Total Reflection Research Articles

Arrays of Bowl-Shaped Janus Particle Film with Structured Colors.

Structural colors generated via total internal reflection (TIR) using nanostructure-free micro-concave shapes have garnered increasing attention. However, the application of large micro-concave structures for structural coloration remains limited. Herein, a flexibly tunable structural color film fabricated by casting polydimethylsiloxane (PDMS) on an array of large poly(glycidyl methacrylate) (PGMA) bowl-shaped particles is reported. The resultant film exhibits tunable red to green structural colors with changing observation angles. Moreover, the color can be further tailored by altering the shape of the film itself. The incorporation of the PDMS layer not only facilitates a shift in the locus of TIR from the bottom surface to the top concave surface of the particles, thereby enabling the generation of structural color, but also confers enhanced flexibility to the film. Further decoration with silver nanoparticles imparts antimicrobial properties, yielding a novel antimicrobial coating material with structural colors. The simple and cost-effective strategy for the production of structural color films provides potential applications in antimicrobial coatings, enabling accessible and customizable structural coloration using big-size micro-concave particles.

IL-1β Induces LDL Transcytosis by a Novel Pathway Involving LDLR and Rab27a.

In early atherosclerosis, circulating LDLs (low-density lipoproteins) traverse individual endothelial cells by an active process termed transcytosis. The CANTOS trial treated advanced atherosclerosis using a blocking antibody for IL-1β (interleukin-1β); this significantly reduced cardiovascular events. However, whether IL-1β regulates early disease, particularly LDL transcytosis, remains unknown. We used total internal reflection fluorescence microscopy to quantify transcytosis by human coronary artery endothelial cells exposed to IL-1β. To investigate transcytosis in vivo, we injected wild-type and knockout mice with IL-1β and LDL to visualize acute LDL deposition in the aortic arch. Exposure to picomolar concentrations of IL-1β induced transcytosis of LDL but not of albumin by human coronary artery endothelial cells. Surprisingly, expression of the 2 known receptors for LDL transcytosis, ALK-1 (activin receptor-like kinase-1) and SR-BI (scavenger receptor BI), was unchanged or decreased. Instead, IL-1β increased the expression of the LDLR (LDL receptor); this was unexpected because LDLR is not required for LDL transcytosis. Overexpression of LDLR had no effect on basal LDL transcytosis. However, knockdown of LDLR abrogated the effect of IL-1β on transcytosis rates while the depletion of Cav-1 (caveolin-1) did not. Since LDLR was necessary but overexpression had no effect, we reasoned that another player must be involved. Using public RNAseq data to curate a list of Rab GTPases affected by IL-1β, we identified Rab27a. Overexpression of Rab27a alone had no effect on basal transcytosis, but its knockdown prevented induction by IL-1β. This was phenocopied by depletion of the Rab27a effector JFC1. In vivo, IL-1β increased LDL transcytosis in the aortic arch of wild-type but not Ldlr-/- or Rab27a-deficient mice. The JFC1 inhibitor nexinhib20 also blocked IL-1β-induced LDL accumulation in the aorta. IL-1β induces LDL transcytosis by a distinct pathway requiring LDLR and Rab27a; this route differs from basal transcytosis. We speculate that induction of transcytosis by IL-1β may contribute to the acceleration of early disease.

A high-sensitivity lab-on-a-chip analyzer for online monitoring of nitrite and nitrate in seawater based on liquid waveguide capillary cells.

