Temperature- and Reagent-Controlled Complementary Syn- and Anti-Selective Enolboration-Aldolization of Substituted Phenylacetates.

In contrast to methyl phenylacetates, methyl arylacetates do not provide syn-aldols in the dicyclohexylboron triflate/triethylamine (Chx2BOTf/Et3N)-mediated enolboration-aldolization reaction. However, a combination of a less bulky boron reagent (dibutylboron triflate, n-Bu2BOTf), a bulky amine (i-Pr2NEt), and ambient temperature is required to obtain syn-aldols from methyl arylacetates. The corresponding anti-aldol products have been synthesized by the enolboration-aldolization of methyl arylacetates in the presence of Chx2BOTf/Et3N at a lower temperature. We report the first example of a complementary syn- and anti-selective enolboration-aldolization of arylacetates.

Individual importance of olfaction decreases with duration of smell loss.

BACKGROUND: The personal importance of a lost neurologic - motor or sensory - function in several conditions has been shown to decrease as the afflicted patient becomes accustomed to not having that function. It is unknown how the importance of olfaction changes with duration of olfactory dysfunction (OD). The aim of this study was to evaluate the association between duration of smell loss and individual significance of olfaction, and whether this relationship would be modulated by other factors, such as etiology of smell loss. METHODS: This is a retrospective study including a total 163 subjects with different degrees of olfactory function. Individual significance of olfaction was measured using the Importance of Olfaction Questionnaire (IOQ). Demographics, olfactory function, duration and etiology of OD were evaluated. Group comparisons, bivariate correlations, analyses of variance and multivariate linear regression were applied to detect differences and associations with the outcome measure of IOQ. RESULTS: A significant negative correlation was found between duration of OD and the IOQ. Other important findings include a significantly higher IOQ in patients with posttraumatic- compared to idiopathic OD and in patients with higher aggravation scores compared to the lower aggravation group. Multivariate regression analysis further confirmed that duration of smell loss was independently associated with IOQ. CONCLUSIONS: The duration of smell loss is negatively correlated with the individual importance of olfaction, suggesting that patients develop coping mechanisms for adjusting to OD.

Histopathological Changes in Oral Tissues Induced by Pesticide Poisoning: A Pilot Study.

OBJECTIVE: The present study evaluated the histopathological changes in oral tissues induced by pesticide poisoning. PATIENTS AND METHODS: This was a cross-sectional pilot study. The sample consisted of oral tissues obtained from deceased patients during autopsy. The study samples were obtained from 10 cases of ingested pesticide poisoning, and the control samples were obtained from road traffic accident cases. All the obtained samples were subjected to histopathological examinations. The changes observed in poisoning cases were compared to those in the road traffic accident cases. RESULTS: Significant degenerative changes were observed in the epithelial cells and connective tissue components, such as collagen, muscles, nerves, vasculature, adipose tissue, and salivary acini and ducts, in the poisoning cases. The oral tissues of the road traffic accident cases did not show any significant degenerative changes. CONCLUSION: The degenerative changes in the study samples can be attributed to the direct contact of the pesticide with the autopsied oral tissues when the poison was consumed. There are instances in which the entire body may not be recovered or may not be in an examinable state. In such cases, an oral autopsy could provide additional evidence for determining the cause of death in suspected poison cases.

Retronasal olfactory testing using candies sent by post and for screening purposes: a feasibility study.

BACKGROUND: The olfactory system is able to detect external odours through the orthonasal- and internal odours through the retronasal route. Flavour perception strongly relies on the sense of smell and this back route. In contrast to orthonasal, retronasal olfactory tests (ROT) are less frequently applied, although testing should be recommended for several reasons. The aim of the present investigation was to propose a suitable form of ROT for home-testing (and postal distribution) and evaluate a retronasal screening test. METHODOLOGY: Initially, 111 participants were tested using a 27-item version of the Candy Smell Test (CST). Fifty-four participants performed retesting, of which 25 subjects did so in a home-setting being supplied with professionally packed "candy-chains". Seven candies were chosen by means of hit rate differences in normosmics and severely hyposmics/anosmics. The 7-CST is designed in a non-forced-choice fashion with same seven flavours to choose from. RESULTS: For the 27-item CST both groups (subjects performing home-testing and those performing retesting at the clinic) showed highly significant test-rest-reliabilities. The 7-CST was capable of discriminating healthy from diseased subjects when being tested in 116 healthy subjects and 47 patients suffering from olfactory dysfunction. CONCLUSION: The CST is suitable for home-testing and postal distribution. The new 7-item CST can be valuable for rapidly revealing anosmics. These findings help in further standardizing ROT, may encourage rhinologists to more routinely evaluate retronasal olfactory abilities and pave the way for larger epidemiologic studies also in regard to food preferences and nutritional behaviour.

