Size dependent electronic structure of LiFePO4 probed using X-ray absorption and Mössbauer spectroscopy.

We present the combined Mössbauer and X-ray absorption spectroscopy investigation of the electronic structure and local site symmetry of Fe in olivine structured LiFePO4 (LFP) with crystallite size (CS). The lattice parameters are found to contract with a decrease in CS, monotonously, whereas the electronic structural parameters exhibit two different regions with a threshold anomaly of around ≈30 nm. 57Fe Mössbauer studies reveal the coexistence of Fe2+ and Fe3+ sites and their relative concentrations are mainly determined by CS, which provides a comprehensive insight into the electronic structure of LFP at the mesoscopic level. The soft X-ray absorption unequivocally unravels the valence states of Fe 3d electrons in proximity to the Fermi level, which are prone to the local lattice distortion. The obtained spectra fingerprint the effect of CS supplying rich information on valency, lithium-ion vacancy concentration, covalency and crystal field. By comparing the spectra with the results of charge-transfer multiplet calculations, which include the full-atomic multiplet theory, we have found that the local symmetry of Fe ions is well described by the D4h point group with intermixing between eg and t2g orbitals. The unique structural and electronic properties of LFP are closely interlinked with changes in the bonding character, which shows the strong dependency on CS. The evolution of 3d states is in overall agreement with the local lattice distortion and provides the origin of the size effects on the electronic structure of olivine phosphate and other transition metal ion-containing materials.

Effect of crystallite size on the phase transition behavior of heterosite FePO4.

For advanced lithium-ion battery technology, olivine-based cathodes are considered to be the most dominant and technologically recognized materials. The extraction of lithium ions from olivine LiFePO4 results in the two-phase mixture with heterosite FePO4 exhibiting a deintercalation potential of 3.45 V vs. Li+/Li over a wide range of lithium content. Here, we report the synthesis and characterization of chemically deintercalated heterosite FePO4 with varying crystallite sizes using different analytical techniques. The decrease in the crystallite size of heterosite FePO4 leads to an increase in the lattice parameters including the unit cell volume. The characteristic behavior in the structural properties of heterosite FePO4 shows a strong dependency on the crystallite size which is correlated with the change in the chemical bonding. The volume expansion of the nano-sized heterosite FePO4 with respect to the bulk counterpart is suggested to be a direct consequence of reduced hybridization between the Fe3d and O2p states. Furthermore, the combined X-ray diffraction and Mössbauer spectroscopic studies reveal the appearance of a new phase namely trigonal FePO4 at the lower crystallite sizes due to the enhanced surface energy kinetics. We also find that the observed trigonal FePO4 phase is more magnetically active than the paramagnetic olivine FePO4. For the unique structural advantage of the heterosite phase as an electrode material, the change in bonding characteristics is very useful and can have strong implications on the electronic properties of heterosite FePO4 at the nanoscale level.

Role of oestrogen receptor-α and -ß in bladder tissue of patients with a clinical diagnosis of benign prostatic hyperplasia.

OBJECTIVES: To study the differential expression of oestrogen receptor (ER) subtypes in human urinary bladder tissue using immunohistochemistry (IHC) methods and to explore their correlation with various measures of lower urinary tract symptoms (LUTS). METHODS: In this prospective case-control study, the case group comprised 34 patients with bothersome LUTS who underwent transurethral resection of prostate (TURP), while the control group comprised 19 age-matched, otherwise healthy patients who underwent cystoscopy to investigate microscopic haematuria. Cystoscopy and bladder biopsy were performed in both groups. IHC evaluation of biopsy specimens was carried out for ER subtypes (ER-α and ER-ß) and for Ki 67 in semi-quantitative fashion. Correlations of receptors with various measures of benign prostatic hyperplasia (BPH)/LUTS were also assessed. RESULTS: Expression of ER-α (in both epithelial and stromas cells) was statistically significantly greater in the case group than in the control group, but ER-ß expression was not significantly different between the groups. Ki 67 expression was also significantly greater in the case group. Comparison of clinical variables according to receptor status showed that International Prostate Symptom Score (IPSS), post-void residual urine volume (PVR) and prostate volume were significantly associated with epithelial and stromal ER-α; however, ER-ß was associated only with PVR. CONCLUSION: We found significant correlation between bladder ER levels (specifically ER-α) and various clinical measures of BPH. We conclude that ER-α is the key mediator that could be responsible for various clinical measures of BPH/LUTS.

Toluene Poisoning Presenting as Bilateral Basal Ganglia Haemorrhage.