Optical detection is an indispensable part of microfluidic systems for nutrient determination in seawater. Coupling total internal reflection capillaries with microfluidic chips is a practical alternative to increase the optical path length for high-sensitivity and a low detection limit in colorimetric assays, which has not been applied in microfluidic devices for seawater nutrients. Here, we present an online microfluidic system which integrated a total internal reflection capillary made of Teflon AF 2400 for the high-sensitivity detection of nitrite and nitrate in seawater. The off-chip capillary lengthens the optical path without changing the internal flow path of the microfluidic chip, enhancing the sensitivity, reducing the detection limit and widening the dynamic range of the system, which significantly improves the performance of the microfluidic system based on wet-chemistry. The detection limit for nitrite is 0.0150 μM using an external 20 cm capillary and 0.0936 μM using an internal 5 cm absorption cell, providing an over 6-fold improvement. Laboratory analysis of surface seawater samples collected from the South China Sea with this system and a one-month online deployment of an autonomous analyzer developed based on this system at a station revealed correlations between the nitrite and nitrate with tide, salinity and chlorophyll over slight variations and narrow ranges, demonstrating the high-sensitivity of this method.

Correlative single-molecule and structured illumination microscopy of fast dynamics at the plasma membrane

Total internal reflection fluorescence (TIRF) microscopy offers powerful means to uncover the functional organization of proteins in the plasma membrane with very high spatial and temporal resolution. Traditional TIRF illumination, however, shows a Gaussian intensity profile, which is typically deteriorated by overlaying interference fringes hampering precise quantification of intensities—an important requisite for quantitative analyses in single-molecule localization microscopy (SMLM). Here, we combine flat-field illumination by using a standard πShaper with multi-angular TIR illumination by incorporating a spatial light modulator compatible with fast super-resolution structured illumination microscopy (SIM). This distinct combination enables quantitative multi-color SMLM with a highly homogenous illumination. By using a dual camera setup with optimized image splitting optics, we achieve a versatile combination of SMLM and SIM with up to three channels. We deploy this setup for establishing robust detection of receptor stoichiometries based on single-molecule intensity analysis and single-molecule Förster resonance energy transfer (smFRET). Homogeneous illumination furthermore enables long-term tracking and localization microscopy (TALM) of cell surface receptors identifying spatial heterogeneity of mobility and accessibility in the plasma membrane. By combination of TALM and SIM, spatially and molecularly heterogenous diffusion properties can be correlated with nanoscale cytoskeletal organization and dynamics.

Insulin-Mimetic Activity of Herbal Extracts Identified with Large-Scale Total Internal Reflection Fluorescence Microscopy

Diabetes mellitus is a spreading global pandemic. Type 2 diabetes mellitus (T2DM) is the predominant form of diabetes, in which a reduction in blood glucose uptake is caused by impaired glucose transporter 4 (GLUT4) translocation to the plasma membrane in adipose and muscle cells. Antihyperglycemic drugs play a pivotal role in ameliorating diabetes symptoms but often are associated with side effects. Hence, novel antidiabetic compounds and nutraceutical candidates are urgently needed. Phytogenic therapy can support the prevention and amelioration of impaired glucose homeostasis. Using total internal reflection fluorescence microscopy (TIRFM), 772 plant extracts of an open-access plant extract library were screened for their GLUT4 translocation activation potential, resulting in 9% positive hits. Based on commercial interest and TIRFM assay-based GLUT4 translocation activation, some of these extracts were selected, and their blood glucose-reducing effects in ovo were investigated using a modified hen’s egg test (Gluc-HET). To identify the active plant part, some of the available candidate plants were prepared in-house from blossoms, leaves, stems, or roots and tested. Acacia catechu (catechu), Pulmonaria officinalis (lungwort), Mentha spicata (spearmint), and Saponaria officinalis (common soapwort) revealed their potentials as antidiabetic nutraceuticals, with common soapwort containing GLUT4 translocation-activating saponarin.

Stimulating Electron Delocalization of Lanthanide Elements through High-Entropy Confinement to Promote Electrocatalytic Water Splitting.

