Nonparametric recursive estimation of the derivative of the regression function with application to sea shores water quality

This paper is devoted to the nonparametric estimation of the derivative of the regression function in a nonparametric regression model. We implement a very efficient and easy to handle statistical procedure based on the derivative of the recursive Nadaraya–Watson estimator. We establish the almost sure convergence as well as the asymptotic normality for our estimates. We also illustrate our nonparametric estimation procedure on simulated data and real life data associated with sea shores water quality and valvometry.

     

A [4 + 4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes

A [4+4] annulation strategy for the synthesis of eight-membered carbocycles is reported that proceeds via a cascade involving two pericyclic processes. In the first step, the [4+2] cycloaddition of a conjugated enyne with an electron-deficient cyclobutene generates a strained six-membered cyclic allene that isomerizes to the corresponding 1,3-cyclohexadiene. In the second step, this bicyclo[4.2.0]octa-2,4-diene intermediate undergoes thermal or acid-promoted 6-electron electrocyclic ring opening to furnish a 2,4,6-cyclooctatrienone. The latter transformation represents the first example of the promotion of 6-electron electrocyclic ring opening reactions by acid.     

EDXRF,FTIR, and XRD characterization of low calcium oxalate urinary stones collected from arid area

Low calcium oxalate urinary stones from the kidney, bladder, and ureter have been collected from the arid area (Taif, Saudi Arabia). After careful washing and drying of the collected stones, the samples were converted into a contamination-free homogenous fine powder with a particles' size smaller than 50 μm. The processed urinary stone powders were studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), laboratory setup and synchrotron radiation X-ray diffraction (XRD), and energy-dispersive X-ray fluorescence (EDXRF). The activated function groups, quantitative phase analysis, and the semi-quantitative elemental analysis of the present urinary stones were identified. Seventeen elements were measured in most of the urinary stone samples. The significant elements are Ca, P, S, Cl, Zn, K, Fe, and Cu, whereas other elements were found alternatively in a few number of urinary stone samples. It was recognized that Ca exists with low concentration, which indicates the presence of different calcium phases even with low percentages. In 33% of the urinary stones, the phosphorus (P) was not measured, but there were high concentrations of sulfur (S) and low concentrations of Ca up to 2.15 ± 0.05%. The ATR-FTIR results indicate that the most compounds of the present urinary stones were urea and cystine combined with low ratios of calcium oxalate and calcium phosphate compounds. The quantitative phase analysis of the XRD of selected samples proves the presence of the cystine, urea, and calcium oxalate phases with different weight percent.     

Phantom and non-phantom dark energy: The cosmological relevance of non-locally corrected gravity

In this Letter we have investigated the cosmological dynamics of non-locally corrected gravity involving a function of the inverse d'Alembertian of the Ricci scalar, f(^□−1R)$f({\square }^{\mathrm{-1}}R)$. Casting the dynamical equations into local form, we derive the fixed points of the dynamics and demonstrate the existence and stability of a one parameter family of dark energy solutions for a simple choice, f(^□−1R)∼exp(α^□−1R)$f({\square }^{\mathrm{-1}}R)\sim \exp (\alpha {\square }^{\mathrm{-1}}R)$. The effective EoS parameter is given by, weff=(α−1)/(3α−1)$w_{\mathrm{eff}}=(\alpha -1)/(3\alpha -1)$ and the stability of the solutions is guaranteed provided that 1/3<α<2/3$1/3<\alpha <2/3$. For 1/3<α<1/2$1/3<\alpha <1/2$ and 1/2<α<2/3$1/2<\alpha <2/3$, the underlying system exhibits phantom and non-phantom behavior respectively; the de Sitter solution corresponds to α=1/2$\alpha =1/2$. For a wide range of initial conditions, the system mimics dust like behavior before reaching the stable fixed point. The late time phantom phase is achieved without involving negative kinetic energy fields. A brief discussion on the entropy of de Sitter space in non-local model is included.     

Quantitative two-dimensional HSQC experiment for high magnetic field NMR spectrometers

The finite RF power available on carbon channel in proton–carbon correlation experiments leads to non-uniform cross peak intensity response across carbon chemical shift range. Several classes of broadband pulses are available that alleviate this problem. Adiabatic pulses provide an excellent magnetization inversion over a large bandwidth, and very recently, novel phase-modulated pulses have been proposed that perform 90° and 180° magnetization rotations with good offset tolerance. Here, we present a study how these broadband pulses (adiabatic and phase-modulated) can improve quantitative application of the heteronuclear single quantum coherence (HSQC) experiment on high magnetic field strength NMR spectrometers. Theoretical and experimental examinations of the quantitative, offset-compensated, CPMG-adjusted HSQC (Q-OCCAHSQC) experiment are presented. The proposed experiment offers a formidable improvement to the offset performance; ¹³C offset-dependent standard deviation of the peak intensity was below 6% in range of ±20 kHz. This covers the carbon chemical shift range of 150 ppm, which contains the protonated carbons excluding the aldehydes, for 22.3 T NMR magnets. A demonstration of the quantitative analysis of a fasting blood plasma sample obtained from a healthy volunteer is given.     

The thawing dark energy dynamics: Can we detect it?

We consider different classes of scalar field models including quintessence and tachyon scalar fields with a variety of generic potentials belonging to the thawing type. We focus on observational quantities like Hubble parameter, luminosity distance as well as quantities related to the Baryon Acoustic Oscillation measurement. Our study shows that with present state of observations, one cannot distinguish amongst various models which in turn cannot be distinguished from cosmological constant. Our analysis indicates that there is a small chance to observe the dark energy metamorphosis in near future.     