Toluene is an aromatic hydrocarbon that is often used as a solvent in paints, paint thinners, glues, disinfectants and as an industrial solvent for the manufacturing of pharmaceuticals, paints and chemicals. Metabolic acidosis is a recognized complication of toluene poisoning. However, we here report an unusual case of toluene poisoning presenting with bilateral intracerebral haemorrhage.

Enabling the Electrochemical Activity in Sodium Iron Metaphosphate [NaFe(PO3)3] Sodium Battery Insertion Material: Structural and Electrochemical Insights.

Sodium-ion batteries are widely pursued as an economic alternative to lithium-ion battery technology, where Fe- and Mn-based compounds are particularly attractive owing to their elemental abundance. Pursuing phosphate-based polyanionic chemistry, recently solid-state prepared NaFe(PO3)3 metaphosphate was unveiled as a novel potential sodium insertion material, although it was found to be electrochemically inactive. In the current work, employing energy-savvy solution combustion synthesis, NaFe2+(PO3)3 was produced from low-cost Fe3+ precursors. Owing to the formation of nanoscale carbon-coated product, electrochemical activity was enabled in NaFe(PO3)3 for the first time. In congruence with the first principles density functional theory (DFT) calculations, an Fe3+/Fe2+ redox activity centered at 2.8 V (vs Na/Na+) was observed. Further, the solid-solution metaphosphate family Na(Fe1-xMnx)(PO3)3 (x = 0-1) was prepared for the first time. Their structure and distribution of transition metals (TM = Fe/Mn) was analyzed with synchrotron diffraction, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy. Synergizing experimental and computational tools, NaFe(PO3)3 metaphosphate is presented as an electrochemically active sodium insertion host material.

Electron microscopic changes of detrusor in benign enlargement of prostate and its clinical correlation.

AIMS: To study the ultra structural changes in bladder musculature in cases of BPE and their clinical relevance. MATERIAL AND METHODS: In this descriptive longitudinal, controlled, observational study patients were enrolled into three groups, group 1, group 2A and group 2B. Control group (group-1) consisted of age matched normal male patients, who underwent surveillance or diagnostic cystoscopy for microscopic hematuria or irritative symptoms. Case group (group-2) comprised of patients with BPE, undergoing TURP. Case group (group-2) was further classified into: Category 2A (patients not on catheter) and cat-egory 2B (patients on catheter). All relevant clinical parameters like IPSS, prostate size, Qmax, PVR were recorded. Cystoscopy and bladder biopsy were performed in all patients. Various ultrastructural parameters like myocytes, fascicular pattern, interstitial tissue, nerve hypertrophy and cell junction pattern were analyzed under electron microscope and they were clinically correlated using appropriate statistical tests. RESULTS: Control group had significant difference as compared to case group in terms of baseline parameters like IPSS, flow rate and prostate size, both preoperatively and postoperatively, except for PVR, which was seen only preoperatively. There was statistically significant difference in ultrastructural patterns between case and control group in all five electron microscopic patterns. However, no significant difference was found between the subcategories of case groups. CONCLUSIONS: BPE is responsible for ultra structural changes in detrusor muscle and these changes remain persistent even after TURP. Nerve hypertrophy, which was not thoroughly discussed in previous studies, is also one of the salient feature of this study.

miR-146a and miR-370 coordinate enterovirus 71-induced cell apoptosis through targeting SOS1 and GADD45ß.

Enterovirus 71 (EV71) is an emerging life-threatening pathogen particularly in the Asia-Pacific region. The major pathogenic feature in EV71-infected cells is apoptosis. However, which molecular mechanism mainly contributes to EV71-induced apoptosis is not investigated thoroughly. MicroRNAs (MiRNAs), the newly discovered molecules, govern a wide range of biological functions through post-transcriptional regulation including viral pathogenesis. Whether miRNAs and messenger RNAs (mRNAs) coordinate to trigger host cell apoptosis in EV71 infection was investigated in this study. We conducted an apoptosis-oriented approach using both mRNA and miRNA profiling and bioinformatic analysis. We identified two major apoptosis-associated signalling pathways, Bcl2 antagonist of cell death (BAD) phosphorylation and p53-dependent apoptosis pathways, in which Son of sevenless homolog 1 (SOS1) and Growth arrest and DNA damage-inducible protein 45ß (GADD45ß) were predicted as targets of miR-146a and miR-370 respectively. Luciferase reporter assays and Western blots demonstrated the negative regulation between miR-146a and SOS1 and between miR-370 and GADD45ß. Silencing of miR-146a restored SOS1 expression and partially attenuated EV71 infection-induced apoptosis. Conversely, ectopic expression of miR-370 decreased virus infection-induced GADD45ß expression and also diminished apoptosis. Finally, the transfection of antagomiR-146a and miR-370 contributed to attenuating EV71 infection-induced apoptosis. Herein we clearly demonstrate that EV71-induced cell apoptosis is partly governed by altered miRNAs.