High-entropy alloys (HEAs) have aroused extensive attention in the field of catalysis. However, due to the integration of multiple active sites in HEA, it exhibits excessive adsorption behavior resulting in difficult desorption of active species from the catalyst surfaces, which hinders the catalytic efficiency. Therefore, adjusting the adsorption strength of the active site in HEA to enhance the catalytic activity is of great importance. By introducing rare-earth (RE) elements into the high-entropy alloy, the delocalization of 4f electrons can be achieved through the interaction between the multimetal active site and RE, which benefits to regulate the adsorption strength of the HEA surface. Herein, the RE Ce-modified hexagonal-close-packed PtRuFeCoNiZn-Ce/C HEAs are synthesized and showed an excellent electrocatalytic activity for hydrogen evolution reaction and oxygen evolution reaction with ultralow overpotentials of 4, 7 and 156, 132 mV, respectively, to reach 10 mA cm-2 in 0.5 M H2SO4 and 1.0 M KOH solutions, and the assembled water electrolysis cell only requires a voltage of 1.43 V to reach 10 mA cm-2, which is much better than the performance of PtRuFeCoNiZn/C. Combined with the results of in situ attenuated total reflection infrared spectroscopy and density functional theory (DFT), the fundamental reasons for the improvement of catalyst activity come from two aspects: (i) local lattice distortion of HEA caused by the introduction of RE with large atomic radius induces 4f orbital electron delocalization of RE elements and enhances electron exchange between RE and active sites. (ii) The electronegativity difference between the RE element and the active site forms a surface dipole in HEA, which optimizes the adsorption of the active intermediate by the HEA surface site. This study provides an insightful idea for the rational design of high-performance HEA- and RE-based electrocatalysts.

Machine learning‐enabled two‐port wideband MIMO hybrid rectangular dielectric resonator antenna for n261 5G NR millimeter wave

SummaryIn this article, a two‐port multiple‐input multiple‐output (MIMO) hybrid rectangular dielectric resonator antenna (DRA) with machine learning (ML) approach for the n261 5G New Radio (NR) application is presented. The proposed antenna is designed on an RT/duroid 5880 (Ɛr = 2.2) substrate activated by 50 Ω, L‐shaped microstrip slot feeds beneath both DRAs. The isolation is more than 19 dB, and the gain is 10 dBi in the operating frequency range. The proposed antenna is optimized through knowledge‐based neural networks (KBNN), artificial neural networks (ANNs), and ML. The optimal design parameters of the proposed antenna are accomplished using the ML optimization approach, which includes ridge regression, ANNs, and KBNN. KBNN ML techniques provide 96.88% accuracy and correctly predict the S‐parameters of the proposed antenna. The MIMO diversity parameters like envelope correlation coefficient (ECC), diversity gain (DG), total active reflection coefficient (TARC), and channel capacity loss (CCL) are calculated and found within the limits. Hence, the proposed antenna is used for 5G NR mm‐wave application.

Position Matters: Pyridine Regioisomers Influence Secondary Structure and Micelle Morphology in Polymer-Homopolypeptide Micelles.

Polymer-homopolypeptide block copolymers are a class of bioinspired materials that combine the processability and stability of synthetic polymers with the biocompatibility and unique secondary structures of peptides, such as α-helices and β-sheets. These properties make them ideal candidates for a wide variety of applications, for example, in the pharmaceutical field, where they are frequently explored as building blocks for polymeric micelle drug delivery systems. While homopolypeptide side chains can be furnished with an array of different moieties to impart the copolymers with desirable properties, such as stimulus responsivity, pyridine derivatives represent an underutilized functional group for this purpose. Additionally, the interplay between polypeptide side chain structure, secondary conformation, and micelle morphology is not yet well understood, particularly in the case of structural regioisomers. Therefore, in this work, a series of polymer-homopolypeptide copolymers were prepared from a poly(ethylene glycol)-b-poly(glutamic acid) (PEG-b-PGA) backbone, where the pendant carboxylic acid groups were covalently conjugated to a series of pyridine regioisomers by carbodiimide coupling. These pyridine regioisomers differed only in the position of the nitrogen heteroatom, ortho, meta or para, relative to the linking group, generating a series of PEG-b-poly(pyridinylmethyl glutamate) (PEG-b-PMG) copolymers. Following self-assembly of the copolymers in aqueous solutions, dynamic light scattering (DLS) revealed differences in micelle hydrodynamic diameter (Dh) (ranging from ∼60 to 120 nm), while transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) revealed distinctive morphologies ranging from ellipsoidal, to cylindrical, and disc-like, suggesting that subtle changes in positional isomers in the polypeptide block may influence the micelle structure. Analysis of the PEG-b-PMG copolymer micelles by circular dichroism (CD) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy revealed that differences in the morphology were associated with changes in polypeptide secondary structure, which in turn was influenced by the position of the pyridine heteroatom. Overall, these findings contribute to the broader understanding of the relationship between polypeptide structure and micelle morphology and serve as useful insight for the rational design of polymer-polypeptide nanoparticles.

