4 nanowire-catalyzed cross coupling transformations are described. Notably, these reactions showed excellent functional group tolerance. Further, the protocol is applied to a one-pot synthesis of benzofurans via a Sonogashira coupling and intramolecular etherification sequence. The catalyst was reused and found to maintain its activity and stability.

A dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by injector port silylation coupled with gas chromatography-tandem mass spectrometry for the determination of nine bisphenols in bottled carbonated beverages.

In the present study, a method has been efficiently developed for the first time to determine nine bisphenol analogues [bisphenol A (BPA), bisphenol C (BPC), bisphenol AF (BPAF), bisphenol E (BPE), bisphenol F (BPF), bisphenol G (BPG), bisphenol M (BPM), bisphenol S (BPS), and bisphenol Z (BPZ)] together in bottled carbonated beverages (collected from the local market of Lucknow, India) using dispersive liquid-liquid microextraction process. This is based on solidification of floating organic droplet (DLLME-SFO) followed by injector port silylation coupled with gas chromatography-tandem mass spectrometry. The process investigated parameters of DLLME-SFO (including the type of extraction and disperser solvents with their volumes, effect of pH, ionic strength, and the sample volume), factors influencing to injection port derivatization like, collision energy, injector port temperature, derivatizing reagent with sample injection volume, and type of organic solvent. BPA, BPF, BPZ, and BPS were detected in each sample; whereas, other bisphenols were also detected in some carbonated beverage samples. After optimizing the required conditions, good linearity of analytes was achieved in the range of 0.097-100ngmL-1 with coefficients of determination (R2)≥0.995. Intra-day and inter day precision of the method was good, with relative standard deviation (% RSD)≤10.95%. The limits of detection (LOD) and limits of quantification (LOQ) values of all bisphenols were ranged from 0.021 to 0.104ngmL-1 and 0.070 to 0.343ngmL-1, respectively. The recovery of extraction was good (73.15-95.08%) in carbonated beverage samples and good enrichment factors (96.36-117.33) were found. Thus, the developed method of microextraction was highly precise, fast, and reproducible to determine the level of contaminants in bottled carbonated beverages.

Comparison of two microextraction methods based on solidification of floating organic droplet for the determination of multiclass analytes in river water samples by liquid chromatography tandem mass spectrometry using Central Composite Design.

Two low density organic solvents based liquid-liquid microextraction methods, namely Vortex assisted liquid-liquid microextraction based on solidification of floating organic droplet (VALLME-SFO) and Dispersive liquid-liquid microextraction based on solidification of floating organic droplet(DLLME-SFO) have been compared for the determination of multiclass analytes (pesticides, plasticizers, pharmaceuticals and personal care products) in river water samples by using liquid chromatography tandem mass spectrometry (LC-MS/MS). The effect of various experimental parameters on the efficiency of the two methods and their optimum values were studied with the aid of Central Composite Design (CCD) and Response Surface Methodology(RSM). Under optimal conditions, VALLME-SFO was validated in terms of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery for which the respective values were (0.011-0.219ngmL-1), (0.035-0.723ngmL-1), (0.050-0.500ngmL-1), (R2=0.992-0.999), (40-56), (80-106%). However, when the DLLME-SFO method was validated under optimal conditions, the range of values of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery were (0.025-0.377ngmL-1), (0.083-1.256ngmL-1), (0.100-1.000ngmL-1), (R2=0.990-0.999), (35-49), (69-98%) respectively. Interday and intraday precisions were calculated as percent relative standard deviation (%RSD) and the values were ≤15% for VALLME-SFO and DLLME-SFO methods. Both methods were successfully applied for determining multiclass analytes in river water samples.

Ionic liquid based vortex assisted liquid-liquid microextraction combined with liquid chromatography mass spectrometry for the determination of bisphenols in thermal papers with the aid of response surface methodology.

