Spontaneous Decoration of Ultrasmall Pt Nanoparticles on Size-Separated MoS2 Nanosheets.

Liquid exfoliation can be considered as a viable approach for the scalable production of 2D materials due to its various benefits, although the polydispersity in the obtained nanosheet size hinders their straightforward incorporation. Size-separation can help alleviate these concerns, however a correlation between nanosheet size and property needs to be established to bring about size-specific applicability. Herein, size-selected aqueous nanosheet dispersions have been obtained via centrifugation-based protocols, and their chemical activity in the spontaneous reduction of chloroplatinic acid is investigated. Growth of ultrasmall Pt nanoparticles was achieved on nanosheet surfaces without a need for reducing agents, and stark differences in the nanoparticle coverage were observed as a function of nanosheet size. Defects in the nanosheets were probed via Raman spectroscopy, and correlated to the observed size-activity. Additionally, the effect of reaction temperature during synthesis was investigated. The electrochemical activity of the ultrasmall Pt nanoparticle decorated MoS2 nanosheets was evaluated for the hydrogen evolution reaction, and enhancement in performance was observed with nanosheet size, and nanoparticle decoration density. These findings shine light on the significance of nanosheet size in controlling spontaneous reduction reactions, and provide a deeper insight to intrinsic properties of liquid exfoliated nanosheets.

Fabrication of sandwich structures of Ag/analyte/MoO3sea urchins for SERS detection of methylene blue dye molecules.

A substrate for surface-enhanced Raman spectroscopy (SERS) in a sandwich configuration, noble metal/analyte/defect-rich metal oxide, is demonstrated for the detection of methylene blue(MB). The sandwich structure (Ag/MB/SUMoO3) is fabricated by physical vapour deposition of Ag nanoparticles over the MB analytes that are adsorbed on sea urchin MoO3(SUMoO3). SUMoO3are grown on a glass substrate by chemical bath deposition. The morphology of the fabricated sandwich structures shows serrated spikes of MoO3from the core region decorated with strings of silver nanoparticles. The silver-decoration and the oxygen defects of SUMoO3promote absorption in the visible region and facilitate charge transfer between MB and SUMoO3, which are beneficial for achieving superior SERS properties in this configuration compared to the contribution from individual components alone. The sandwich structure is able to detect the MB molecule up to 100 nM with an enhancement factor of 8.1 × 106. The relative standard deviation of SERS intensity for the 1618 cm-1peak of MB across the substrate is 29.2%. The configuration offers stability to SERS substrate under ambient conditions. The combined effect of charge transfer, surface plasmon resonance, and MB resonance results in the improved SERS detection of MB molecules with the Ag/MB/SUMoO3sandwich structure.

Unusual Presentation of Ileal Intussusception Due to Submucosal Lipoma in a Child and its Management.

Idiopathic intussusception is the most common form of intussusception in infants and young children. In older children and adults, intussusception being rare, the lead point is usually an underlying bowel pathology (Meckel's diverticulum, hemangioma, carcinoids, polyps, submucous lipomas, etc.) and these are called pathological lead points (PLP's). The management of an obese child with recurrent abdominal pain for over 2 years, diagnosed with ileo-ileal intussusception due to submucosal lipoma is reported here.

Gold Nanorods as an Efficient Substrate for the Detection and Degradation of Pesticides.

The rapid, ultralow detection, degradation, and complete removal of pesticides demand the design of potential substrates. Herein, we discussed gold nanorods (Au NRs) as the potential substrate for the naked eye detection and degradation of two common and broad-spectrum pesticides, chlorpyrifos (CPF) and malathion (MLT), up to 0.15 ppt concentration within 2 min. Under certain environmental conditions, both the pesticides degraded and adsorbed on the surface of Au NRs. The degraded moieties of CPF and MLT on the surface of Au NRs formed side-to-side and end-to-end interactions, respectively, leading to a long-range assembly. This shows that no external agent is required, and only CPF and MLT analytes are quite enough for the formation of assembly of Au NRs. Assembly of Au NRs is confirmed by transmission electron microscopy (TEM) analysis, and degradation is supported by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and gas chromatography-mass spectrometry (GC-MS) analyses. Au NRs were recovered and reused for four consecutive cycles. The fast and ultralow detection of pesticides demonstrates that Au NRs are a potential substrate for the detection and degradation of pesticides.

