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.

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.

Sex differences in major adverse cardiovascular and cerebrovascular event risk among central retinal artery occlusion patients.

To estimate the association between central retinal artery occlusion (CRAO) and major adverse cardiovascular and cerebrovascular events (MACCE), including their clinical characteristics, blood markers, and the contribution of CRAO to MACCE, as well as to assess any sex differences. This retrospective cohort study included continuous new-onset CRAO patients and 1:4 controls during the same period. Correlations of CRAO with the incidence of MACCE during follow-up and the sex-related differences were studied. One hundred and twenty-four CRAO patients and four hundred and ninety-six controls were enrolled. Neutrophil-to-lymphocyte ratio (NLR, P = 0.014) and high-sensitivity C-reactive protein (hs-CRP, P = 0.038) were tended to be higher in CRAO patients. After the follow-up period, 78 patients experienced MACCE. Multivariate Cox regression analysis showed that CRAO was a predictor of the occurrence of MACCE (HR 2.321, 95% CI 1.439-3.744, P = 0.001). Sex subgroups indicated that age, diabetes, current smoking, CRAO, NLR and hs-CRP increased the risk factor of MACCE in males (All P < 0.05) and CRAO, NLR, low-density lipoprotein cholesterol (LDL-C) and hs-CRP were independent influencing factors for females (All P < 0.05). New-onset CRAO significantly increases the probability of MACCE and is associated with a poor prognosis. The sex-related differences suggested that effective prevention of the occurrence of MACCE in high-risk patients requires that attention be given to individualized risk factors corresponding to sexes.

Effects of the degree of substitution of octenyl succinic anhydride on the physicochemical characteristics of adlay starch.

Impact of octenyl succinic anhydride (OSA) esterification on the structural, thermal, pasting, and emulsifying characteristics of adlay starch was investigated. The degree of substitution (DS) increased significantly from 0.008 to 0.025 with increasing OSA quantity, and the bands intensity at 1724 cm-1 and 1572 cm-1 in Fourier transform infrared spectroscopy increased with increasing DS. OSA modified starch showed unaltered orthorhombic diffraction pattern and morphological structure in native adlay starch, but gelatinization temperatures and enthalpy decreased significantly. Higher DS values lowered iodine binding capacity (from 1.37 to 0.77) and a shift in the maximum absorbance wavelength toward the shortwave direction was observed (from 530 nm to 510 nm). Significant increases were observed in peak, through, breakdown and final viscosities upon OSA esterification, while the pasting temperature decreased. Furthermore, contact angles increased significantly from 27.4° to 73.4° with increasing DS, and OSA-starch exhibited superior emulsion stability. Therefore, esterification with OSA effectively modified adlay starch to meet industrial demands and enhance its functional properties.

The prevalence of subclinical hypothyroidism in a pre-diabetes population and an analysis of related factors.

BACKGROUND: To investigate the prevalence and related influencing factors of subclinical hypothyroidism (SCH) in a pre-diabetes (PreDM) population. PATIENTS AND METHODS: A multi-stage stratified cluster random sampling method was used to select the adult Han population in Gansu Province for investigation. General data and related biochemical indices were recorded and SPSS software was used for statistical analyses. RESULTS: This study selected 2876 patients, including 548 with SCH and 433 with PreDM. In the PreDM population, the levels of thyroid stimulating hormone (TSH), serum phosphorus, TPOAb and TgAb in the SCH group were higher than those in the euthyroid group (P < 0.05). The level of TPOAb in females of SCH group was higher than that in males (P < 0.05). The positive rates of TPOAb and TgAb in females were higher than those in males in the total population and SCH population. The prevalence of SCH in the PreDM group under 60 was significantly higher than that in the normal glucose tolerance (NGT) group (26.02% vs. 20.40%, χ2 = 5.150, P < 0.05). We defined SCH as a TSH level of >4.20 mIU/L. Using this criterion, the prevalence of SCH in the total population of PreDM was higher than that in the NGT population (χ2 = 8.611, P < 0.05), the prevalence of SCH in the PreDM population generally showed an upward trend. However, we performed a separate analysis considering the accepted impact of age on TSH redefining SCH as TSH >8.86 mIU/L (for individuals over age 65). However, allowing for the expected rise in TSH levels in individuals over age 65, the prevalence of SCH in the elderly over 65 years of age decreased significantly (NGT population from 27.48% to 9.16%, PreDM population from 34.18% to 6.33%, P < 0.05). Logistic regression analysis showed that the risk factors for SCH in the PreDM population were female gender, fasting plasma glucose and TSH (all P < 0.05). Risk factors for SCH in the impaired fasting glucose (IFG) population were female gender, OGTT 2 h, TSH and TPOAb (all P < 0.05). CONCLUSION: The prevalence of SCH in the PreDM population not considering the known physiological increase in age related TSH was relatively high and was significant in female and the IFG population. However, the effect of age on these findings needs to attract more attention.