Study of novel Zn-MOF-II modified polymeric membrane in wastewater treatment containing oily waste and humic acid (NOM)

ABSTRACT The prime objective of the present work was to synthesise the polymeric membrane with Zn-MOF-II nanoparticles using the phase inversion method to purify oily wastewater and NOM. The dead-end filtration system was utilised to analyse the performance of fabricated membranes (without and with Zn-MOF-II), various feeds of 100 ppm concentration used, such as organic pollutants and oil effluent at 250 kPa and atmospheric temperature conditions. The following study involves the compaction factor, pure water flux, all mixed matrix membrane permeability, humic acid rejection, and oil–water emulsion rejection, contact angle, and liquid–liquid displacement porosimetry (LLDP). Scanning electron microscopy (SEM) and Fourier transforms infrared spectroscopy-attenuated total reflection (FTIR-ATR) goniometer were used to characterise the polymeric membranes. The FTIR-ATR spectra of the modified membrane exhibit a characteristic peak between 2,900 and 3,000 cm−1 associated with the presence of the –COOH group. The nanoparticles and polymer matrix were well compatible, as evidenced by SEM images of the polymeric membrane containing Zn-MOF-II nanoparticles. The maximum value of percentage rejection of oily wastewater (above 88.89%) and humic acid (above 86.88%) was obtained for the polymeric membrane containing Zn-MOF-II nanoparticles.

Nanoparticle Uptake and Bioaccumulation in Pisum sativum L. (Green Pea) Analyzed via Dark-Field Microscopy, Infrared Spectroscopy, and Principal Component Analysis Combined with Machine Learning

The green pea (Pisum sativum L.) is an economically, nutritionally, and culturally important legume. It is a crop that is subject to various investigations due to its popularity with the development of various protocols in different topics, except for nano-biotechnological studies. This work was carried out to evaluate the uptake, distribution, translocation, and bioaccumulation of the single-walled carbon nanotubes (CNTs) and gold nanoparticles (AuNPs) within the economically important plant Pisum sativum morphologically and anatomically with a dark-field microscopy system. Data were analyzed for morphological parameters such as stem, tendril, root length, number, shape, width-length of the stipules, and root-stem-stipule. Our results proved the stimulation for growth and anatomical parameters such as CNTs aggregates and AuNPs particles at paranchyma, cortex, spongia cells, starch formation and accumulation in lenticels, stoma cells, and stomatal pores. In this study, we compared the utilization of the entire available Attenuated Total Reflectance—Fourier Transform Infrared Spectroscopy (ATR-FTIR) spectral range (525–4000 cm−1) for conducting principal component analysis (PCA) without excluding any specific spectral wavenumbers with the spectral range chosen based on larger PCA loadings. The results demonstrate that for both chosen spectral ranges of the PCA score plots, utilizing only the first three principal components (PCs), we effectively visually separated three groups: (1) plants treated with Au NPs, (2) plants treated with CNTs, and (3) control plants without nanoparticle treatment using ATR-FTIR spectral data from combined samples of root, stem, and leaves from the Pisum sativum plant. Our investigation shows that green pea, a species of the Fabaceae family, is low-cost, fast, and non-toxic and requires an environmentally safe process in the area of nanotechnology in bio-application regarding the green synthesis of nanoparticles; it is a step for green mining, phytoremediation, delivering drugs, and biomolecules. Our findings show that green pea and the Fabaceae family have more advantages for the biological synthesis of C-Au nanoparticles and guide soil health, agricultural development, pharmaceuticals, drug delivery science, and other types of medicinal investigations with a new approach, while a lot of economic plants in the Fabaceae family will be available for the green synthesis of more NPs with single and rapid protocols and will be a popular family in nano-biotechnological studies in the next few decades.