Current mapping of lead phthalocyanine thin films in the presence of gaseous dopants.

The structural organization and its effect on conducting pathways in lead phthalocyanine (PbPc) thin films, a nonplanar phthalocyanine, deposited on Si and highly oriented pyrolytic graphite (HOPG) substrates in the presence of iodine and ammonia vapors are presented. Two-dimensional grazing incidence X-ray diffraction studies reveal that the crystalline ordering in pristine PbPc films on Si and HOPG substrates undergoes a drastic molecular rearrangement and surface reconstruction upon iodine doping. The structural rearrangement leads to morphological changes and higher surface roughness in iodine doped PbPc (I-PbPc) films. The obvious enhancement in the current values of I-PbPc is attributed to the introduction of holes as charge carriers. Nanoscale current mapping reveals the presence of percolation pathways in I-PbPc films, on both Si and HOPG substrates, being responsible for the observed high conductance in contrast to the isolated conducting domains in the pristine PbPc system. The broad distribution of current values across various conducting domains on Si is attributed to a mixture of crystalline phases and disordered fractions of I-PbPc, while the narrow distribution of current values observed in the case of HOPG arises from the majorly disordered PbPc molecules. These films also show enhanced sensitivity towards ammonia that is almost four times higher in magnitude than for pristine PbPc films. The current maps show that the adsorption of ammonia molecules disrupts the iodine percolation pathways, thereby imposing a detrimental effect on the conductivity of the PbPc films.

Designing Metallic MoO2 Nanostructures on Rigid Substrates for Electrochemical Water Activation.

In situ growth of metallic MoO2 films on fluorine-doped tin oxide (FTO) and MoO2 powder in solution was achieved simultaneously by a simple hydrothermal process employing citric acid as the surfactant. The growth mechanism of MoO2 nanostructures (NSs) at the heterogeneous interface and in homogeneous medium proceeds in a different manner in which seeds grow in a preferred orientation on FTO, whereas they propagate in all directions in solution. The high lattice matching of FTO and MoO2 favours the film growth which could not be obtained on other conventional substrates. The disc morphology of MoO2 nanostructures was changed to other diverse morphology by varying the synthesis conditions, particularly by the addition of nitric acid. A competitive effect of nitric acid and citric acid on the structure direction produced various shapes. The electrochemical water activation studies show that hydrogen-annealed MoO2 is an excellent hydrogen evolution reaction (HER) catalyst with good stability. H-MoO2 film/FTO displays a low onset overpotential of72 mV with a Tafel slope of 84.1 mV dec-1 , whereas the powder form exhibits an onset overpotential of 46 mV with a Tafel slope of 71.6 mV dec-1 . The large active surface area, exposure of fringe facets of (110) and the lesser electrochemical charge-transfer resistance offered by the hydrogen-annealed MoO2 NSs play a major role in the enhanced HER activity.

Films of Reduced Graphene Oxide with Metal Oxide Nanoparticles Formed at a Liquid/Liquid Interface as Reusable Surface Enhanced Raman Scattering Substrates for Dyes.

Free standing, thin films of reduced graphene oxide (rGO) with ZnO, CuO and SnO(2) nanostructures are prepared at a water/toluene interface utilizing simple interfacial reaction and self-assembly. rGO-ZnO, rGO-CuO and rGO-SnO(2) films exhibit unique morphologies such as hexagonal cylinders, elongated splinters, and balls, respectively, wrapped by rGO layers. The hybrid films exhibit surface enhanced Raman scattering (SERS) of rhodamine 6G dye with enhancement factors one order higher than bare metal oxide caused by a synergic effect of charge transfer between the dye, metal oxide and rGO. Doping with Ag+ ions improves SERS enhancement in rGO-Ag­ZnO hybrid films, exploiting the electromagnetic effect of metal surface plasmons. Detection sensitivity up to 10 µM dye with an enhancement factor of 104 is shown. The enhanced photodegradation rate by the hybrid films is utilized for UV induced regeneration of the used SERS substrate and is demonstrated for successive use of different analytes.

Hybrid materials of ZnO nanostructures with reduced graphene oxide and gold nanoparticles: enhanced photodegradation rates in relation to their composition and morphology.

