Role of multiparametric MRI in predicting muscle invasiveness in urinary bladder neoplasms with pathological correlations.

Urinary bladder cancer (BC) is one of the most frequent malignancies and the ninth most common malignancy worldwide. The objective of this study is to assess the role of multiparametric magnetic resonance imaging (mp-MRI) in predicting the invasiveness of urinary bladder space occupying lesions. Thirty-five patients diagnosed with bladder masses underwent an mp-MRI study. The results of three image sets were analysed and compared with the histopathological results as a reference standard: T2-weighted image (T2WI) plus dynamic contrast-enhanced (DCE), T2WI plus diffusion-weighted images (DWI), and mp-MRI, including T2WI plus DWI and DCE. The diagnostic accuracy of mp-MRI was evaluated using receiver operating characteristic curve analysis. We discovered a highly significant correlation between muscle invasiveness as staged by HPE (Histopathological examination) and mp-MRI utilising a VI-RADS score >3 (p 0.001) with a sensitivity of 100% and a specificity of 85.7%. With a diagnostic accuracy of 77.14%, a sensitivity of 92.31%, a specificity of 72.72%, a positive predictive value of 66.67%, and a negative predictive value of 94.11%, In terms of muscle invasiveness, there is good concordance between HPE staging and mp-MRI utilising the VI-RADS score. The mean apparent diffusion coefficient (ADC) values were higher in low grades than in high grades. The ROC curve study revealed a very strong correlation between HPE grade and ADC (p = 0.045). In 77.14% of patients, Mp-MRI correctly identified the local T stage. Mp-MRI is imaging biomarker for invasiveness and grade of tumour. The tumours with high grade are more invasive. However, the diagnostic accuracy of mp-MRI in determining muscle invasiveness is not very high and it overstages the disease in some cases (33.3%). Its clinical usefulness in determining muscle invasiveness before TURBT and histopathological examination can be questioned.

Design and evaluation of in situ gel eye drops containing nanoparticles of Gemifloxacin Mesylate.

Traditional eye drops used for topically administering drugs have poor ocular bioavailability due to the biological barriers of the eye. There is an interest to design and develop novel drug delivery systems that would extend the precorneal residence time, reduce the frequency of administration and decrease dose-related toxicity. This study aimed to prepare Nanoparticles of Gemifloxacin Mesylate and incorporate them into an in situ gel. The nanoparticles were prepared by ionic gelation technique, using 32 factorial design. Sodium tripolyphosphate (STPP) was used to crosslink Chitosan. The optimized formulation of the nanoparticles (GF4) contained 0.15% Gemifloxacin Mesylate, 0.15% Chitosan and 0.20% STPP, producing 71 nm particle size and 81.11% entrapment efficiency. The prepared nanoparticles showed biphasic release, with an initial burst release of 15% in 1.0 hr and a cumulative drug release of 90.53% at the end of 24 hrs. After that, the prepared nanoparticles were incorporated into an in situ gel, using Poloxamer 407, producing a sustained drug release with efficient antimicrobial activity against gram-positive and gram-negative bacteria as confirmed by the cup plate method.

Evaluation of renal space occupying lesions with multiparametric MRI and its correlation with histopathology findings- an observational study.

The term multiparametric MRI, is a useful tool in reference to an approach that takes advantage of the added value of different MR imaging acquisitions to yield anatomic and pathophysiologic information about renal space occupying lesions and to evaluate patients with different tumors, including genitourinary malignancies. The role of multiparametric MRI is continuously growing because of its ability to detect and characterize renal space occupying lesions as well as to assess response to treatment. An observational study was carried out in 50 patients who presented with renal mass, based on clinical suspicion and prior imaging diagnosis of neoplastic renal space occupying lesion. Total renal space occupying lesions were 50, of which, 38 were males & 12 were females. The age range of the study population was 30-80 years. In our study, Agreement analysis between mpMRI diagnosis and HPE diagnosis of different RCC subtypes was statistically significant. So, multiparametric MRI had a role in differentiating the subtypes of RCC which had fair agreement with HPE. The present study results state that the renal mass lesions has different ADC values for different lesions because of the change in tissue contents and there was a statistically significant difference in ADC values between low and high-stage RCCs. Histologic and radiologic profiles of renal space occupying lesions and diverse subtypes of RCC can be used as biologic indicators of clinical behavior, response to treatment, and prognosis.

Marine phytoplankton responses to oil and dispersant exposures: Knowledge gained since the Deepwater Horizon oil spill.