The prevalence of subclinical hypothyroidism (SCH) in the pre-diabetic population was analysed by cross-sectional survey. There is a great deviation in the diagnosis of SCH in the elderly with physiologically increased thyroid stimulating hormone, which needs to be redefined.

[Preparation and application of graphene oxide functionalized melamine-formaldehyde aerogel coated solid-phase microextraction tube].

Many solid-phase microextraction (SPME) sorbents have been developed from aerogels because of their low densities, large surface areas, and high porosities. Melamine-formaldehyde (MF) aerogel, made from melamine and formaldehyde by a sol-gel reaction, is one of the typical organic aerogels. MF aerogel has better mechanical strength, chemical stability and extraction performance than inorganic aerogels. The performance of the aerogel is limited in some fields, while composite aerogels can meet different requirements such as good mechanical strength and strong adsorption performance. Graphene oxide (GO) is a two-dimensional nanomaterial composed of a single layer of carbon atoms and provides π-π interaction by a large π-electron. In addition, the oxygen-containing groups at the edge of the lamellar structure improve the hydrophilicity of the material and can interact with various compounds. To improve the extraction performance of MF aerogel for polycyclic aromatic hydrocarbons (PAHs), GO/MF aerogels were prepared by functionalizing MF aerogel with GO. In this study, 1.2612 g of melamine and 80 mg of sodium carbonate were dissolved in 30 mL of water, and the mixture was heated to 80 ℃ under stirring. Then, 2.8 mL formaldehyde solution (37%) was slowly added, and a clear solution was obtained gradually. Next, 50 mg of GO powder was ultrasonically dispersed in 10.0 mL of water and evenly mixed with the above solution. After adjusting the pH to 1.5, the sol-gel process was performed for 48 h, then the gel was aged at room temperature for 24 h. The gel was then soaked in ethanol, acetone, and cyclohexane in turn to replace the solvent. Finally, the GO/MF aerogel was obtained by freeze-drying for 24 h. The GO/MF aerogel was characterized by scanning electron microscopy (SEM) and X-ray photoelectric spectroscopy (XPS), confirming that GO was successfully introduced into MF aerogel, while retaining its three-dimensional network and porous structure. GO/MF aerogel was coated onto the surface of a stainless steel wire to be used as sorbent. Four such wires were placed into a polyetheretherketone (PEEK) tube (0.75 mm i. d., 30 cm length) for in-tube (IT) SPME. The tube was combined with a high-performance liquid chromatography (HPLC) unit to construct an IT-SPME-HPLC online system. When the six-way valve was in the Load state, sample solution achieved online enrichment with analytes while it flowed through the extraction tube. After extraction, the valve was turned to the Inject state, and the analytes were eluted into the chromatographic column by the mobile phase at a flow rate of 1.0 mL/min for separation and detection with the detector. Under the same extraction conditions (sampling volume=30 mL, sampling rate=1.00 mL/min, and concentration of polycyclic aromatic hydrocarbons (PAHs, viz. naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorine (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla) and pyrene (Pyr))=5.00 µg/L), GO/MF aerogel-based tube was compared with that of MF aerogel-based tube. GO enhanced the enrichment efficiency of MF aerogel towards PAHs from 1.1 to 2.5 times, due to the increased number of adsorption sites and enhanced π-π interaction with PAHs. IT-SPME was affected by the sampling volume, sampling rate, concentration of organic solvent in sample, desorption solvent, desorption rate, and desorption time. To obtain accurate results, the main extraction and desorption conditions (sampling volume, sampling rate, organic solvent concentration, desorption time) were investigated carefully. As the sampling volume in the extraction tube was increased, the extraction efficiency was found to increase gradually until saturation. In this study, the extraction efficiency was investigated for sampling volumes ranging from 30 to 80 mL, and 70 mL was selected as a suitable sampling volume to achieve satisfactory extraction efficiency. The sampling rate affects not only the extraction efficiency, but also the extraction time. When the sample flows through the extraction tube at a low rate, it requires a long test time. Although the increase in sampling rate reduces the extraction time, it often decreases extraction efficiency. In addition, large sampling rate leads to high pressure in the tube, which in turn reduces the service life of the tube. Therefore, the effect of sampling rate (1.25-2.50 mL/min) on extraction efficiency was investigated, and good extraction efficiency and short test time were achieved when the sampling rate was 2 mL/min. High hydrophobic PAHs have poor solubility in water. An appropriate amount of organic solvent in the sample solution can improve the solubility of PAHs to obtain accurate analytical results. However, the extraction efficiency was affected by the added organic solvent. Thus, the effect of volume fraction of methanol (0, 0.5%, 1%, 2%, 3%, and 5%, v/v) on the extraction efficiency was investigated. The sample solution without methanol afforded better extraction efficiency and satisfactory repeatability. After online extraction, the desorption directly affects the desorption efficiency. The peak areas of the eight PAHs were investigated with different desorption times (0.2, 0.4, 0.6, 0.8, 1.0, and 2.0 min), and a desorption time of 2.0 min was required to fully desorb all analytes and reduce their residuals. The IT-SPME-HPLC-DAD method was established under the optimized conditions, and the limits of detection (LODs), linear equations, linear ranges, and correlation coefficients were obtained. The LODs of the eight PAHs were in the range of 0.001-0.005 µg/L, the quantitative ranges of the analytes were 0.003-15.0 µg/L for Fla and Pyr, 0.010-20.0 µg/L for Phe and Ant, and 0.017-20.0 µg/L for Nap, Acy, Ace and Flu, the enrichment factors were in the range of 2029-2875, and the analytical precision was satisfactory (intra-day RSD%≤4.8%, and inter-day RSD≤8.6%). Compared with some reported methods, the method reported herein provided higher sensitivity, wider linear range, and shorter test time. This method was applied to the detection of PAHs in common drinking water, including bottled mineral water and water from drinking fountain. The satisfactory recovery (76.3%-132.8%) obtained proves that the method is suitable for the determination of trace PAHs in real water samples, with high sensitivity, rapid testing, online detection, and good accuracy. The extraction tube also exhibited satisfactory durability and chemical stability.