Structural,M?ssbauer spectroscopy,magnetic properties,and thermal measurements of Y(3-x)Dy_x Fe_5O_(12)

Yttrium iron garnet powder samples((3-x)Dy_x Fe_5O_(12)), where part of yttrium ions are substituted by dysprosium ions with different concentrations are prepared by the solid state reaction method. The properties of the prepared samples are examined by different methods such as x-ray diffraction(XRD), Mssbauer spectroscopy, macroscopic magnetization measurements, and thermal measurements. The XRD measurements show that all the samples reveal the presence of a single garnet phase with a BCC structure. Room temperature Mssbauer spectra indicate that iron ions occupy three magnetic sites, i.e., two octahedral sites and one tetrahedral site. The saturation magnetization and the initial magnetic susceptibility decrease with the increase of Dy~(3+) substitution. The Curie temperature obtained from the thermal measurements seems to be independent of Dy~(3+) substitution.     

Biodegradable Nanoparticles Loaded with Levodopa and Curcumin for Treatment of Parkinson’s Disease

Background: Parkinson’s disease (PD) is the second most common age-related neurodegenerative disorder. Levodopa (L-DOPA) remains the gold-standard drug available for treating PD. Curcumin has many pharmacological activities, including antioxidant, anti-inflammatory, antimicrobial, anti-amyloid, and antitumor properties. Copolymers composed of Poly (ethylene oxide) (PEO) and biodegradable polyesters such as Poly (ε-caprolactone) (PCL) can self-assemble into nanoparticles (NPs). This study describes the development of NH₂–PEO–PCL diblock copolymer positively charged and modified by adding glutathione (GSH) on the outer surface, resulting in a synergistic delivery of L-DOPA curcumin that would be able to pass the blood–brain barrier. Methods: The NH₂–PEO–PCL NPs suspensions were prepared by using a nanoprecipitation and solvent displacement method and coated with GSH. NPs were submitted to characterization assays. In order to ensure the bioavailability, Vero and PC12 cells were treated with various concentrations of the loaded and unloaded NPs to observe cytotoxicity. Results: NPs have successfully loaded L-DOPA and curcumin and were stable after freeze-drying, indicating advancing into in vitro toxicity testing. Vero and PC12 cells that were treated up to 72 h with various concentrations of L-DOPA and curcumin-loaded NP maintained high viability percentage, indicating that the NPs are biocompatible. Conclusions: NPs consisting of NH₂–PEO–PCL were characterized as potential formulations for brain delivery of L-DOPA and curcumin. The results also indicate that the developed biodegradable nanomicelles that were blood compatible presented low cytotoxicity.     

Analytical Performance and Greenness Evaluation of Five Multi-Level Design Models Utilized for Impurity Profiling of Favipiravir,a Promising COVID-19 Antiviral Drug

In 2018, the discovery of carcinogenic nitrosamine process related impurities (PRIs) in a group of widely used drugs led to the recall and complete withdrawal of several medications that were consumed for a long time, unaware of the presence of these genotoxic PRIs. Since then, PRIs that arise during the manufacturing process of the active pharmaceutical ingredients (APIs), together with their degradation impurities, have gained the attention of analytical chemistry researchers. In 2020, favipiravir (FVR) was found to have an effective antiviral activity against the SARS-COVID-19 virus. Therefore, it was included in the COVID-19 treatment protocols and was consequently globally manufactured at large-scales during the pandemic. There is information indigence about FVR impurity profiling, and until now, no method has been reported for the simultaneous determination of FVR together with its PRIs. In this study, five advanced multi-level design models were developed and validated for the simultaneous determination of FVR and two PRIs, namely; (6-chloro-3-hydroxypyrazine-2-carboxamide) and (3,6-dichloro-pyrazine-2-carbonitrile). The five developed models were classical least square (CLS), principal component regression (PCR), partial least squares (PLS), genetic algorithm-partial least squares (GA-PLS), and artificial neural networks (ANN). Five concentration levels of each compound, chosen according to the linearity range of the target analytes, were used to construct a five-level, three-factor chemometric design, giving rise to twenty-five mixtures. The models resolved the strong spectral overlap in the UV-spectra of the FVR and its PRIs. The PCR and PLS models exhibited the best performances, while PLS proved the highest sensitivity relative to the other models.     

Characterization of Volatile Flavor Compounds in Supercritical Fluid Separated and Identified in Gurum (Citrulluslanatus Var. colocynthoide) Seed Oil Using HSME and GC–MS

In this study, the volatile compound profiles of gurum seed oil were determined using two methods: supercritical CO₂ extraction (SFE) and the screw press process (SPP). For volatile compounds extraction and identification, headspace solid-phase micro-extraction (HS-SPME) and GC–MS were used, respectively. A total number of 56 volatile compounds were revealed and identified in oil extracted by SFE, while only 40 compounds were detected in extracted oil by SPP. Acids, aldehydes, esters, ketones, furans, and other components were present in the highest ratio in oil extracted by SFE. In contrast, alcohols and alkenes were found in the highest proportion in oil extracted by SPP. In this study, it was observed that SFE showed an increase in the amounts of volatile compounds and favorably impacted the aroma of gurum seed oil. The results reveal that different extraction methods significantly impact the volatile components of gurum seed oil, and this study can help evaluate the quality of the oil extracted from gurum seeds.