The Deepwater Horizon oil spill of 2010 brought the ecology and health of the Gulf of Mexico to the forefront of the public's and scientific community's attention. Not only did we need a better understanding of how this oil spill impacted the Gulf of Mexico ecosystem, but we also needed to apply this knowledge to help assess impacts from perturbations in the region and guide future response actions. Phytoplankton represent the base of the food web in oceanic systems. As such, alterations of the phytoplankton community propagate to upper trophic levels. This review brings together new insights into the influence of oil and dispersant on phytoplankton. We bring together laboratory, mesocosm and field experiments, including insights into novel observations of harmful algal bloom (HAB) forming species and zooplankton as well as bacteria-phytoplankton interactions. We finish by addressing knowledge gaps and highlighting key topics for research in novel areas.

Photophysiological and light absorption properties of phytoplankton communities in the river-dominated margin of the northern Gulf of Mexico.

Spatial and temporal variability in photophysiological properties of phytoplankton were examined in relationship to phytoplankton community composition in the river-dominated continental margin of the northern Gulf of Mexico (NGOM). Observations made during five research cruises in the NGOM included phytoplankton photosynthetic and optical properties and associated environmental conditions and phytoplankton community structure. Distinct patterns of spatial and temporal variability in photophysiological parameters were found for waters dominated by different phytoplankton groups. Photophysiological properties for locations associated with dominance by a particular group of phytoplankton showed evidence of photoacclimation as reflected by differences in light absorption and pigment characteristics in relationship to different light environments. The maximum rate of photosynthesis normalized to chlorophyll ( PmaxB) was significantly higher for communities dominated (>60% biomass) by cyanobacteria + prochlorophyte (cyano + prochl). The initial slope of the photosynthesis-irradiance (P-E) curve normalized to chlorophyll ( αB) was not clearly related to phytoplankton community structure and no significant differences were found in PmaxB and αB between different geographic regions. In contrast, maximum quantum yield of carbon fixation in photosynthesis (Φcmax) differed significantly between regions and was higher for diatom-dominated communities. Multiple linear regression models, specific for the different phytoplankton communities, using a combination of environmental and bio-optical proxies as predictor variables showed considerable promise for estimation of the photophysiological parameters on a regional scale. Such an approach may be utilized to develop size class-specific or phytoplankton group-specific primary productivity models for the NGOM.

An Uncanny Dehydrogenation Mechanism: Polar Bond Control over Stepwise or Concerted Transition States.

The mechanism of the dehydrogenation of N-heterocycles with the recently established bifunctional catalyst (iPrPNP)Fe(CO)(H) was investigated through experiments and density functional theory calculations (iPrPNP = iPr2PCH2CH2NCH2CH2PiPr2). In this system, the saturated N-heterocyclic substrates are completely dehydrogenated to the aromatic products. Calculations indicate that dehydrogenation barriers of the C-C bonds are very high in energy (ΔG‡ = 37.4-42.2 kcal/mol), and thus dehydrogenation only occurs at the C-N bond (ΔG‡ = 9.6-22.2 kcal/mol). Interestingly, substrates like piperidine with relatively unpolarized C-N bonds are dehydrogenated through a concerted proton/hydride transfer bifunctional transition state involving the nitrogen on the PNP ligand. However, substrates with polarized C-N bonds entail stepwise (proton then hydride) bifunctional dehydrogenation.

Rapid oxidative hydrogen evolution from a family of square-planar nickel hydride complexes.

A series of square-planar nickel hydride complexes supported by bis(phosphinite) pincer ligands with varying substituents (-OMe, -Me, and -Bu t ) on the pincer backbone have been synthesized and completely characterized by NMR spectroscopy, IR spectroscopy, elemental analysis, and X-ray crystallography. Their cyclic voltammograms show irreversible oxidation peaks (peak potentials from 101 to 316 mV vs. Fc+/Fc) with peak currents consistent with overall one-electron oxidations. Chemical oxidation by the one-electron oxidant Ce(NBu4)2(NO3)6 was studied by NMR spectroscopy, which provided quantitative evidence for post-oxidative H2 evolution leading to a solvent-coordinated nickel(ii) species with the pincer backbone intact. Bulk electrolysis of the unsubstituted nickel hydride (3a) showed an overall one-electron stoichiometry and gas chromatographic analysis of the headspace gas after electrolysis further confirmed stoichiometric production of dihydrogen. Due to the extremely high rate of the post-oxidative chemical process, electrochemical simulations have been used to establish a lower limit of the bimolecular rate constant (kf > 107 M-1 s-1) for the H2 evolution step. To the best of our knowledge, this is the fastest known oxidative H2 evolution process observed in transition metal hydrides. Quantum chemical calculations based on DFT indicate that the one-electron oxidation of the nickel hydride complex provides a strong chemical driving force (-90.3 kcal mol-1) for the production of H2 at highly oxidizing potentials.