Carbonized metal-organic framework-74/carbon aerogel composites for the efficient extraction of triazole fungicides from fruits and vegetables.

To improve the extraction efficiency, availability, and stability of metal-organic framework (MOF) for pipette-tip solid-phase extraction (PT-SPE), a carbonized MOF-74/carbon aerogel composite (CMOF-74/CA) was developed. A carbon aerogel with a surface area of 547.7 m2 g-1 was prepared by carbonizing a watermelon peel. After that, via a hydrothermal reaction, the MOF-74 was in situ grown on the surface. After the pyrolysis at 700 °C for 2 h, the CMOF-74/CA composite was obtained. Through regulating the concentration of reactants, a series of MOF-74/CA and CMOF-74/CA materials were prepared. These materials were used to extract hexaconazole and diniconazole in fruits and vegetables before gas chromatography-flame ionization detection (GC-FID). The adsorbent type and amount, sample pH, and the desorption solvent type and volume were optimized factor by factor. Under the optimized conditions, a PT-SPE-GC-FID method was established. Moreover, good linearity in the concentration ranges of 0.098-200.0 mg kg-1 and 0.196-200.0 mg kg-1, and detection limits ranging between 0.033 and 0.065 mg kg-1 were achieved for two triazole fungicides (TFs). The relative standard deviations (n = 3) for intra-day and inter-day tests were in the ranges of 3.1-3.2% and 3.0-3.4%, respectively. The method showed satisfactory analytical performance in different samples with good relative recoveries in the range of 72.6-116%. Compared with some methods, it displayed wider linearity, better or comparable sensitivity, and enhanced analytical precision.

Carbon aerogels derived from waste paper for pipette-tip solid-phase extraction of triazole fungicides in tomato, apple and pear.