Design of colon-targeted drug delivery of dexamethasone: Formulation and in vitro characterization of solid dispersions

Colon-targeted drug delivery continues to generate increasing attention for its prospects in treating inflammatory bowel disease (IBD). This study aimed to develop and evaluate colon-targeted solid dispersions of dexamethasone (DEX-SDs) in vitro to reduce its systemic exposure. This would ultimately improve the therapeutic efficacy of DEX while minimizing its adverse effects. Different DEX-SDs formulations were prepared utilizing Eudragit S100 (EU S100) and a combination of hydroxypropyl methyl cellulose (HPMC) and EU S100 to tune its drug release profile suitable for colonic delivery. The fabricated formulations were extensively characterized via Attenuated Total Reflectance – Fourier Transform Infrared Spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and polarized light microscopy (PLM). The different characterization techniques strongly suggest preparing solid solution-type solid dispersions of DEX with the other polymers (DEX-SDs). In addition, the in vitro dissolution of DEX-SDs was evaluated using two dissolution media (pH 1.2 and 7.4). The in vitro release of DEX-SDs was low in the acidic media and higher and sustained in the basic medium, leading to the conclusion that the developed DEX-SDs may represent an effective technology can overcome challenges related to poor drug solubility and bioavailability.

Femtosecond laser darkened copper surfaces: Characterization for possible application as laser beam blocker

This study focuses on the optical and mechanical properties of copper surfaces darkened by femtosecond laser irradiation, with regard to their applicability as laser beam blockers. Copper surfaces were processed with a Ti-Sapphire laser (1 kHz repetition rate, ∼100–600 mJ/cm2 fluence), while scanning parameters were optimized for low reflectivity and processing speed. A total reflectivity below 6 % was obtained for the 250–2500 nm wavelength range. SEM imaging and ion beam etching showed submicron period structures covered with high density nanoparticles, with a total depth of ∼3–4 μm. Numerical reflectivity simulations suggest that besides the structures, the formation of oxides also contributes to the observed darkening. Thermal and mechanical stability, chemical resistance and laser damage threshold were studied. Temperatures above 200 °C caused surface degradation. Scratch tests showed that the nanostructured layers could withstand ∼60 MPa contact pressure. The surfaces could resist 48 h treatment with various acids at 10−3 M concentration. The laser damage threshold for the applied femtosecond laser showed that the surface could withstand the unfocused beam of most high-frequency femtosecond lasers. The results indicate that laser darkened copper can be a promising candidate for use in laser beam blockers.

High-performance Chinese ink flower-shaped evaporator: Intensified heat through light concentration to achieve water-energy balance

Maintaining a water-energy balance is crucial for maximizing efficiency in 3D interfacial solar-driven evaporation. Regrettably, the inherent flaw of 3D evaporators results in insufficient water supply capacity. Herein, taking inspiration from metals that can reflect light, aluminum foil (AF) was utilized to create a light-collecting device with internal reflection capabilities. A 3D sola flower (SF) evaporator with Chinese ink absorption coating and PDA surface hydrophilic treatment (IPSF) was designed. The experimental and simulated results show that by applying surface hydrophilic treatment and using a light-collecting device, a notable increase in temperature on the side of the 3D evaporator is visible, indicating the successful implementation of the spotlight effect. Therefore, it is possible to achieve a water-energy balance and attain a high evaporation rate. The evaporation rate of IPSF was 2.31 kg m−2 h−1 before concentrating light under one sun and 3.5 wt% brine. Comparably, it rose to 3.95 kg m−2 h−1 after concentrating (IPSFCL), marking a 71 % enhancement. This innovative light-collecting device and water-energy balance engineering provides a novel strategy and technique for designing 3D evaporators and can be applied in different environmental conditions.