Application of Climate Assessment Tool (CAT) to Estimate Climate Variability Impacts on Nutrient Loading from Local Watersheds.

A vast amount of future climate scenario datasets, created by climate models such as general circulation models (GCMs), have been used in conjunction with watershed models to project future climate variability impact on hydrological processes and water quality. However, these low spatial-temporal resolution datasets are often difficult to downscale spatially and disaggregate temporarily, and they may not be accurate for local watersheds (i.e., state level or smaller watersheds). This study applied the US-EPA (Environmental Protection Agency)'s Climate Assessment Tool (CAT) to create future climate variability scenarios based on historical measured data for local watersheds. As a case demonstration, CAT was employed in conjunction with HSPF (Hydrological Simulation Program-FORTRAN) model to assess the impacts of the potential future extreme rainfall events and air temperature increases upon nitrate-nitrogen (NO3-N) and orthophosphate (PO4) loads in the Lower Yazoo River Watershed (LYRW), a local watershed in Mississippi, USA. Results showed that the 10 and 20% increases in rainfall rate, respectively, increased NO3-N load by 9.1 and 18% and PO4 load by 12 and 24% over a 10-year simulation period. In contrast, simultaneous increases in air temperature by 1.0 oC and rainfall rate by 10% as well as air temperature by 2.0 oC and rainfall rate by 20% increased NO3-N load by 12% and 20%%, and PO4 load by 14 and 26 %, respectively. A summer extreme rainfall scenario was created if a 10% increase in rainfall rate increased the total volume of rainwater for that summer by 10% or more. When this event occurred, it could increase the monthly loads of NO3-N and PO4, by 31 and 41%, respectively, for that summer. Therefore, the extreme rainfall events had tremendous impacts on the NO3-N and PO4 loads. It is apparent that CAT is a flexible and useful tool to modify historical rainfall and air temperature data to predict climate variability impacts on water quality for local watersheds.

Is robot-assisted radical cystectomy superior to standard open radical cystectomy? An Indian perspective.

INTRODUCTION: Open radical cystectomy (ORC) has been the standard treatment for muscle-invasive bladder cancer, but this is associated with significant morbidity and mortality. Robot-assisted radical cystectomy (RARC) has been proposed as minimally invasive alternative with improved morbidity and acceptable oncological outcomes, but a large series featuring RARC and their comparison with ORC is still lacking in India despite more than a decade of its inception. We have conducted this study with an objective to see the feasibility of RARC in the Indian context and compare it with contemporary standard. METHODS: This is a prospective cohort study conducted at two tertiary cancer institutes. We have evaluated the patients pertaining to operative and early post-operative factors from January 2014 to December 2015. Necessary statistical tests applied to see comparability of the arms and their outcomes. RESULTS: A total of 170 patients underwent surgery for carcinoma bladder (45 ORC while 125 RARC). Intraoperative blood loss (RARC and ORC: 228 and 529 ml) and average transfusion rate were lower with RARC. A trend towards benefit was noted in favour of robotic arm in terms of mean complication rate (RARC and ORC: 54 and 39%). CONCLUSIONS: The present study has shown comparable surgical and early post-operative outcomes with clear advantage of robotic approach in terms of intraoperative blood transfusion and lymph node yield. Although the study was non-randomised in nature, it should provide substantial evidence on safety and feasibility of RARC in the Indian context and a reference point of evidence to look ahead.

Identify temporal trend of air temperature and its impact on forest stream flow in Lower Mississippi River Alluvial Valley using wavelet analysis.

Characterization of stream flow is essential to water resource management, water supply planning, environmental protection, and ecological restoration; while air temperature variation due to climate change can exacerbate stream flow and add instability to the flow. In this study, the wavelet analysis technique was employed to identify temporal trend of air temperature and its impact upon forest stream flows in Lower Mississippi River Alluvial Valley (LMRAV). Four surface water monitoring stations, which locate near the headwater areas with very few land use disturbances and the long-term data records (60-90 years) in the LMRAV, were selected to obtain stream discharge and air temperature data. The wavelet analysis showed that air temperature had an increasing temporal trend around its mean value during the past several decades in the LMRAV, whereas stream flow had a decreasing temporal trend around its average value at the same time period in the same region. Results of this study demonstrated that the climate in the LMRAV did get warmer as time elapsed and the streams were drier as a result of warmer air temperature. This study further revealed that the best way to estimate the temporal trends of air temperature and stream flow was to perform the wavelet transformation around their mean values.