Binary and ternary hybrid systems of ZnO possessing nanoparticle and nanorod morphologies on reduced graphene oxide (rGO) and rGO with Au nanoparticles are explored as photocatalysts and a comparative study of their photodegradation performance is presented. Various preparation methods such as solution phase and hydrothermal routes have been employed to produce rGO-ZnO hybrids and rGO-Au-ZnO hybrids to impart different morphologies and defect states in ZnO. All the hybrids exhibit faster photodegradation kinetics and the rGO-Au-ZnO system exhibits the highest rate, five times faster than bare ZnO, followed by the binary systems, rGO-ZnO nanoparticles and nanorods. Various factors such as structure, morphology, charge transfer and adsorption are considered to explain the observed kinetics. Excited state electron transfer from ZnO to both rGO and Au levels facilitates faster dye degradation for rGO-Au-ZnO and is reflected as highly quenched band edge and defect state photoluminescence. Intimate physical interfaces formed between rGO, Au and ZnO in the hybrid material during in situ reactions favour charge transfer across the components. The charge transfer contribution even dominates the adsorption factor and the rGO-Au-ZnO system with a slightly lower adsorption capacity than the rGO-ZnO system exhibits a higher degradation rate. A power law dependence of the photodegradation rate on light intensity is also expressed.

Reproductive health of women with and without disabilities in South India, the SIDE study (South India Disability Evidence) study: a case control study.

BACKGROUND: Evidence shows that women with disability have adverse pregnancy outcomes compared to those without a disability. There is a lack of published data on reproductive health of women with disability in India till date. The objective of the South India Disability Evidence (SIDE) Study was to compare reproductive health parameters including pregnancy experience, health access during pregnancy and type of delivery among women with disability compared to women with no disability. METHODS: The study was conducted in one district each in two States (Andhra Pradesh and Karnataka) in 2012. A case-control design was used to identify appropriate age and sex-matched controls for women with disability identified through a population-based survey. Trained key informants first listed women with disabilities who were then examined by a medical team to confirm the diagnosis. Trained research investigators administered questionnaire schedules to both groups of women to collect information on reproductive health and outcomes of any pregnancy experienced in the past two years. RESULTS: A total of 247 women with disability and 324 age-matched controls aged 15-45 years were recruited for the study. 87% of the women with disability had a physical disability. The mean age of women with disability was 29.86 against 29.71 years among women without a disability. A significantly lower proportion of women with disability experienced pregnancy (36.8%) compared to women without a disability (X (2) -16.02 P <0.001). The odds ratio for suffering from diabetes among women with disability compared to women without a disability was 19.3(95% CI: 1.2- 313.9), while it was 9.5 (95% CI: 2.2-40.8) for depression. A higher proportion of women without a disability (7.7%) compared to women with a disability (5.3%) reported a successful pregnancy in the past two years. There were no statistically significant differences between women with and without a disability with regard to utilization of antenatal care and pregnancy outcomes. CONCLUSIONS: The study provides evidence on some reproductive health parameters of women with disability in India for the first time ever. The findings will help in formulating policy and to develop specific interventions to improve pregnancy outcomes for women with disability in India.

Access to health care and employment status of people with disabilities in South India, the SIDE (South India Disability Evidence) study.

BACKGROUND: Data shows that people with disability are more disadvantaged in accessing health, education and employment opportunities compared to people without a disability. There is a lack of credible documented evidence on health care access and barriers to access from India. The South India Disability Evidence (SIDE) Study was undertaken to understand the health needs of people with disabilities, and barriers to accessing health services. METHODS: The study was conducted in one district each in two States (Andhra Pradesh and Karnataka) in 2012. Appropriate age and sex-matched people without a disability were recruited to compare with people with disability who were identified through a population-based survey and available government disability records by trained key informants. These people were then examined by a medical team to confirm the diagnosis. Investigators administered questionnaire schedules to people with and without a disability to harness information on employment and health service access, utilization and barriers. RESULTS: A total of 839 people with disabilities and 1153 age and sex matched people without a disability, aged 18 years or more were included. People with disability had significantly lower employment rates. On univariate analysis, people with disability (18.4%) needed to visit a hospital significantly more often in the preceding year compared to people without a disability (8.8%) (X2- 40.0562; P < =0.001). However adjusted odds ratios did not show a statistically significant difference. Significant differences were also observed with respect to past hospitalization. People with disabilities had 4.6 times higher risk of suffering from diabetes and 5.8 times higher risk of suffering from depression compared to people without a disability and the risk was significantly higher in males compared to females with disability. People with disability faced significantly more barriers to accessing health services compared to people without a disability. Barriers included ignorance regarding availability of services, costs of services and transportation. CONCLUSIONS: This study highlights the challenges that people with disability face in accessing health-care and employment opportunities. The study findings have public health implications and should be used for planning need-based appropriate strategies to improve health care access for people with disabilities.