Role of oral pentosan polysulphate in the reduction of local side effects of BCG therapy in patients with non-muscle-invasive bladder cancer: a pilot study.

OBJECTIVE: To assess the role of oral pentosan polysulphate (PPS) in the reduction of bacille Calmette-Guérin (BCG)-related local side effects in patients with high grade Ta/T1 non-muscle-invasive bladder cancer (NMIBC). PATIENTS AND METHODS: A total of 32 symptomatic patients receiving BCG instillation were randomized into three groups: group A received placebo (vitamin B complex tablet) thrice daily; group B received PPS 100 mg thrice daily; and group C received PPS 100 mg once daily and placebo (vitamin B complex tablet) twice daily for 6 weeks. A visual analogue scale (VAS) score for bladder pain, Overactive Bladder-Validated 8 Question Screener (OAB-V8) scores and dysuria were evaluated in the three groups before and during each weekly visit for BCG instillation. RESULTS: The mean ± sd post-treatment VAS scores were significantly lower in groups B (4.4 ± 1.2) and C (5.8 ± 0.8) than in group A (8 ± 0.4). In addition, the post-treatment VAS score was significantly lower in group B than in group C (P<0.01). The mean post-treatment OAB-V8 score was significantly lower only in group B (decreased from 15.5 to 9.7). Dysuria decreased in groups B and C but persisted in group A. CONCLUSION: The present study shows that oral PPS (100 mg) thrice daily is effective in relieving BCG-related local side effects.

Pneumatic cystolithotripsy versus holmium:yag laser cystolithotripsy in the treatment of pediatric bladder stones: a prospective randomized study.

PURPOSE: Holmium:yttrium-aluminum-garnet (Ho:YAG) laser and Pneumatic cystolithotripsy (CL) are the most widely practiced transurethral procedures for treatment of pediatric bladder stones. The aim of our study was to compare the safety and efficacy of Ho:YAG laser CL and pneumatic CL in the treatment of pediatric bladder stones. METHODS: In this prospective randomized study from January 2012 to April 2015, 25 male children with bladder stones <3 cm were consecutively randomized into two treatment groups: group A (pneumatic CL) consisted of 13 patients and group B (Ho:YAG CL) consisted of 12 patients. Operative time, duration of stay and complications were recorded. Patients were followed up prospectively. RESULTS: The mean operative time was significantly lower in group B (25.6 vs. 31.6 min) for stones <1.5 cm (p = 0.040). However, for stones between 1.5 and 3 cm in size, the mean operating times were similar in both the groups (49.4 min in Ho:YAG vs. 44.6 min in pneumatic, p = 0.40). There was no difference in complication rates and hospital stay in both the groups. No major complications were seen in both the groups. CONCLUSIONS: We found that Ho:YAG CL was more effective than pneumatic CL for treating bladder stones smaller than 1.5 cm.

Impact of high energy photons on physical, structural and magnetic properties of Mn0.65Zn0.35Fe2-xNdxO4 nanoparticles.

Ultrafine powders of Nd+3 doped Mn-Zn ferrite powders with composition Mn0.65Zn0.35Fe2-xNdxO4 (x = 0.04, 0.06, 0.08) were prepared using the combustion method of preparation. Monophasic nanoparticle formation was confirmed by X-ray diffraction. The particle size was determined using a Transmission electron microscope (TEM). The nanopowders were investigated for their physical, structural, and magnetic properties and then radiated with gamma photons obtained from Co60 source with a dose of 500Gy, 750Gy and 1000Gy. The characterization of radiated powders showed preservation of spinel structure with breaking down of crystallites into finer crystals with increment in amorphous content. Structural and physical parameters were drastically altered due to high-energy photon exposure. The breaking down of larger particles was observed as a result of photon energy impact on the samples. The Saturation magnetization of ferrite nanoparticles was observed to increase with increasing gamma radiation dose. Mössbaure spectra showed the dominance of Fe+3 in the high spin state.

Recurrent Pericardial Effusion Due to Panhypopituitarism: A Rare Case Report.