Follicular helper T cells promote liver pathology in mice during Schistosoma japonicum infection.

Following Schistosoma japonicum (S. japonicum) infection, granulomatous responses are induced by parasite eggs trapped in host organs, particular in the liver, during the acute stage of disease. While excessive liver granulomatous responses can lead to more severe fibrosis and circulatory impairment in chronically infected host. However, the exact mechanism of hepatic granuloma formation has remained obscure. In this study, we for the first time showed that follicular helper T (Tfh) cells are recruited to the liver to upregulate hepatic granuloma formation and liver injury in S. japonicum-infected mice, and identified a novel function of macrophages in Tfh cell induction. In addition, our results showed that the generation of Tfh cells driven by macrophages is dependent on cell-cell contact and the level of inducible costimulator ligand (ICOSL) on macrophages which is regulated by CD40-CD40L signaling. Our findings uncovered a previously unappreciated role for Tfh cells in liver pathology caused by S. japonicum infection in mice.

Synthesis and evaluation of duocarmycin SA analogs incorporating the methyl 1,2,8,8a-tetrahydrocyclopropa[c]imidazolo[4,5-e]indol-4-one-6-carboxylate (CImI) alkylation subunit.

The design, synthesis, and evaluation of methyl 1,2,8,8a-tetrahydrocyclopropa[c]imidazolo[4,5-e]indol-4-one-6-carboxylate (CImI) derivatives are detailed representing analogs of duocarmycin SA and yatakemycin containing an imidazole replacement for the fused pyrrole found in the DNA alkylation subunit.

Factors affecting institutional delivery in rural Chitwan district of Nepal: a community-based cross-sectional study.

BACKGROUND: Health facility delivery is considered a critical strategy to improve maternal health. The Government of Nepal is promoting institutional delivery through different incentive programmes and the establishment of birthing centres. This study aimed to identify the socio-demographic, socio-cultural, and health service-related factors influencing institutional delivery uptake in rural areas of Chitwan district, where high rates of institutional deliveries co-exist with a significant proportion of home deliveries. METHODS: This community-based cross-sectional study was conducted in six rural Village Development Committees of Chitwan district, which are characterised by relatively low institutional delivery rates and the availability of birthing centres. The study area represents both hilly and plain areas of Chitwan. A total of 673 mothers who had given birth during a one-year-period were interviewed using a structured questionnaire. Univariate and multivariable logistic regression analysis using stepwise backward elimination was performed to identify key factors affecting institutional delivery. RESULTS: Adjusting for all other factors in the final model, advantaged caste/ethnicity [aOR: 1.98; 95% CI: 1.15-3.42], support for institutional delivery by the husband [aOR: 19.85; 95% CI: 8.53-46.21], the decision on place of delivery taken jointly by women and family members [aOR: 5.43; 95% CI: 2.91-10.16] or by family members alone [aOR: 4.61; 95% CI: 2.56-8.28], birth preparations [aOR: 1.75; 95% CI: 1.04-2.92], complications during the most recent pregnancy/delivery [aOR: 2.88; 95% CI: 1.67-4.98], a perception that skilled health workers are always available [aOR: 2.70; 95% CI: 1.20-6.07] and a birthing facility located within one hour's travelling distance [aOR: 2.15; 95% CI: 1.26-3.69] significantly increased the likelihood of institutional delivery. On the other hand, not knowing about the adequacy of physical facilities significantly decreased the likelihood of institutional delivery [aOR: 0.14; 95% CI: 0.05-0.41]. CONCLUSION: With multiple incentives present, the decision to deliver in a health facility is affected by a complex interplay of socio-demographic, socio-cultural, and health service-related factors. Family decision-making roles and a husband's support for institutional delivery exert a particularly strong influence on the place of delivery, and this should be emphasized in the health policy as well as development and implementation of maternal health programmes in Nepal.

The endoplasmic reticulum stress marker, glucose-regulated protein-78 (GRP78) in visceral adipocytes predicts endometrial cancer progression and patient survival.