A sensitive, rapid and efficient ionic liquid-based vortex assisted liquid-liquid microextraction (IL-VALLME) with Liquid Chromatography Mass spectrometry (LC-MS/MS) method is proposed for the determination of bisphenols in thermal paper. Extraction factors were systematically optimized by response surface methodology. Experimental factors showing significant effects on the analytical responses were evaluated using design of experiment. The limit of detection for Bisphenol-A (BPA) and Bisphenol-S (BPS) in thermal paper were 1.25 and 0.93µgkg-1 respectively. The dynamic linearity range for BPA was between 4 and 100µgkg-1 and the determination of coefficient (R2) was 0.996. The values of the same parameters were 3-100µgkg-1 and 0.998 for BPS. The extraction recoveries of BPA and BPS in thermal paper were 101% and 99%. Percent relative standard deviation (% RSD) for matrix effect and matrix match effects were not more than 10%, for both bisphenols. The proposed method uses a statistical approach for the analysis of bisphenols in environmental samples, and is easy, rapid, requires minimum organic solvents and efficient.

Vortex-assisted surfactant-enhanced emulsification microextraction combined with LC-MS/MS for the determination of glucocorticoids in water with the aid of experimental design.

An efficient and inexpensive method using vortex-assisted surfactant-enhanced emulsification microextraction (VASEME) based on solidification of floating organic droplet coupled with ultraperformance liquid chromatography-tandem mass spectrometry is proposed for the analysis of glucocorticoids in water samples (river water and hospital wastewater). VASEME was optimized by the experimental validation of Plackett-Burman design and central composite design, which has been co-related to experimental design. Plackett-Burman design showed that factors such as vortex time, surfactant concentration, and pH significantly affect the extraction efficiency of the method. Method validation was characterized by an acceptable calibration range of 1-1000 ng L-1, and the limit of detection was in the range from 2.20 to 8.12 ng L-1 for glucocorticoids. The proposed method was applied to determine glucocorticoids in river water and hospital wastewater in Lucknow, India. It is reliable and rapid and has potential application for analysis of glucocorticoids in environmental aqueous samples. Graphical Abstract Low density based extraction of gluococorticoids by using design of experiment.

Genotoxicity assessment of pulp and paper mill effluent before and after bacterial degradation using Allium cepa test.

A lignin peroxidases-producing Serratia liquefaciens was used for bioremediation of pulp and paper (P&P) mill effluent. The treatment led to reduction of chemical oxygen demand (COD), colour, lignin and phenolic content by 84%, 72%, 61% and 95%, respectively. The effluent detoxification was studied by genotoxicity assays using Allium cepa L. (onion) root tip cells. Genotoxicity studies included measuring mitotic index (MI), chromosomal aberrations (CA) and nuclear abnormalities (NA) in root tip cells following treatment with 25, 50, 75 and 100% (v/v) of effluent. The root tip cells grown in untreated effluent showed a significant decrease in MI from 69% (control) to 32%, 27%, 22% and 11% at 25%, 50%, 75% and 100% effluent concentration, respectively. This indicated that the untreated effluent was highly cytotoxic in nature. Further, root tip cells, when treated with different concentrations of effluent showed various CA and NA including c-mitosis, stickiness, chromosome loss, chromosome break, anaphase bridge, multipolar anaphase, vagrant chromosomes, micronucleated and binucleated cells. The MI observed in root tip cells grown in bacterial treated effluents at similar concentrations (25, 50, 75 and 100% v/v) showed an increase of 33%, 36%, 42% and 66%. CA showed a substantial decrease and in some instances, complete absence of CA was also observed. The findings suggest that S. liquefaciens culture could be a potential bacterial culture for bioremediation of P&P mill effluent, as it is effective in substantial lowering of pollutants load as well as reduces the cytotoxic and genotoxic effects of effluent.

Selective solid-phase extraction using molecularly imprinted polymer as a sorbent for the analysis of fenarimol in food samples.