Ecological and human health risk assessment of heavy metal contamination in soils of major industrial estates of Tamil Nadu, India

ABSTRACT This study endeavoured to determine the current status of heavy metal contamination in soils around leather industrial areas of Tamil Nadu and the associated environmental and human health risks. Accordingly, 31 soil samples were examined using the total reflection X-ray fluorescence (TXRF) spectroscopy technique. From TXRF results, the mean concentrations of heavy metals (mg kg−1, dry weight) were obtained in the trend of Fe (9234.03) > Al (592.00) > Cr (194.99) > Sr (148.76) > Mn (137.61) > Cl (81.79) > Zn (38.97) > Cu (38.33) > V (36.78) > Pb (31.18) > Ni (9.81) > As (1.12). The pollution indices such as geo-accumulation index (Igeo), contamination factor (CF), and enrichment factor (EF) revealed the significant contaminants in the study area. The hazard index (HI) indicated that non-carcinogenic risk (NCR) due to heavy metals were negligible for both adults and children (HI < 1). In addition, total cancer risk (TCR) showed carcinogenic risk (CR) for adults (TCR = 1.38 × 10−4) and children (TCR = 1.27 × 10−3) are moderate and higher, respectively. Multivariate statistical analyses such as Pearson correlation analysis (CA), hierarchical cluster analysis (HCA), and factor analysis (FA) revealed that the heavy metals derived from various sources such as lithogenic and anthropogenic. Overall, special concern is advised to the inhabitants, especially with regard to children, in the study area about the health risks due to the anthropogenic inputs.

ATR‐FTIR Spectroscopy Preprocessing Technique Selection for Identification of Geographical Origins of Gastrodia elata Blume

ABSTRACTGastrodia elata Blume from different regions varies in growth conditions, soil types, and climate, which directly affects the content and quality of its medicinal components. Accurately identifying the origin can effectively ensure the medicinal value of G. elata Bl., prevent the circulation of counterfeit products, and thus protect the interests and health of consumers. Attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy is a rapid and effective method for verifying the authenticity of traditional Chinese medicines. However, the presence of scattering effects in the spectra poses challenges in establishing reliable discrimination models. Therefore, employing appropriate scattering correction techniques is crucial for improving the quality of spectral data and the accuracy of discrimination models. This study uses two ensemble preprocessing approaches; the first type is series fusion of scatter correction technologies (SCSF), and another method is sequential preprocessing through orthogonalization (SPORT). Four discriminant models were established using a single scattering correction technique and two ensemble preprocessing approaches. The results show that the data‐driven version of the soft independent modeling of class analogy (DD‐SIMCA) model built based on multiplicative scatter correction (MSC) preprocessing has a sensitivity of 0.98 and a specificity of 0.91, able to effectively distinguish whether a sample of G. elata Bl. originates from Zhaotong. In addition, three discriminant models including support vector machine (SVM), partial least squares discriminant analysis (PLS‐DA), and three gradient boosting machine (GBM) algorithms built using the ensemble preprocessing approach have good classification and generalization capabilities. Among them, the SCSF‐PLS‐DA model has the best performance with 99.68% and 98.08% accuracy for the training and test sets, respectively, and F1 of 0.97; the SPORT‐SVM model achieved the second‐best classification ability. The results show that the ensemble preprocessing approach used can improve the success rate of G. elata Bl. geographical origin classification.