OBJECTIVE: Currently, accurately identifying endometrial cancer patients at high risk for recurrence remains poor. To ascertain if changes in the endoplasmic reticulum (ER) stress marker, glucose-regulated-protein-78 (GRP78) can serve as a prognosticator in endometrial cancer, we examined GRP78 expression in patient samples to determine its association with clinical outcome. METHODS: A retrospective cohort study was conducted in endometrial cancer patients. Archived specimens of visceral adipocytes and paired endometrial tumors were analyzed by immunohistochemistry for GRP78 and another ER stress marker, C/EBP homologous protein (CHOP). Expression of these markers was correlated with clinico-pathological information and outcomes. RESULTS: GRP78 expression in visceral adipocytes was detected in 95% of the 179 endometrial cancer patients with analyzable visceral adipocytes. Within individual samples, 24% of adipocytes (range, 0-90%, interquartile range 18%-38%) exhibited GRP78 expression. High visceral adipocyte GRP78 expression positively correlated with advanced-stage disease (p=0.007) and deep myometrial invasion (p=0.004). High visceral adipocyte GRP78 expression was significantly associated with decreased disease-free survival (DFS) in multivariate analyses (hazard ratio 2.88, 95% CI 1.37-6.04, p=0.005). CHOP expression paralleled the GRP78 expression in adipocytes (r=0.55, p<0.001) and in the tumor (p=0.018). CONCLUSIONS: Our study demonstrates that the ER stress markers, GRP78 and CHOP, are elevated in endometrial cancer patients. Furthermore, GRP78 expression levels in visceral adipocytes from these patients were significantly correlated to disease stage and patient survival. Our results demonstrate, for the first time, that the GRP78 levels in endometrial cancer patients may be a prognosticator and aid with clinical risk stratification and focused surveillance.

Mixed ß-pyrrole substituted meso-tetraphenylporphyrins and their metal complexes: optical nonlinearity using degenerate four wave mixing technique.

We have investigated the roles of structural modification and polar effects in the optical nonlinearities of a series of selectively mixed ß-pyrrole functionalized tetraphenylporphyrin, MTPP(CHO)(R)2 (R = H, Br, 2-thienyl, phenyl (Ph), phenylethynyl (PE) compounds and their metal (Cu(II), Zn(II)) complexes in toluene. In the present study, we have used phase conjugation geometry of the four wave mixing process to measure the third order nonlinear susceptibility (χ(3)) and the second order hyperpolarizabilty ((γ)) with picosecond laser pulse excitation at 532 nm. An increase in the values of χ(3) and (γ) for electron-withdrawing groups was observed whereas an opposite trend was noticed for the electron-donating groups at the ß-pyrrole positions. In the Cu(II) and Zn(II) complexes of substituted free base porphyrins, the distortion of the macrocyclic ring may be responsible for the reduction of the values of χ(3) and (γ). From fluorescence measurements, it has been found that the electron-donating and electron-withdrawing substituted groups at ß-pyrrole positions and also the macrocyclic ring distortion of the porphyrin lead to increased radiationless transitions.

Synthesis and Characterization of Naringin Functionalized Nano-Hydroxyapatite for Bone Tissue Engineering.

Bone is a unique nanocomposite tissue composed of organic and inorganic materials. Bone grafting is a common surgical method used to improve bone regeneration in dentistry and orthopedic surgery. Because standard therapies have substantial drawbacks, nanomaterials provide alternative options for bone repair. Owing to its high bioactivity, osteoconductivity, biocompatibility, and topography that matches the architecture of real bone, hydroxyapatite nanoparticles (n-HA) are commonly used in bone treatment. We report here the synthesis and characterization of Naringin (NA) functionalized n-HA using HRTEM, FTIR, XRD, and UV-visible spectroscopy. The obtained results indicated that the n-HA can be functionalized with Naringin and they might be used as a bone regenerative material in medical and dental fields.

Projection of Sediment Loading from Pearl River Basin, Mississippi into Gulf of Mexico under a Future Climate with Afforestation.