In order to develop environmentally friendly, economical and facile preparation method of carbon aerogels (CAs), the waste printing paper as the raw material was combined with graphene oxide and carboxylic multi-walled carbon nanotubes to produce CAs (ρ = 44 mg cm-3). The CAs with different composition were investigated, the addition of graphene oxide led to the reduction of adsorption sites and the reduction of extraction performance. But the carbon nanotubes made CAs have a better pore structure. The CAs as adsorbent were loaded into a pipette-tip for solid-phase extraction of hexaconazole and diniconazole. Coupled with gas chromatography, an analytical method was established under the optimized conditions. The limits of detection were between 0.08 and 0.32 mg kg-1, the linear ranges were 0.96-200.0 mg kg-1 and 0.24-200.0 mg kg-1. The relative recoveries were in the range of 81.0-119%. The results indicated that the method had potential application for the determination of triazole fungicides.

Intermittent Fasting to the Eye: A New Dimension Involved in Physiological and Pathological Changes.

Intermittent fasting (IF) is gaining popularity as a therapeutic dietary strategy that regulates metabolism and can alter the development of metabolic disorders. An increasing amount of research has connected ocular diseases to IF and discovered that it has a direct and indirect effect on the eye's physiological structure and pathological alterations. This article summarizes the progress of research on IF in regulating the physiological structures of the ocular vasculature, the anterior segment of the eye, the retina, and the choroid. We explored the therapeutic potential of IF for various common ocular diseases. In the future, a comprehensive study into the fundamental processes of IF will provide a direct and rigorous approach to eye disease prevention and therapy.

Repurposing Vitamin C for Cancer Treatment: Focus on Targeting the Tumor Microenvironment.

Based on the enhanced knowledge on the tumor microenvironment (TME), a more comprehensive treatment landscape for targeting the TME has emerged. This microenvironment provides multiple therapeutic targets due to its diverse characteristics, leading to numerous TME-targeted strategies. With multifaced activities targeting tumors and the TME, vitamin C is renown as a promising candidate for combination therapy. In this review, we present new advances in how vitamin C reshapes the TME in the immune, hypoxic, metabolic, acidic, neurological, mechanical, and microbial dimensions. These findings will open new possibilities for multiple therapeutic avenues in the fight against cancer. We also review the available preclinical and clinical evidence of vitamin C combined with established therapies, highlighting vitamin C as an adjuvant that can be exploited for novel therapeutics. Finally, we discuss unresolved questions and directions that merit further investigation.

Extraction performance-structure relationship of polyamidoamine dendrimers on silica for online solid-phase extraction of organic pollutants.

Polyamidoamine dendrimers with different generations (G1-G5) were synthesized in situ on silica progressively via Michael addition and amidation reactions. A sequence of materials was characterized by elemental analysis and Brunauer-Emmett-Teller test, the content of each element (C, H and N) was increased but the surface area was reduced gradually from G1 to G5. These materials were separately packed in a stainless steel column (10 × 4.0 mm, i.d.) for SPE. These SPE columns were combined with high performance liquid chromatography (HPLC) to establish an online SPE-HPLC analysis. According to the chemical structures of materials, polycyclic aromatic hydrocarbons (PAHs) and bisphenols as model analytes were selected to investigate the extraction performance and the extraction mechanism, so as to reveal the extraction performance-structure relationship of G1-G5. The extraction performance was improved with the increase of functional groups from G1 to G4 or G5, the hydrophobic effect played main role accompanied with possible weak hydrophilic, hydrogen-bonding and electrostatic interactions in extraction mechanism. The adsorption capacity, enrichment factor, partition coefficient and extraction efficiency for PAHs and bisphenols reached to 17.52 µg g-1 and 2.70 µg g-1, 5353 and 3002, 5066 and 1197, and 90.09% and 60.05% respectively. Compared with commercial SPE materials, these dendrimer-grafted silica materials were inferior to C18, but better than silica. Furthermore, the G4 and G5 were separately selected to develop two online SPE-HPLC analytical methods for determining trace PAHs and bisphenols in real water samples, and satisfactory results were obtained.

CircFUNDC1 knockdown alleviates oxygen-glucose deprivation-induced human brain microvascular endothelial cell injuries by inhibiting PTEN via miR-375.

