Strain evolution from the ferroelectric to the relaxor state in (0.67 - x)BiFeO3-0.33BaTiO3-xBi(Mg0.5Zr0.5)O3 lead-free ceramics.

The BiFeO3-BaTiO3 solid solution exhibits enhanced electric properties due to its modified phase structure with relaxor characteristics and reduced leakage current. Despite these advancements, the underlying mechanism behind the phase transition from a ferroelectric to a relaxor state in BF-BT ceramics remains largely unexplored. Here, the evolution of strain in (0.67 - x)BiFeO3-0.33BaTiO3-xBi(Mg0.5Zr0.5)O3 ceramics is investigated, with a focus on the strain transition from a ferroelectric to a relaxor phase. A strengthening of relaxor behavior is observed in the modified rhombohedral (R) and pseudocubic (PC) phase structure, resulting in optimal strain (Suni = 0.25%, Spos = 0.24%) at x = 0.04. The enhanced strain is attributed to the promotion of domain switching and the presence of strong random fields, with polar nanoregions integrating into a long-range ordered matrix. Furthermore, a gradual increase in strain with rising temperature is noted, driven by increased polarization and the expansion of ferroelectric domains. This study underscores the critical role of structural modifications in augmenting the electric response of BF-BT ceramics, thereby advancing the development of lead-free piezoelectric materials.

Recent advances in micro- and nanomaterial-based adsorbents for pipette-tip solid-phase extraction.

There are a lot of review papers of sample pretreatment, but the comprehensive review on pipette-tip solid-phase extraction (PT-SPE) is lacking. This review (133 references) is mainly devoted to the development of different types of micro- and nanosorbent-based PT-SPE, including silica materials, carbon materials, organic polymers, molecularly imprinted polymers, and metal-organic frameworks. Each section mainly introduces and discusses the preparation methods, advantages and limitations of adsorbents, and their applications to environmental, biological, and food samples. This review also demonstrates the advantages of PT-SPE like convenience, speed, less organic solvent, and low cost. Finally, the future application and development trend of PT-SPE are prospected.

Poly(ionic liquid)-hybridized silica aerogel for solid-phase microextraction of polycyclic aromatic hydrocarbons prior to gas chromatography-flame ionization detection.

Using poly(ionic liquid) (PIL) and tetraethyl orthosilicate (TEOS) as the co-precursors, PIL-hybridized silica aerogel was prepared via sol-gel method for solid-phase microextraction (SPME). The ratio between PIL and TEOS was regulated to achieve the best extraction effect. The aerogel was coated onto the surface of stainless steel wire to get SPME fiber. Coupled to gas chromatography-flame ionization detector (GC-FID), the fiber was separately evaluated by the determination of alkanes, polycyclic aromatic hydrocarbons (PAHs), as well as BTEX (benzene, toluene, ethylbenzene, and xylenes) in immersion mode. The extraction performance of PAHs was attributed to π stacking and hydrophobic effect. After optimization of main extraction and desorption conditions, the SPME-GC-FID method was established towards eight PAHs, and it provided low detection limits (0.005 µg L-1, 0.010 µg L-1) and wide linear ranges (0.016-20.00 µg L-1, 0.033-20.00 µg L-1) with good linear coefficients (0.9991-0.9998). The method was applied to detect trace PAHs in real water samples, with relative recoveries of 86.2-119.2%. Furthermore, PIL-hybridized silica aerogel exhibits some superiorities like higher sensitivity, shorter extraction time, and better repeatability over other extraction coatings. The present work not only extends the range of aerogel materials but also promoted their further applications in sample preparation. Graphical abstract.

Triazine-based organic polymers@SiO2 nanospheres for sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons.

Triazine-based organic polymers@SiO2 nanospheres were prepared and applied as an extraction coating onto stainless steel wires and the wires were filled into polyetheretherketone tube for in-tube solid-phase microextraction. Taking polycyclic aromatic hydrocarbons as targets, main factors affecting extraction performance of the tube were investigated through coupling to high performance liquid chromatography. Under the optimum conditions, an online analytical method for polycyclic aromatic hydrocarbons was established with large linear ranges (0.010-20 µg/L), low limits of detection (0.003-0.010 µg/L), high enrichment factors (533-2954), and good repeatability (relative standard deviations <1.7% for intraday test, <5.0% for interday test). The analysis method was successfully applied to the detection of trace targets in real water samples and the relative recoveries ranged from 82.9 to 119.9%, which demonstrated the applicability of extraction tube in sample preparation.