Flower-like Ag-decked non-stoichiometric Bi2O3-x/rGO hybrid nanocomposite SERS substrates for an effective detection of Rhodamine 6G dye molecules.

In early years, SERS-active substrates were generally noble metals. However, their practical applications were limited due to their poor biocompatibility, low uniformity and high cost. Recently, the utilization of semiconductor SERS-active substrates has greatly expanded the applications of SERS in many fields. However, metal-free SERS-active substrates have a low enhancement factor (EF), which can be overcome by adjusting their oxygen deficiency or through the effective preparation of non-stoichiometric semiconducting oxide materials. This is the key strategy and may work as an efficient and simple way to achieve high sensitivity and obtain an enhancement factor (G-factor) comparable to that of noble metals. Here, we report the preparation of flower-like rGO-Bi2O3/Bi2O2.75 and rGO-Ag-Bi2O3/Bi2O2.75 hybrid thin film nanocomposites using a liquid/liquid interface method (LLI) for the first time. In addition to the synergic effect of different enhancement mechanisms, the 3-D flower-like morphology of the substrate shows more favourable properties to improve the G-factor due to the existence of more hotspots. The rGO-Ag-Bi2O3/Bi2O2.75 hybrid thin-film nanocomposites show an EF of 1.8 × 109 with a detection ability of up to 1 nM towards Rhodamine 6G (R6G), which is highly toxic to humans and the aquatic environment.

Excited state electron transfer from aminopyrene to graphene: a combined experimental and theoretical study.

The quenching of the fluorescence of 1-aminopyrene (1-Ap) by reduced graphene oxide (rGO) has been investigated using spectroscopic techniques. In spite of the upward curvature in the Stern-Volmer plot, the unchanged spectral signature of the absorption of 1-Ap in the presence of rGO and the decrease in fluorescence lifetime with increasing rGO concentration point toward the dynamic nature of the quenching. Detailed analysis of steady state and time-resolved spectroscopic data has shown that the quenching arises due to the photoinduced electron transfer from 1-Ap to rGO. This is again supported by estimating the Gibb's free energy change for the ground as well as excited state electron transfer. Ab initio calculations under the density functional theory (DFT) formalism reveal that the possibility of π-π stacking is very slim in the 1-Ap-rGO system and the electron density resides completely on 1-Ap in the highest occupied molecular orbital (HOMO) and on graphene in the lowest unoccupied molecular orbital (LUMO), supporting the experimental findings of the intermolecular electron transfer between 1-Ap and rGO in the excited state.

Usefulness of The Bethesda System of Reporting Thyroid Cytopathology in Surgical Planning.

The Bethesda system for reporting thyroid cytopathology (TBSRTC) has attempted to standardize thyroid fine needle aspiration cytology (FNAC) reporting internationally into six diagnostic categories and help in clinical decision making. But there exists a significant variation in the reporting percentage and rates of malignancies in each category across the centres which complicates clinical decision making. To study the usefulness of TBSRTC in surgical planning of thyroid nodules and to correlate TBSRTC with final histopathology. 85 patients with thyroid nodules who underwent surgery were evaluated prospectively. Preoperatively FNAC and TBSRTC reporting was done and following surgery histopathology was correlated with cytology. Distribution of 85 patients amongst the six categories of TBSRTC was as follows: 2.35% in Category I, 68.23% II, 7.05% III, 16.47% IV, 2.35% V and 3.52% VI. In 93% (79) of patients TBSRTC correlated with histopathology whereas in 7% (6) it did not. Risk of malignancy calculated was 0% in II, 33.33% in III, 7.14% in IV and 100% in V and VI categories. Sensitivity, specificity, Positive Predictive Value and Negative Predictive Value of TBSRTC was 100% for V, VI categories, whereas it was 100%, 78%, 15% and 100% respectively for III, IV. The diagnostic accuracy in our study is 100% for Category V and VI whereas it is 79% for Category III and IV. TBSRTC proved to be a very good screening platform for triaging patients with thyroid nodules into benign and malignant groups, as it is directly related to risk of malignancy in each category. It has helped in appropriate surgical planning in 96.4% of our patients.