Highly Selective Formation of n-Butanol from Ethanol through the Guerbet Process: A Tandem Catalytic Approach.

A highly selective (>99%) tandem catalytic system for the conversion of ethanol (up to 37%) to n-butanol, through the Guerbet process, has been developed using a bifunctional iridium catalyst coupled with bulky nickel or copper hydroxides. These sterically crowded nickel and copper hydroxides catalyze the key aldol coupling reaction of acetaldehyde to exclusively yield the C4 coupling product, crotonaldehyde. Iridium-mediated dehydrogenation of ethanol to acetaldehyde has led to the development of an ethanol-to-butanol process operated at a lower temperature.

Evolution of a thienopyrimidine antitubercular relying on medicinal chemistry and metabolomics insights.

The metabolic instability of an antitubercular small molecule CD117 was addressed through iterative alteration of a key sulfide substituent and interrogation of the effect on growth inhibition of cultured Mycobacterium tuberculosis. This process was informed by studies of the intramycobacterial metabolism of CD117 and its inactive carboxylic acid derivative. Isoxazole 4e and thiazole 4m demonstrated significant gains in mouse liver microsomal stability with slight losses in whole-cell activity. This work illustrates the challenges of antitubercular hit evolution, requiring a balance of chemical and biological insights.

Prediction of the curing time to achieve maturity of the nano-cement based concrete using the Weibull distribution model: A complementary data set.

This data article provides a comparison data for nano-cement based concrete (NCC) and ordinary Portland cement based concrete (OPCC). Concrete samples (OPCC) were fabricated using ten different mix design and their characterization data is provided here. Optimization of curing time using the Weibull distribution model was done by analyzing the rate of change of compressive strength of the OPCC. Initially, the compressive strength of the OPCC samples was measured after completion of four desired curing times. Thereafter, the required curing time to achieve a particular rate of change of the compressive strength has been predicted utilizing the equation derived from the variation of the rate of change of compressive strength with the curing time, prior to the optimization of the curing time (at the 99.99% confidence level) using the Weibull distribution model. This data article complements the research article entitled "Prediction of the curing time to achieve maturity of the nano-cement based concrete using the Weibull distribution model" [1].

Cobb syndrome: A rare cause of paraplegia.

Cobb syndrome is an exceedingly rare clinical condition defined by the presence of a vascular skin nevus and an angioma in the spinal canal at the same metamere. We report the case of a 14-year-old boy who presented with sudden onset paraplegia. Physical examination showed port-wine stains over buttock and thigh. Magnetic resonance (MR) angiogram of the dorso-lumbar spine revealed a large arteriovenous malformation (AVM) at D11-D12 to L2-L3 levels. These concurrent findings led to the diagnosis of Cobb's syndrome. The patient received orally administered prednisolone therapy and underwent endovascular embolization of spinal angioma. Cobb's syndrome is a rare disease entity and literature search revealed only a few case reports and series mentioning this condition to date. The importance lies in the recognition that cutaneous vascular lesions may clue to an associated spinal cord angioma or AVM that may lead to weakness or paralysis.

MRI characterization of temporal lobe epilepsy using rapidly measurable spatial indices with hemisphere asymmetries and gender features.

INTRODUCTION: The paucity of morphometric markers for hemispheric asymmetries and gender variations in hippocampi and amygdalae in temporal lobe epilepsy (TLE) calls for better characterization of TLE by finding more useful prognostic MRI parameter(s). METHODS: T1-weighted MRI (3 T) morphometry using multiple parameters of hippocampus-parahippocampus (angular and linear measures, volumetry) and amygdalae (volumetry) including their hemispheric asymmetry indices (AI) were evaluated in both genders. The cutoff values of parameters were statistically estimated from measurements of healthy subjects to characterize TLE (57 patients, 55% male) alterations. RESULTS: TLE had differential categories with hippocampal atrophy, parahippocampal angle (PHA) acuteness, and several other parametric changes. Bilateral TLE categories were much more prevalent compared to unilateral TLE categories. Female patients were considerably more disposed to bilateral TLE categories than male patients. Male patients displayed diverse categories of unilateral abnormalities. Few patients (both genders) had combined bilateral appearances of hippocampal atrophy, amygdala atrophy, PHA acuteness, and increase in hippocampal angle (HA) where medial distance ratio (MDR) varied among genders. TLE had gender-specific and hemispheric dominant alterations in AI of parameters. Maximum magnitude of parametric changes in TLE includes (a) AI increase in HA of both genders, (b) HA increase (bilateral) in female patients, and (c) increase in ratio of amygdale/hippocampal volume (unilateral, right hemispheric), and AI decrease in MDR, in male patients. CONCLUSION: Multiparametric MRI studies of hippocampus and amygdalae, including their hemispheric asymmetry, underscore better characterization of TLE. Rapidly measurable single-slice parameters (HA, PHA, MDR) can readily delineate TLE in a time-constrained clinical setting, which contrasts with customary three-dimensional hippocampal volumetry that requires many slice computation.

Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds.

The reductions of aldehydes, ketones, and esters to alcohols are important processes for the synthesis of chemicals that are vital to our daily life, and the reduction of CO2 to methanol is expected to provide key technology for carbon management and energy storage in our future. Catalysts that affect the reduction of carbonyl compounds often contain ruthenium, osmium, or other precious metals. The high and fluctuating price, and the limited availability of these metals, calls for efforts to develop catalysts based on more abundant and less expensive first-row transition metals, such as nickel and iron. The challenge, however, is to identify ligand systems that can increase the thermal stability of the catalysts, enhance their reactivity, and bypass the one-electron pathways that are commonly observed for first-row transition metal complexes. Although many other strategies exist, this Account describes how we have utilized pincer ligands along with other ancillary ligands to accomplish these goals. The bis(phosphinite)-based pincer ligands (also known as POCOP-pincer ligands) create well-defined nickel hydride complexes as efficient catalysts for the hydrosilylation of aldehydes and ketones and the hydroboration of CO2 to methanol derivatives. The hydride ligands in these complexes are substantially nucleophilic, largely due to the enhancement by the strongly trans-influencing aryl groups. Under the same principle, the pincer-ligated nickel cyanomethyl complexes exhibit remarkably high activity (turnover numbers up to 82,000) for catalytically activating acetonitrile and the addition of H-CH2CN across the C═O bonds of aldehydes without requiring a base additive. Cyclometalation of bis(phosphinite)-based pincer ligands with low-valent iron species "Fe(PR3)4" results in diamagnetic Fe(II) hydride complexes, which are active catalysts for the hydrosilylation of aldehydes and ketones. Mechanistic investigation suggests that the hydride ligand is not delivered to the carbonyl substrates but is important to facilitate ligand dissociation prior to substrate activation. In the presence of CO, the amine-bis(phosphine)-based pincer ligands are also able to stabilize low-spin Fe(II) species. Iron dihydride complexes supported by these ligands are bifunctional as both the FeH and NH moieties participate in the reduction of C═O bonds. These iron pincer complexes are among the first iron-based catalysts for the hydrogenation of esters, including fatty acid methyl esters, which find broad applications in industry. Our studies demonstrate that pincer ligands are promising candidates for promoting the first-row transition metal-catalyzed reduction of carbonyl compounds with high efficiency. Further efforts in this research area are likely to lead to more efficient and practical catalysts.

Tuberculosis Drug Development: History and Evolution of the Mechanism-Based Paradigm.

Modern tuberculosis (TB) chemotherapy is widely viewed as a crowning triumph of anti-infectives research. However, only one new TB drug has entered clinical practice in the past 40 years while drug resistance threatens to further destabilize the pandemic. Here, we review a brief history of TB drug development, focusing on the evolution of mechanism(s)-of-action studies and key conceptual barriers to rational, mechanism-based drugs.

Reversible catalytic dehydrogenation of alcohols for energy storage.

Reversibility of a dehydrogenation/hydrogenation catalytic reaction has been an elusive target for homogeneous catalysis. In this report, reversible acceptorless dehydrogenation of secondary alcohols and diols on iron pincer complexes and reversible oxidative dehydrogenation of primary alcohols/reduction of aldehydes with separate transfer of protons and electrons on iridium complexes are shown. This reactivity suggests a strategy for the development of reversible fuel cell electrocatalysts for partial oxidation (dehydrogenation) of hydroxyl-containing fuels.

A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste.

To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite.

A molecular iron catalyst for the acceptorless dehydrogenation and hydrogenation of N-heterocycles.

A well-defined iron complex (3) supported by a bis(phosphino)amine pincer ligand efficiently catalyzes both acceptorless dehydrogenation and hydrogenation of N-heterocycles. The products from these reactions are isolated in good yields. Complex 3, the active catalytic species in the dehydrogenation reaction, is independently synthesized and characterized, and its structure is confirmed by X-ray crystallography. A trans-dihydride intermediate (4) is proposed to be involved in the hydrogenation reaction, and its existence is verified by NMR and trapping experiments.