Introduction: A female patient, 48 years of age, with a complaint of recurrent episodes of diffuse chest pain, vertigo, and shortness of breath in the last five years, presented needing immediate medical attention. Case Presentation: The patient was evaluated and suspected of severe hypotension, cold hands, and feet with distended neck veins and muffled heart sounds. ECG revealed low voltage complexes and large pericardial effusion with a collapse in the diastole of the right auricle and ventricle. The provisional diagnosis was kept as pericardial effusion with hemodynamic compromise. Detailed history disclosed that she had suffered similar events five years before, during which a pericardial tap was performed, and the patient was on anti-tuberculosis treatment for nine months. The symptoms continued despite the treatments. She had a history of severe postpartum hemorrhage, failure of lactation, and early menopause with a history of hysterectomy dated ten years back. The biochemical study indicated decreased LH, FSH, TSH, ACTH, and serum cortisol levels. MRI brain revealed empty sella. The hormonal replacement was started with clinical improvement. Conclusions: Although hypothyroidism is an extremely rare cause of pericardial effusion, detailed history and further investigations are imperative to form a definitive diagnosis.

Iron-based fluorophosphate Na2FePO4F as a cathode for aqueous zinc-ion batteries.

Aqueous zinc-ion batteries form a key post-Li-ion batteries to cater the rising demand for grid storage. Fe-based compounds can be used as economical cathodes for zinc-ion batteries. Herein, we explored iron-based flourophosphate as a potential polyanionic cathode. Involving the Fe3+/2+ redox process, it can reversibly intercalate Zn2+ yielding a capacity of ∼80 mA h g-1, involving a solid-solution mechanism. Polyanionic Fe-based phosphate frameworks can be harnessed as potential low-cost cathodes for secondary zinc-ion batteries.

Antioxidant properties, phenolics and flavonoids content of some economically important plants from North-west Indian Himalaya.

The present study investigated antioxidant properties, total phenolic and flavonoid contents in methanol extract of the leaf, stem bark, and fruit of Olea ferruginea Royle, Olea europaea L., and Tilia europaea L. grow naturally in the north-west Indian Himalaya. Phenolics and flavonoids content was found to be maximum in methanol extracts of stem bark and leaf (9.28 mg GAE/g fw and 14.73 mg QE/g fw, respectively) of O. ferruginea plants. Ferric reducing antioxidant power and DPPH radical scavenging activity were found to be maximum in leaf and stem bark (38.88 mM AAE/g fw and 20.31 mM AAE/g fw, respectively) of O. ferrugenia plants, whereas maximum ABTS radical scavenging activity (4.52 mM AAE/g fw) was recorded with stem bark of T. europaea plants. These tree species were found rich in natural compounds and also possess antioxidant activities. Therefore, their pharmaceutical and local uses for the health benefits are suggested.

Evaluating the role of extracellular vesicles as a biomarker under transmission electron microscope in prostate cancer and benign prostate hyperplasia patients.

OBJECTIVES: To our knowledge, EVs (extracellular vesicles) are heterogenous encapsulated nanoparticles generated by the biological cells. EVs can be found in blood, urine and tissue of origin. They contain DNAs, RNAs, proteins specific to the cell of origin. It has been found that in PCa, increase in number of EVs can modulate phenotype and function of the recipient cells. METHODS: This prospective randomized double-blind pilot study was conducted in the SMS Medical College, Jaipur in collaboration with All India Institute of Medical Sciences, New Delhi. For morphometric analysis, the number of extracellular vesicles per micrograph were counted under transmission electron microscope. RESULTS: Out of 16 patients taken in our study, six were in group 1 (BPH group) and 10 were in group 2 (PCa group). The mean number of EVs was significantly higher in the cells of group 2 in comparison to the group 1. Among the PCa patients, mean number of EVs were 25, 30, 35, 43, 46 for the Gleason score 6, 7, 8, 9, 10 respectively. In our study the mean number of EVs in the newly diagnosed PCa group was less as compared to the CSPC and CRPC group. CONCLUSIONS: EVs are membrane bound particles shed regularly from the cells in the extracellular milieu under normal physiological and pathological conditions. In our study the number of EVs were more in the PCa cells in comparison with the BPH cells and among the PCa cells they bear a positive correlation with the Gleason score, thus EVs have the potential to become a biomarker.

Plasma polymerized functional supermagnetic Fe3O4 nanostructured templates for laccase immobilization: A robust catalytic system for bio-inspired dye degradation.