Response to immune checkpoint blockade improved in pre-clinical model of breast cancer after bariatric surgery.

Bariatric surgery is a sustainable weight loss approach, including vertical sleeve gastrectomy (VSG). Obesity exacerbates tumor growth, while diet-induced weight loss impairs progression. It remains unknown how bariatric surgery-induced weight loss impacts cancer progression or alters response to therapy. Using a pre-clinical model of obesity followed by VSG or diet-induced weight loss, breast cancer progression and immune checkpoint blockade therapy were investigated. Weight loss by VSG or weight-matched dietary intervention before tumor engraftment protected against obesity-exacerbated tumor progression. However, VSG was not as effective as diet in reducing tumor burden despite achieving similar weight and adiposity loss. Leptin did not associate with changes in tumor burden; however, circulating IL-6 was elevated in VSG mice. Uniquely, VSG tumors displayed elevated inflammation and immune checkpoint ligand PD-L1+ myeloid and non-immune cells. VSG tumors also had reduced T lymphocytes and markers of cytolysis, suggesting an ineffective anti-tumor microenvironment which prompted investigation of immune checkpoint blockade. While obese mice were resistant to immune checkpoint blockade, anti-PD-L1 potently impaired tumor progression after VSG through improved anti-tumor immunity. Thus, in formerly obese mice, surgical weight loss followed by immunotherapy reduced breast cancer burden. Finally, we compared transcriptomic changes in adipose tissue after bariatric surgery from patients and mouse models. A conserved bariatric surgery-associated weight loss signature (BSAS) was identified which significantly associated with decreased tumor volume. Findings demonstrate conserved impacts of obesity and bariatric surgery-induced weight loss pathways associated with breast cancer progression.

As the number of people classified as obese rises globally, so do obesity-related health risks. Studies show that people diagnosed with obesity have inflammation that contributes to tumor growth and their immune system is worse at detecting cancer cells. But weight loss is not currently used as a strategy for preventing or treating cancer. Surgical procedures for weight loss, also known as 'bariatric surgeries', are becoming increasingly popular. Recent studies have shown that individuals who lose weight after these treatments have a reduced risk of developing tumors. But how bariatric surgery directly impacts cancer progression has not been well studied: does it slow tumor growth or boost the anti-tumor immune response? To answer these questions, Sipe et al. compared breast tumor growth in groups of laboratory mice that were obese due to being fed a high fat diet. The first group of mice lost weight after undergoing a bariatric surgery in which part of their stomach was removed. The second lost the same amount of weight but after receiving a restricted diet, and the third underwent a fake surgery and did not lose any weight. The experiments found that surgical weight loss cuts breast cancer tumor growth in half compared with obese mice. But mice who lost the same amount of weight through dietary restrictions had even less tumor growth than surgically treated mice. The surgically treated mice who lost weight had more inflammation than mice in the two other groups, and had increased amounts of proteins and cells that block the immune response to tumors. Giving the surgically treated mice a drug that enhances the immune system's ability to detect and destroy cancer cells reduced inflammation and helped shrink the mice's tumors. Finally, Sipe et al. identified 54 genes which were turned on or off after bariatric surgery in both mice and humans, 11 of which were linked with tumor size. These findings provide crucial new information about how bariatric surgery can impact cancer progression. Future studies could potentially use the conserved genes identified by Sipe et al. to develop new ways to stimulate the anti-cancer benefits of weight loss without surgery.

Prevalence of cataract in an older population in India: the India study of age-related eye disease.