In the present communication, a non-covalent fenarimol-imprinted polymer was synthesized by precipitation polymerization technique using methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, and azobisisobutyronitrile (AIBN) as an initiator in different porogenic solvent. Binding study of molecularly imprinted and non-imprinted polymer (MIP and NIP) showed that MIP possesses a higher affinity towards this analyte compared to NIP. The binding affinity of MIP was calculated by static and kinetic adsorption study. Further, a MIP based cartridge was designed to use in extraction process, necessary for specific determination and quantification of the fungicide in food matrices. Under the optimum conditions, developed method was found to be linear (R(2)=0.9999-0.9994). Limit of detection (LOD) and limit of quantitation (LOQ) in samples were 0.03-0.06 and 0.12-0.21 µg mL(-1), respectively. The rate of recovery of fenarimol was 91.16-99.52% on MIPs. The validated method of molecularly imprinted solid-phase extraction (MISPE) cartridge was successfully applied to the food matrices and compared with commercial sorbent (RP18 and Oasis HLB). However we feel, this method has promising applications in the routine analysis of food samples in industry.

Assessment of Nano Cellulose from Peach Palm Residue as Potential Food Additive: Part II: Preliminary Studies.

High consumption of dietary fibers in the diet is related to the reduction of the risk of non-transmitting of chronic diseases, prevention of the constipation etc. Rich diets in dietary fibers promote beneficial effects for the metabolism. Considering the above and recognizing the multifaceted advantages of nano materials, there have been many attempts in recent times to use the nano materials in the food sector including as food additive. However, whenever new product for human and animal consumption is developed, it has to be tested for their effectiveness regarding improvement in the health of consumers, safety aspects and side effects. However, before it is tried with human beings, normally such materials would be assessed through biological tests on a living organism to understand its effect on health condition of the consumer. Accordingly, based on the authors' finding reported in a previous paper, this paper presents body weight, biochemical (glucose, cholesterol and lipid profile in blood, analysis of feces) and histological tests carried out with biomass based cellulose nano fibrils prepared by the authors for its possible use as food additive. Preliminary results of the study with mice have clearly brought out potential of these fibers for the said purpose.

Malrotation of midgut in adults, an unsuspected and neglected condition--An analysis of 64 consensus confirmed cases.

INTRODUCTION: Malrotation of midgut is considered to be a condition of childhood. This study evaluated malrotation in adults with recurrent abdominal pain (RAP). METHODS: Sixty-four consensus-confirmed cases of intestinal malrotation were reviewed. The diagnosis was based on radiological criteria, and the consensus was arrived at by at least three of the five authors in any individual case. RESULTS: Abnormal duodenojejunal junction (DJJ) was a consensus finding in 64 cases referred for RAP. Most were in their fourth decade of life, and 12 were beyond 60 years. Besides RAP, intolerance to food was the next common symptom. Acute intestinal obstruction was seen in 16. Forty-two of 64 patients consented for surgery. Ladd's procedure was the commonest. All patients who underwent surgery were symptom free except for two, of which, one had liver cyst and the other had hernia. Of those who refused surgery (22), all had continued symptoms and 10 patients took alternative therapies. On follow up of initially unwilling patients (for surgery) with abnormal DJJ, only eight consented for surgery; three underwent open Ladd's procedure, and one had laparoscopic Ladd's done. CONCLUSION: Malrotation is not uncommon as a cause of RAP in adults.

Fast agitated directly suspended droplet microextraction technique for the rapid analysis of eighteen organophosphorus pesticides in human blood.