Mesoporous silica hybridized by ordered mesoporous carbon for in-tube solid-phase microextraction.

To enhance the extraction performance, a mesoporous silica was modified with ordered mesoporous carbon for solid-phase microextraction. Three stainless-steel wires coated with the mesoporous material were placed in a polyetheretherketone tube for getting an extraction tube. The tube was coupled to high-performance liquid chromatography with diode array detector, and the online analysis system was constructed. Then its extraction performance was evaluated using hydrophobic polycyclic aromatic hydrocarbons, phthalates, and hydrophilic neonicotinoids. The best selectivity was presented for polycyclic aromatic hydrocarbons. Several main conditions were optimized such as sampling volume, sampling rate, methanol concentration in the sample, and desorption time, a rapid and sensitive analytical method was established toward polycyclic aromatic hydrocarbons. The analytical method exhibited wide linear range from 0.017 to 15 µg/L with acceptable correlation coefficients more than 0.9990, limits of detection in 0.005-0.020 µg/L, limits of quantification ranging from 0.017 to 0.066 µg/L as well as large enrichment factors of 377-2314. It was successfully applied to detect trace polycyclic aromatic hydrocarbons in some real water samples including tap water, snow water, and domestic sewage.

Application of biocharcoal aerogel sorbent for solid-phase microextraction of polycyclic aromatic hydrocarbons in water samples.

A facile method was introduced for preparing a biocharcoal aerogel, which was derived from pomelo peel as the only raw material. The inner spongy layer of pomelo peel was freeze-dried for maintaining three-dimensional structure and then carbonized under high temperature and oxygen-limited conditions. The morphological structure and graphitization degree of biocharcoal aerogel were characterized using a scanning electron microscope and Raman spectrum. After sifting and grinding, the biocharcoal aerogel as an adsorbent was coated onto the surface of stainless steel wires. Through placing the wires into a polyetheretherketone tube, the in-tube solid-phase microextraction device was obtained. Coupled with high-performance liquid chromatography, it exhibited good extraction performance for polycyclic aromatic hydrocarbons, then an online analytical method was established with low limits of detection (0.005-0.050 ng/mL), wide linear ranges (0.017-15 ng/mL) with superior correlation coefficients higher than 0.9990, high enrichment factors (1128-3425), and acceptable intra- and inter-day repeatabilities (relative standard deviations ≤ 6.7%, n = 3). The method was applied to detect polycyclic aromatic hydrocarbons in bottled water samples, environmental water samples, and soft drinks with satisfactory recoveries (83.3-120.9%). This research not only developed a new carbon aerogel but also evaluated its adsorption performance in sample preparation.

Core-shell silica@pyridyl conjugated microporous polymer as a stationary phase for high performance liquid chromatography.

BACKGROUND: Because of the advantages of good selectivity, high sensitivity, and fast analysis, high performance liquid chromatography (HPLC) has become one of the modern analytical techniques in wide application range, such as biological analysis, environmental detection, pharmaceutical and food inspection, agriculture and other fields. The stationary phase greatly decides the chromatographic separation performance, so the development of novel stationary phase is most important for HPLC. RESULTS: Pyridyl conjugated microporous polymers (P-CMP) with one to four layers were modified on the surface of amino silica to obtain a novel core-shell material (SiO2@P-CMP) by the layer-by-layer assembly strategy and Chichibabin reaction. The relationship between the structure of SiO2@P-CMP and chromatographic performance was carefully investigated, and the retention mechanism was revealed. The interactions including π-π stacking, hydrophobic effect and hydrogen bond gradually enhanced with the increase of P-CMP layers on the silica surface. Compared with C18 column, SiO2@P-CMP columns displayed better separation selectivity for polycyclic aromatic hydrocarbons (PAHs). According to the relative retention values (α), the separation performance of SiO2@P-CMP columns (α = 1.144-1.884) for PAH isomers and other analytes was obviously better than that of C18 column (α = 0.998-1.487). Furthermore, the SiO2@P-CMP column with four layers was selected to separate different types of analytes (eight PAHs, four bisphenols, four estrogens and nine phthalates), and the peak order of analytes was different from that on the C18 column due to the influence of hydrogen-bonding and π-π interactions. The relative standard deviations (n = 10) of retention time and peak area on SiO2@P-CMP column were between 0.28 % and 1.98 %. SIGNIFICANCE AND NOVELTY: Pyridyl conjugated microporous polymer was introduced as the stationary phase for the first time in HPLC. The proposed column displayed better separation characteristics compared to Zorbax SB-C18 column. It provided a new idea for the separation of small molecules and the development of chromatographic packing or extraction material.