PURPOSE: To describe the prevalence of cataract in older people in 2 areas of north and south India. DESIGN: Population-based, cross-sectional study. PARTICIPANTS: Randomly sampled villages were enumerated to identify people aged ≥ 60 years. Of 7518 enumerated people, 78% participated in a hospital-based ophthalmic examination. METHODS: The examination included visual acuity measurement, dilatation, and anterior and posterior segment examination. Digital images of the lens were taken and graded by type and severity of opacity using the Lens Opacity Classification System III (LOCS III). MAIN OUTCOME MEASURES: Age- and gender-standardized prevalence of cataract and 95% confidence intervals (CIs). We defined type of cataract based on the LOCS III grade in the worse eye of: ≥ 4 for nuclear cataract, ≥ 3 for cortical cataract, and ≥ 2 for posterior subcapsular cataract (PSC). Any unoperated cataract was based on these criteria or ungradable dense opacities. Any cataract was defined as any unoperated or operated cataract. RESULTS: The prevalence of unoperated cataract in people aged ≥ 60 was 58% in north India (95% CI, 56-60) and 53% (95% CI, 51-55) in south India (P = 0.01). Nuclear cataract was the most common type: 48% (95% CI, 46-50) in north India and 38% (95% CI, 37-40) in south India (P<0.0001); corresponding figures for PSC were 21% (95% CI, 20-23) and 17% (95% CI, 16-19; P = 0.003), respectively, and for cortical cataract 7.6% (95% CI, 7-9) and 10.2% (95% CI, 9-11; P<0.004). Bilateral aphakia/pseudophakia was slightly higher in the south (15.5%) than in the north (13.2%; P<0.03). The prevalence of any cataracts was similar in north (73.8%) and south India (71.8%). The prevalence of unoperated cataract increased with age and was higher in women than men (odds ratio [OR], 1.8). Aphakia/pseudophakia was also more common in women, either unilateral (OR, 1.2; P<0.02) or bilateral (OR, 1.3; P<0.002). CONCLUSIONS: We found high rates of unoperated cataract in older people in north and south India. Posterior subcapsular cataract was more common than in western studies. Women had higher rates of cataract, which was not explained by differential access to surgery.

Inverse association of vitamin C with cataract in older people in India.

OBJECTIVE: To examine the association between vitamin C and cataract in the Indian setting. DESIGN: Population-based cross-sectional analytic study. PARTICIPANTS: A total of 5638 people aged ≥60 years. METHODS: Enumeration of randomly sampled villages in 2 areas of north and south India to identify people aged ≥60 years. Participants were interviewed for socioeconomic and lifestyle factors (tobacco, alcohol, household cooking fuel, work, and diet); attended a clinical examination, including lens photography; and provided a blood sample for antioxidant analysis. Plasma vitamin C was measured using an enzyme-based assay in plasma stabilized with metaphosphoric acid, and other antioxidants were measured by reverse-phase high-pressure liquid chromatography. MAIN OUTCOME MEASURES: Cataract and type of cataract were graded from digital lens images using the Lens Opacity Classification System III (LOCS III), and cataract was classified from the grade in the worse eye of ≥4 for nuclear cataract, ≥3 for cortical cataract, and ≥2 for posterior subcapsular cataract (PSC). Any cataract was defined as any unoperated or operated cataract. RESULTS: Of 7518 enumerated people, 5638 (75%) provided data on vitamin C, antioxidants, and potential confounders. Vitamin C was inversely associated with cataract (adjusted odds ratio [OR] for highest to lowest quartile = 0.61; 95% confidence interval (CI), 0.51-0.74; P=1.1×10(-6)). Inclusion of other antioxidants in the model (lutein, zeaxanthin, retinol, ß-carotene, and α-tocopherol) made only a small attenuation to the result (OR 0.68; 95% CI, 0.57-0.82; P < 0.0001). Similar results were seen with vitamin C by type of cataract: nuclear cataract (adjusted OR 0.66; CI, 0.54-0.80; P < 0.0001), cortical cataract (adjusted OR 0.70; CI, 0.54-0.90; P < 0.002), and PSC (adjusted OR 0.58; CI, 0.45-0.74; P < 0.00003). Lutein, zeaxanthin, and retinol were significantly inversely associated with cataract, but the associations were weaker and not consistently observed by type of cataract. Inverse associations were also observed for dietary vitamin C and cataract. CONCLUSIONS: We found a strong association with vitamin C and cataract in a vitamin C-depleted population. FINANCIAL DISCLOSURE(S): The author(s) have no proprietary or commercial interest in any materials discussed in this article.