BACKGROUND: The maintenance of human brain microvascular endothelial cell (HBMEC) function is crucial to improve the outcomes of ischemic stroke (IS). Emerging evidence shows that circular RNAs (circRNAs) are involved in IS progression. This study aimed to investigate the role of circRNA FUN14 domain containing 1 (circFUNDC1) in oxygen-glucose deprivation (OGD)-treated HBMECs. METHODS: The expression of circFUNDC1, miR-375 and phosphatase and tensin homolog (PTEN) mRNA was detected by quantitative real-time PCR (qPCR). Cell viability, apoptosis, migration and angiogenesis were determined by CCK-8 assay, flow cytometry assay, transwell assay and tube formation assay. The protein level of PTEN was detected by western blot. The relationship between miR-375 and circFUNDC1 or PTEN was confirmed by pull-down assay, dual-luciferase reporter assay and RIP assay. Exosomes were identified by transmission electron microscopy (TEM) and nanoparticle tracking analysis (NTA). RESULTS: CircFUNDC1 expression was increased in peripheral blood of IS patients and OGD-treated HBMECs. CircFUNDC1 knockdown alleviated OGD-induced cell apoptosis and promoted OGD-blocked cell viability, migration and angiogenesis of HBMECs. MiR-375 was a target of circFUNDC1, and miR-375 restoration played similar effects with circFUNDC1 knockdown. The inhibition of miR-375 reversed the effects of circFUNDC1 knockdown. In addition, PTEN was a downstream target of miR-375, and PTEN overexpression abolished the effects of miR-375 restoration. The expression of circFUNDC1 was elevated in serum-derived exosomes of IS patients, and circFUNDC1 harbored diagnostic values. CONCLUSION: CircFUNDC1 knockdown alleviates OGD-induced HBMECs injuries by inhibiting PTEN via enriching miR-375.

[Recent advance of new sample preparation materials in the analysis and detection of environmental pollutants].

To successfully analyze complex samples and detect trace targets, sample pretreatment is essential. Efficient sample pretreatment techniques can remove or reduce interference from the sample matrix. It can also enrich analytes, thereby improving analytical accuracy and sensitivity. In recent years, various sample preparation techniques, including SPE, magnetic dispersion SPE, pipette tip SPE, stir bar extraction, fiber SPME, and in-tube SPME, have received increasing attention in environmental analysis and monitoring. The extraction efficiency mainly depends on the type of adsorbent material. Therefore, the development of efficient adsorbents is a crucial step toward sample preparation. This review summarizes and discusses the research advances in extraction materials over recent years. These extraction materials contain inorganic adsorbents, organic adsorbents, and inorganic-organic hybrid materials such as graphene, graphene oxide, carbon nanotubes, inorganic aerogels, organic aerogels, triazinyl-functionalized materials, triazine-based polymers, molecularly imprinted polymers, covalent organic frameworks, metal-organic frameworks, and their derivatives. These materials have been applied to extract different types of pollutants, including metal ions, polycyclic aromatic hydrocarbons, plasticizers, alkanes, phenols, chlorophenols, chlorobenzenes, polybrominated diphenyl ethers, perfluorosulfonic acids, perfluorocarboxylic acids, estrogens, drug residues, and pesticide residues, from environmental samples (such as water and soil samples). These sample preparation materials possess high surface areas, numerous adsorption sites, and allow extraction via various mechanisms, such as π-π, electrostatic, hydrophobic, and hydrophilic interactions, as well as hydrogen and halogen bond formation. Various sample pretreatment techniques based on these extraction materials have been combined with various detection methods, including chromatography, mass spectrometry, atomic absorption spectroscopy, fluorescence spectroscopy, and ion mobility spectroscopy, and have been extensively used for the determination of environmental pollutants. The existing challenges associated with the development of sample preparation techniques are proposed, and prospects for such extraction materials in environmental analysis and monitoring are discussed. Major trends in the field, including the development of efficient extraction materials with high enrichment ability, good selectivity, excellent thermal stability, and chemical stability, are discussed. Green sample pretreatment materials, environmentally friendly synthesis methods, and green sample pretreatment methods are also explored. Rapid sample pretreatment methods that can be conducted within minutes or seconds are of significant interest. Further, online sample pretreatment and automatic analysis methods have attracted increasing attention. Besides, real-time analysis and in situ detection have been important development directions, and are expected to be widely applicable in environmental analysis, biological detection, and other fields. Modern synthesis technology should be introduced to synthesize specific extraction materials. Controllable preparation methods for extraction materials, such as the in situ growth or in situ preparation of extraction coatings, will acquire importance in coming years. It will also be important to adopt high-performance materials from other fields for sample pretreatment. Organic-inorganic hybrid extraction materials can combine the advantages both organic materials and inorganic materials, and mutually compensate for any disadvantages. Extraction materials doped with nanomaterials are also promising. Although existing sample pretreatment techniques are relatively efficient, it is still imperative to develop novel sample preparation methods.