Sediment load in rivers is recognized as both a carrier and a potential source of contaminants. Sediment deposition significantly changes river flow and morphology, thereby affecting stream hydrology and aquatic life. We projected sediment load from the Pearl River basin (PRB), Mississippi into the northern Gulf of Mexico under a future climate with afforestation using the SWAT (Soil and Water Assessment Tool)-based HAWQS (Hydrologic and Water Quality System) model. Three simulation scenarios were developed in this study: (1) the past scenario for estimating the 40-year sediment load from 1981 to 2020; (2) the future scenario for projecting the 40-year sediment load from 2025 to 2064, and (3) the future afforestation scenario that was the same as the future scenario, except for converting the rangeland located in the middle section of the Pearl River watershed of the PRB into the mixed forest land cover. Simulations showed a 16% decrease in sediment load for the future scenario in comparison to the past scenario due to the decrease in future surface runoff. Over both the past and future 40 years, the monthly maximum and minimum sediment loads occurred, respectively, in April and August; whereas the seasonal sediment load followed the order: spring > winter > summer > fall. Among the four seasons, winter and spring accounted for about 86% of sediment load for both scenarios. Under the future 40-year climate conditions, a 10% reduction in annual average sediment load with afforestation was observed in comparison to without afforestation. This study provides new insights into how a future climate with afforestation would affect sediment load into the northern Gulf of Mexico.

Carbon Dot-NaCl Crystals for White-Light Generation and Fabry-Perot Lasing.

Phosphor materials with broad spectral range and an average emission lifetime (20 µs) have been achieved from carbon dots (CDs)-NaCl crystals. A one-pot synthesis pathway has been developed for CDs-NaCl crystals formation at room temperature. Precursor for CDs materials was screened at room temperature by oxidation methodology from different simple sugar molecules. CDs (size less than 10 nm) prepared from the fructose sugar exhibit most intense emission. Utilizing ripe banana peel (contains ∼27% of fructose) as a precursor for the carbon dot formation, white-light emission with a CIE index of (0.29, 0.34) has been achieved from the single source with CDs-NaCl crystals upon excitation at 430 nm. The crystals also function as Fabry-Perot (F-P) mode resonator for lasing, with a laser threshold value of 0.9 mW and a resonating Q-factor of 207. These results outline a new approach for realizing F-P lasing and white light emission from a non-toxic green source with a quick, facile and low-cost synthesis procedure.

Reprogramming natural proteins using unnatural amino acids.

Unnatural amino acids have gained significant attention in protein engineering and drug discovery as they allow the evolution of proteins with enhanced stability and activity. The incorporation of unnatural amino acids into proteins offers a rational approach to engineer enzymes for designing efficient biocatalysts that exhibit versatile physicochemical properties and biological functions. This review highlights the biological and synthetic routes of unnatural amino acids to yield a modified protein with altered functionality and their incorporation methods. Unnatural amino acids offer a wide array of applications such as antibody-drug conjugates, probes for change in protein conformation and structure-activity relationships, peptide-based imaging, antimicrobial activities, etc. Besides their emerging applications in fundamental and applied science, systemic research is necessary to explore unnatural amino acids with novel side chains that can address the limitations of natural amino acids.

Coupling Pressure Sensing with Optical Coherence Tomography to Evaluate the Internal Nasal Valve.

PURPOSE: To evaluate endoscopic long-range optical coherence tomography system combined with a pressure sensor to concurrently measure internal nasal valve cross-sectional area and intraluminal pressure. METHODS: A pressure sensor was constructed using an Arduino platform and calibrated using a limiter-controlled vacuum system and industrial absolute pressure gauge. Long-range optical coherence tomography imaging and pressure transduction were performed concurrently in the naris of eight healthy adult subjects during normal respiration and forced inspiration. The internal nasal valve was manually segmented using Mimics software and cross-sectional area was measured. Internal nasal valve cross-sectional area measurements were correlated with pressure recordings. RESULTS: Mean cross-sectional area during forced inspiration was 6.49 mm2. The mean change in pressure between normal respiration and forceful inspiration was 12.27 mmHg. The direct correlation between pressure and cross-sectional area as measured by our proposed system was reproducible among subjects. CONCLUSIONS: Our results demonstrate a direct correlation between internal nasal valve cross-sectional area and nasal airflow during inspiration cycles. Endoscopic long-range optical coherence tomography coupled with a pressure sensor serves as a useful tool to quantify the dynamic behavior of the internal nasal valve.

Gingival Fenestration Management: A Rarefied Case Entity and Literature Review.

Dehiscence and fenestration are commonly confronted alveolar defects. But the combined mucosal and alveolar fenestration is uncommonly reported in the literature as they less often cause pain, and in majority of the cases, only aesthetic complaint is present. This article highlights the case report of a 28-year-old female patient who presented with aesthetic concern about gingival/mucosal fenestration in her right lower central incisor. She had a history of surgical endodontic treatment in the same tooth. In this case, mucosal fenestration was treated with regenerative therapy using bioactive glass with platelet-rich fibrin and free connective tissue graft. The treatment resulted in excellent aesthetic outcome and satisfactory bone healing.