Fe3O4 magnetic nanoparticles, synthesized using co-precipitation method, were epoxy functionalized via plasma polymerization of 2,3-epoxypropylmethacrylate (EPMA) precursor. The EPMA-functionalized Fe3O4 nanoparticles (EPMA-f-MN) were employed as templates for facile, one-step covalent immobilization of laccase enzyme at room temperature. Samples were rigorously characterized by FTIR, TGA, SEM, TEM, XRD techniques, while Mössbauer spectroscopy (MöS) and vibrating sample magnetometry (VSM) confirmed the supermagnetic nature of Fe3O4 nanoparticles. Activities of free and immobilized laccase (ImLac) were assayed by spectrophotometrically monitoring the enzymatic reduction of substrate 2,2-azino-bis(3-ethylthiazoline-6-sulfonate) (ABTS) at 420 nm, corresponding to the λmax of ABTS.+. In addition to possessing higher thermal stability and a broader pH tolerance window compared to free laccase, the supermagnetic property of the Fe3O4 renders the ImLac system conveniently recoverable and recyclable. Practical applicability of ImLac towards catalytic degradation of industrial dyes was also ably demonstrated using Acid Blue 193 (AB 193) as a commercially used model textile dye, which belongs to the family of azo dyes. Over 95% degradation of the dye was achieved within a period of 4 hours. ImLac could be used for more than 10 dye degradation cycles with >90 % of retention in enzyme activity.

Percutaneous nephrolithotomy in previously operated patients: A prospective study.

PURPOSE: To determine the effect of previous renal stone surgery on result and complications of percutaneous nephrolithotomy (PCNL). MATERIALS AND METHODS: Total 300 patients were enrolled in the study. We enrolled 100 surgery-naive cases (those with no history of any renal surgery) as control and labeled them as Group A. Group B comprised 100 cases who had PCNL in the past. Group C constituted 100 patients who had open renal stone surgery in the past. Stones were classified using Guy's stone score. PCNL was performed by standard technique in prone position and technical features encountered during operation and outcomes were compared between groups. Complications were graded using modified Clavien grading system. RESULTS: There were no differences between the three groups in age, gender, body mass index, stone burden, and stone opacity. Multiple calyceal stones and distorted pelvicalyceal system anatomy were more in Group C, but stone score showed no statistically significant difference from other groups. The mean operative time (68.91 ± 21.27 min) and fluoroscopy time (264.40 ± 74.90 s) were longer in Group C, but there was no statistically significant difference between the groups. Multiple access was significantly more common in Group C compared to the other two groups (P < 0.001). Access location too did not show any statistically significant difference between the groups. Postoperative complications were more in previous stone surgery patients, but did not show statistically significant difference. CONCLUSION: PCNL is a safe and effective treatment modality for patients with renal stones regardless of history of previous PCNL or open renal surgery.

TiO2-Doped Ni0.4Cu0.3Zn0.3Fe2O4 Nanoparticles for Enhanced Structural and Magnetic Properties.

TiO2 (0-10 wt %)-doped nanocrystalline Ni0.4Cu0.3Zn0.3Fe2O4 (Ni-Cu-Zn) ferrites were synthesized using the sol-gel route of synthesis. The cubic spinel structure of the ferrites having the Fd3m space group was revealed from the analysis of Rietveld refined X-ray diffraction (XRD) data. The secondary phase of TiO2 with a space group of I41/amd was observed within the ferrites with doping, x > 3 wt %. The values of lattice parameter were enhanced with the addition of TiO2 up to 5 wt % and reduced further for the highest experimental doping of 10 wt %. Field emission scanning electron microscopy (FESEM) images exhibit the spherical shape of the synthesized particles with some agglomeration, while the compositional purity of prepared ferrite samples was confirmed by energy-dispersive X-ray spectroscopy (EDX) and elemental mapping. The cubic spinel structure of the prepared ferrite sample was confirmed by the Raman and Fourier transform infrared (FTIR) spectra. UV-visible diffuse reflectance spectroscopy was utilized to study the optical properties of the ferrites. The value of band gap energy for the pristine sample was less than those of the doped samples, and there was a decrement in band gap energy values with an increase in TiO2 doping, which specifies the semiconducting nature of prepared ferrite samples. A magnetic study performed by means of a vibrating sample magnetometer (VSM) demonstrates that the values of saturation magnetization of the ferrites decrease with the addition of TiO2 content, and all investigated ferrites show the characteristics of soft magnetic materials at room temperature. The Mössbauer study confirms the decrease in the magnetic behavior of the doped ferrites due to the nonmagnetic secondary phase of TiO2.