A new sample preparation technique named as fast agitated directly suspended droplet microextraction (FA-DSDME) was proposed as an improved version of directly suspended droplet microextraction (DSDME) for the extraction and pre-concentration of wide-range organophosphorus pesticides (OPPs) from human blood prior to liquid chromatography tandem mass spectrometric (LC-MS/MS) analysis. In this method, instead of protecting the unwanted rupturing of extraction droplet (organic solvent), it was deliberately splintered into fine droplets by providing automated high-speed agitation to the biphasic extraction system (extraction solvent and sample solution). Fine organic droplets were then recollected into one, not by using a centrifuge machine but just by giving a very slow stirring to the bottom of the extraction system. The present method has surmounted the problem of prolonged extraction time associated with old DSDME. Under optimum extraction conditions, the method showed good sensitivity with low detection limits ranging from 0.0009 to 0.122µgL(-1). Mean recoveries were achieved in the range of 86-109% at three levels of spiking concentration (low, middle and high) from linearity range of individual analyte. Intra-day and inter-day precisions were ≤4.68 and ≤9.57 (%RSD) respectively. Enrichment factor (EF) for each analyte varied from 30 to 132 which prove the ability of this technique to pre-concentrate the extracted analytes up to a good extent. The sample matrices have shown an insignificant influence on method's sensitivity. The proposed method may find immense use in epidemiological, toxicological, regulatory and forensic laboratories.

The polyomavirus puzzle: is host immune response beneficial in controlling BK virus after adult hematopoietic cell transplantion?

BK virus (BKV), a ubiquitous human polyomavirus, usually does not cause disease in healthy individuals. BKV reactivation and disease can occur in immunosuppressed individuals, such as those who have undergone renal transplantation or hematopoietic cell transplantation (HCT). Clinical manifestations of BKV disease include graft dysfunction and failure in renal transplant recipients; HCT recipients frequently experience hematuria, cystitis, hemorrhagic cystitis (HC), and renal dysfunction. Studies of HCT patients have identified several risk factors for the development of BKV disease including myeloablative conditioning, acute graft-versus-host disease, and undergoing an umbilical cord blood (uCB) HCT. Although these risk factors indicate that alterations in the immune system are necessary for BKV pathogenesis in HCT patients, few studies have examined the interactions between host immune responses and viral reactivation in BKV disease. Specifically, having BKV immunoglobulin-G before HCT does not protect against BKV infection and disease after HCT. A limited number of studies have demonstrated BKV-specific cytotoxic T cells in healthy adults as well as in post-HCT patients who had experienced HC. New areas of research are required for a better understanding of this emerging infectious disease post HCT, including prospective studies examining BK viruria, viremia, and their relationship with clinical disease, a detailed analysis of urothelial histopathology, and laboratory evaluation of systemic and local cellular and humoral immune responses to BKV in patients receiving HCT from different sources, including uCB and haploidentical donors.

Bio-composites of cassava starch-green coconut fiber: part II-Structure and properties.

Development of any new material requires its complete characterization to find potential applications. In that direction, preparation of bio-composites of cassava starch containing up to 30 wt.% green coconut fibers from Brazil by thermal molding process was reported earlier. Their characterization regarding physical and tensile properties of both untreated and treated matrices and their composites were also reported. Structural studies through FTIR and XRD and thermal stability of the above mentioned composites are presented in this paper. FT-IR studies revealed decomposition of components in the matrix; the starch was neither chemically affected nor modified by either glycerol or the amount of fiber. XRD studies indicated increasing crystallinity of the composites with increasing amount of fiber content. Thermal studies through TGA/DTA showed improvement of thermal stability with increasing amount of fiber incorporation, while DMTA showed increasing storage modulus, higher glass transition temperature and lower damping with increasing fiber content. Improved interfacial bonding between the matrix and fibers could be the cause for the above results.

Primary marginal zone B-cell lymphoma of appendix.

Primary lymphomas of appendix are extremely rare tumors. The first case of primary lymphoma of appendix was reported by Warren in the year 1898. Incidence of primary lymphoma of appendix is 0.015% of all gastrointestinal lymphomas. This is a report of primary marginal zone B-cell lymphoma of appendix which presented as appendicular mass. As some cases are incidentally discovered, this case emphasizes that histological examination of all appendicectomy specimens is mandatory.