Dendritic mesoporous silica nanospheres@porous carbon for in-tube solid-phase microextraction to detect polycyclic aromatic hydrocarbons in tea beverages.

It is pretty necessary to detect effectively polycyclic aromatic hydrocarbons (PAHs, including naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene) in foods due to their widespread distribution, trace concentration, and harmful risk to humans beings. Herein, dendritic mesoporous silica nanospheres@porous carbon was developed for solid-phase microextraction of PAHs. Firstly, three-dimensional dendritic mesoporous silica nanospheres (DMSNs) with high surface area and large pore volume were synthesized via an oil-water biphase stratification approach, then porous carbon was further prepared by utilizing DMSNs and asphalt as the template and carbon source, respectively. A core-shell DMSNs@porous carbon material was successfully developed and characterized by Raman spectroscopy, elemental analysis, Brunauer-Emmett-Teller test, scanning electron microscopy, and transmission electron microscopy. DMSNs@porous carbon was proved to be a potential extraction material based on large surface area (442 m2 g-1), suitable pore sizes (about 45 nm), and high carbon content (17.36%). Subsequently, it was developed as an extraction coating and applied to online in-tube solid-phase microextraction of PAHs from tea beverages. Through coupling with high-performance liquid chromatography, an analytical method was established under optimal extraction conditions and desorption, low limits of detection (0.010-0.070 µg L-1), wide linear ranges in 0.033-10 µg L-1, and excellent correlation coefficients (most of the r reach 0.999) were received. The relative standard deviations (RSDs, n = 3) of intra-day test and inter-day test were obtained corresponding to the ranges of 0.1-2.5% and 1.0-4.1%. Finally, the method was used for detecting trace PAHs in different tea beverages from the market.

Recent Advances of Triazine-Based Materials for Adsorbent Based Extraction Techniques.

This review mainly focused on the synthesis and properties of triazine-based materials as well as the state-of-the-art development of these materials in adsorption-based extraction techniques in the past 5 years, such as solid-phase extraction, magnetic solid-phase extraction, solid-phase microextraction and stir bar sorptive extraction, and the detection of various pollutants, including metal ions, drugs, estrogens, nitroaromatics, pesticides, phenols, polycyclic aromatic hydrocarbons and parabens. In the triazine-functionalized composites, triazine-based polymers and covalent triazine frameworks have been developed as the adsorbents with potential for environmental pollutants, mainly relying on the large surface area and the affinity of triazinyl groups with the targets. Triazine-based adsorbents have satisfactory sensitivity and selectivity towards different types of analytes, attributed from various mechanisms including π-π, electrostatics, hydrogen bonds, and hydrophobic and hydrophilic effects. The prospects of the materials for adsorption-based extraction were also presented, which can offer an outlook for the further development and applications.

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.

Polyaniline/titanium dioxide nanorods functionalized carbon fibers for in-tube solid-phase microextraction of phthalate esters prior to high performance liquid chromatography-diode array detection.

To improve extraction performance of carbon fibers (CFs) towards phthalate esters (PAEs), titanium dioxide (TiO2) nanorods array was in-situ grown on the surface of CFs, then polyaniline (PANI) was used to modify it. PANI/TiO2 nanorods-CFs were placed into a polyetheretherketone tube for solid-phase microextraction (SPME). Combining the tube to high performance liquid chromatography (HPLC), it was evaluated and displayed good extraction performance for several PAEs. Compared with bare CFs, TiO2 nanorods and PANI, PANI/TiO2 nanorods presented best performance, attributed to the unique advantages between high surface area of TiO2 nanorods and multiple adsorption interactions (like π-π stacking, hydrogen bond) of PANI. After the optimization of the important factors (sampling volume, sampling rate, sample pH, concentrations of organic solvent and salt in sample, and desorption time), the online in-tube SPME-HPLC method was established. It provided low limits of detection (0.01-0.05 µg L-1) and wide linear ranges (0.03-30, 0.10-30, 0.17-30 µg L-1) with correlation coefficients larger than 0.9991. The relative standard deviations (n=6) between intra-day and inter-day tests were in the ranges of 3.5-10.3% and 4.7-13.9%, respectively. The method was successfully used to determine seven PAEs in real water samples. Besides of satisfactory durability, the material also exhibited superior extraction performance than some materials.

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.