Irradiation of PMMA intraocular lenses by a 365 nm UV lamp

Abstract Intraocular lens (IOL) made on Polymethylmethacrylate (PMMA) has been irradiated by a UV lamp at different exposure times, in air and at room temperature. The macromolecular modifications induced in the lens have been investigated using attenuated total reflectance (ATR) coupled to Fourier transform infrared (FT-IR) spectroscopy and Optical spectroscopy. Particular attention was devoted to the study of chemical modifications by UV irradiation, which induced chain scissions in the superficial PMMA layers. Results demonstrated that the lens transmission to the visible radiation is not particularly reduced by a long exposition to UV radiation at a fluence of 200 mJ/cm2, up to 19 h.

O-294 Human oocyte survival, early embryo development, metabolic fingerprinting, and pregnancy outcomes following ultra-rapid or standard vitrification and thawing

Abstract Study question Is ultra-rapid vitrification and thawing superior to standard vitrification in terms of preserving oocyte viability, embryo competence and enhancing pregnancy outcomes? Summary answer Ultra-rapid vitrification and thawing preserves oocyte viability and embryo quality as confirmed by their euploidy, non-invasive biomarkers in the culture media, and favorable pregnancy outcomes. What is known already Cryopreservation and vitrification protocols for oocytes and embryos have varying cooling rates, cryoprotectant chemical composition and concentration. While vitrification avoids intracellular ice crystal formation, the elevated concentrations of cryoprotectants may be cytotoxic. Over the past 20 years, parameters for vitrification protocols were optimized to improve efficiency and viability of human oocytes and embryos, however few studies have evaluated the metabolic and secretome profiles in addition to embryology and pregnancy outcomes, particularly following ultra-rapid vitrification and thawing. Mid-infrared spectroscopy is a great option for characterizing environmental components and metabolic profiles using the more spectrally complex fingerprint region from 1450-500 cm-1. Study design, size, duration This prospective study included 1,214 donor oocytes collected between January 2022 and November 2023. Sibling oocytes were assigned to standard or ultra-rapid vitrification and thawing. Corresponding blastocysts underwent the same type of vitrification following trophectoderm biopsies for PGT-A. Spent embryo culture fluid was collected on day 1, 3, and 5 for spectroscopy and PCR analysis, as well as on day 6 for metabolic fingerprinting. Clinical pregnancy was assessed 5 days following single embryo transfer. Participants/materials, setting, methods Vitrified oocyte survival was assessed one hour after thawing. Secretome profiling of day 1, 3, and 5 embryos was conducted by Attenuated Total Reflection Fournier Transform Infrared (ATR-FTIR) spectroscopy. Metabolic profiling of blastocysts (day 6) was conducted by Fournier Transform Infrared (FTIR) spectroscopy. Embryology and pregnancy data together with lipid, protein, and nucleic acid expression profiles were evaluated using the Shapiro-Wilk test followed by the student t-test (parametric variables) or the Mann-Whitney U-Test (non-parametric variables). Main results and the role of chance There was 100% survival in oocytes subject to ultra-rapid vitrification-thawing (n = 531) compared to 94.5% in oocytes that underwent standard vitrification (n = 634). There were no significant differences in the fertilization rates following intracytoplasmic sperm injection (81.3% with ultra-rapid and 83.2% with standard vitrification) or potential to reach day 3 of embryo development[RL1]. Ultra-rapid vitrification-thawing produced significantly more blastocysts than standard vitrification-thawing (67.3% vs. 53.0%, respectively) but both techniques had similar euploidy rates (61.8% vs. 61.4%, respectively; p &amp;gt; 0.05). Spectra in the 4000-450 cm-1 region revealed there were no significant differences in lipid and protein expression profiles of day 1, 3, 5 and 6 embryos. The similar result obtained for the culture media for day 1,3,5 and 6 day embryo development with no significant difference. Day 3 blastomere biopsy samples and Day5, Day 6 trophectoderm biopsy sample showed no significant differences for total protein concentration, lipid and nucleic acid experssion profiles in both group.This finding was corroborated by PCR analysis showing no significant difference in nucleic acid profiles. Finally, clinical pregnancy rates were 65.22% with ultra-rapid and 56.5% [RL2] with standard vitrification. (p &amp;lt; 0.05) Limitations, reasons for caution While both our ultra-rapid and standard vitrification-thawing protocols appear to preserve embryo competence to the blastocyst stage and euploidy, future studies should evaluate whether RNA expression levels are altered with these approaches. Wider implications of the findings This study shows competent and euploid embryos can be generated following ultra-rapid vitrification and provides embryo metabolites that can serve as non-invasive biomarkers for the identification of healthy embryos before embryo transfer. Trial registration number NA