Peripheral blood transcriptomic analysis identifies potential inflammation and immune signatures for central retinal artery occlusion.

Central retinal artery occlusion (CRAO) is an acute retinal ischaemic disease, but early diagnosis is challenging due to a lack of biomarkers. Blood samples were collected from CRAO patients and cataract patients. Gene expression profiles were distinct between arterial/venous CRAO blood (A-V group) and venous CRAO/control blood (V-C group) samples. Differentially expressed genes (DEGs) were subjected to GO and KEGG enrichment analyses. Hub genes were identified by Cytoscape and used to predict gene interactions via GeneMANIA. Immune cell infiltration was analysed by CIBERSORT. More than 1400 DEGs were identified in the A-V group and 112 DEGs in the V-C group compared to controls. The DEGs in both groups were enriched in the ribosome pathway, and those in the V-C group were also enriched in antigen processing/MHC pathways. Network analysis identified ribosomal proteins (RPS2 and RPS5) as the core genes of the A-V group and MHC genes (HLA-F) as the core genes of the V-C group. Coexpression networks showed ribosomal involvement in both groups, with additional immune responses in the V-C group. Immune cell analysis indicated increased numbers of neutrophils and T cells. Ribosomal and MHC-related genes were identified as potential CRAO biomarkers, providing research directions for prevention, diagnosis, treatment and prognosis.

Plasmalogens and Octanoylcarnitine Serve as Early Warnings for Central Retinal Artery Occlusion.

Central retinal artery occlusion (CRAO) is a kind of ophthalmic emergency which may cause loss of functional visual acuity. However, the limited treatment options emphasize the significance of early disease prevention. Metabolomics has the potential to be a powerful tool for early identification of individuals at risk of CRAO. The aim of the study was to identify potential biomarkers for CRAO through a comprehensive analysis. We employed metabolomics analysis to compare venous blood samples from CRAO patients with cataract patients for the venous difference, as well as arterial and venous blood from CRAO patients for the arteriovenous difference. The analysis of metabolites showed that PC(P-18:0/22:6(4Z,7Z,10Z,13Z,16Z,19Z)), PC(P-18:0/20:4(5Z,8Z,11Z,14Z)) and octanoylcarnitine were strongly correlated with CRAO. We also used univariate logistic regression, random forest (RF), and support vector machine (SVM) to screen clinical parameters of patients and found that HDL-C and ApoA1 showed significant predictive efficacy in CRAO patients. We compared the predictive performance of the clinical parameter model with combined model. The prediction efficiency of the combined model was significantly better with area under the receiver operating characteristic curve (AUROC) of 0.815. Decision curve analysis (DCA) also exhibited a notably higher net benefit rate. These results underscored the potency of these three substances as robust predictors of CRAO occurrence.

Contribution of irreversible non-180° domain to performance for multiphase coexisted potassium sodium niobate ceramics.

Despite the dominance of lead-based piezoelectric materials with ultrahigh electric-field-induced strain in actuating applications, seeking eco-friendly substitutes with an equivalent performance remains an urgent demand. Here, a strategy of regulating the irreversible non-180° domain via phase engineering is introduced to optimize the available strain (the difference between the maximum strain and the remnant strain in a unipolar strain curve) in the lead-free potassium-sodium niobate-based piezoelectric ceramics. In situ synchrotron X-ray diffraction and Rayleigh analysis reveal the contribution of the non-180° domain to available strain in the tetragonal-orthorhombic-rhombohedral phase boundary. The reducing orthorhombic phase and increasing rhombohedral/tetragonal phase accompanied by the reduced irreversible non-180° domain are obtained with increasing doping of Sb5+, resulting in an enlarged available strain due to the significantly lowered remnant strain. This optimization is mainly attributed to the reduced irreversible non-180° domain wall motion and the increased lattice distortion, which are beneficial to decrease extrinsic contribution and enhance intrinsic contribution. The mesoscopic structure of miniaturized nanosized domain with facilitated domain switching also contributes to the enhancement of available strain due to the improved random field and decreased energy barrier. The study will shed light on the design of lead-free high-performance piezoelectric ceramics for actuator applications.