Modifying Specific Ion Effects: Studies of Monovalent Ion Interactions with Amines.

Specific ion effects in the interactions of monovalent anions with amine groups─one of the hydrophilic moieties found in proteins─were investigated using octadecylamine monolayers floating at air-aqueous solution interfaces. We find that at solution pH 5.7, larger monovalent anions induce a nonzero pressure starting at higher areas/molecules, i.e., a wider "liquid expanded" region in the monolayer isotherms. Using X-ray fluorescence at near total reflection (XFNTR), an element- and surface-specific technique, ion adsorption to the amines at pH 5.7 is confirmed to be ion-specific and to follow the conventional Hofmeister series. However, at pH 4, this ion specificity is no longer observed. We propose that at the higher pH, the amine headgroups are only partially protonated, and large polarizable ions such as iodine are better able to boost amine protonation. At the lower pH, on the other hand, the monolayer is fully protonated, and electrostatic interactions dominate over ion specificity. These results demonstrate that ion specificity can be modified by changing the experimental conditions.

Probing buried interface band dispersion of a MgO/Fe heterostructure with hard X-ray angle-resolved photoemission

Abstract Interface band dispersion of a MgO(2 nm)/Fe(50 nm) heterostructure was detected by hard X-ray angle-resolved photoemission spectroscopy (HARPES) with the excitation photon energy of 3.29 keV by utilizing X-ray total reflection (TR). By subtracting bulk-sensitive band dispersion of the buried Fe(001) obtained by HARPES in the non-TR condition from near-interface-sensitive Fe(001) band dispersion obtained by TR-HARPES, the band-folding of Fe and the O 2p -Fe 3d hybridization at the heterointerface were clearly unveiled. These results suggest that HARPES can probe not only bulk band but also buried interface band of heterojunctions.

Bio-Based Polyurethane Networks Containing Sunflower Oil Based Polyols

This work focused on the preparation and investigation of polyurethane (SO-PU)-containing sunflower oil glycerides. By transesterification of sunflower oil with glycerol, we synthesized a glyceride mixture with an equilibrium composition, which was used as a new diol component in polyurethanes in addition to poly(ε-caprolactone)diol (PCLD2000). The structure of the glyceride mixture was characterized by physicochemical methods, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), nuclear magnetic resonance spectroscopy (NMR), and size exclusion chromatography (SEC) measurements. The synthesis of polyurethanes was performed in two steps: first the prepolymer with the isocyanate end was synthesized, followed by crosslinking with an additional amount of diisocyanate. For the synthesis of the prepolymer, 4,4’-methylene diphenyl diisocyanate (MDI) or 1,6-hexamethylene diisocyanate (HDI) were used as isocyanate components, while the crosslinking was carried out using an additional amount of MDI or HDI. The obtained SO-PU flexible polymer films were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The so-obtained flexible SO-PU films were proved to be suitable for the preparation of potentially biocompatible and/or biodegradable scaffolds. In addition, the stress versus strain curves for the SO-PU polymers were interpreted in terms of a mechanical model, taking into account the yield and the strain hardening.