Three-Dimensional DNA Hydrogel Mediated Dual-Mode Sensing Method for Quantification of Epithelial Cell Adhesion Molecule in Biological Fluid Samples.

Monitoring changes in the expression of marker proteins in biological fluids is essential for biomarker-based disease diagnosis. Epithelial cell adhesion molecule (EpCAM) has been identified as a broad-spectrum biomarker for various chronic diseases and as a therapeutic target. However, the development of simple and reliable methods for quantifying EpCAM changes in biological fluids faces challenges due to the variability of its expression across different diseases, the presence of soluble forms, and matrix effects. In this paper, a surface-enhanced Raman scattering (SERS)-fluorescence (FL) dual-mode sensing method was established for quantification of trace EpCAM in biological fluids based on bimetallic Au@Ag nanoparticles and nitrogen-doped quantum dots encapsulated DNA hydrogel hybrid with graphene oxide (Au@Ag-NQDs/GO). The DNA hydrogel was constructed based on three-dimensional (3D) structure DNA-mediated strategy using an aptamer DNA (AptDNA) linker. The interaction of the AptDNA with EpCAM triggered the disassembly of the DNA hydrogel. Consequently, the release of Au@Ag nanoparticles induced an "on-off" switch in the SERS signal while the weakened FL quenching effect in Au@Ag-NQDs/GO system achieved "off-on" switch of FL signal, enabling the simultaneous SERS-FL quantification of EpCAM. The established dual-mode method exhibited outstanding sensitivity and stability in quantifying EpCAM in the range of 0.5-60.0 pg/mL, with the limits of detection (LODs) of SERS and FL as 0.17 and 0.35 pg/mL, respectively. When applied for real sample analysis, the method showed satisfactory specificity and recoveries in cancer cells lysate, serum, and urine samples with RSDs of 2.8-6.3%, 4.0-6.3%, and 2.8-5.7%, respectively. The developed SERS-FL sensing method offered a sensitive, reliable, and practical quantification strategy for trace EpCAM in diverse biological fluid samples, which would benefit the early diagnosis of disease and further health management.

Enrichment-Sensing All-in-One Strategy Integrated in the La(OH)3-Au@AgNPs Substrate for Rapid Surface-Enhanced Raman Spectroscopy Analysis of Purine Components.

Improving the speediness of complex sample analysis has attracted much research interest in analytical science. In this work, an enrichment-sensing all-in-one strategy was presented for rapid surface-enhanced Raman spectroscopy (SERS) analysis of purine components by using the La(OH)3-Au@AgNPs nanocomposite. Two-dimensional (2D) La(OH)3 nanosheets with nanothickness and accessible active sites not only acted as efficient media for the rapid enrichment of analytes but also provided flat planes for the intensive decoration of Au@AgNPs nanoparticles to amplify the SERS signals of adsorbed analytes. The nanocomposite could realize the rapid enrichment-sensing of purine components in 1 min, including mercaptopurine, thioguanine, adenine, and purine. Subsequently, the surface adsorption behaviors were explored by density functional theory and the enhancement mechanisms were simulated by the finite-difference time-domain method. Moreover, the nanocomposite also exhibited good SERS performances with relative standard deviations (RSDs) of uniformity less than 6.5% (n = 23), RSDs of batch-to-batch stability less than 7.3% (n = 9), and long-term stability over 9 weeks with RSDs within 6.6%. Finally, the enrichment-sensing strategy was applied for the rapid SERS analysis of two projects: mercaptopurine in tablets and adenine in beers with detection limits of 6.0 and 0.76 µg/L and spiked recoveries of 90.9-100 and 84.2-101%, respectively. Benefiting from the high-performance enrichment medium and closely packed plasmonic nanoparticles, the enrichment-sensing all-in-one strategy possesses great potential for rapid on-site detection in food safety and pharmaceutical analysis.

Contractile Hairpin DNA-Mediated Dual-Mode Strategy for Simultaneous Quantification of Lactoferrin and Iron Ion by Surface-Enhanced Raman Scattering and Fluorescence Analysis.

DNA-mediated self-assembly technology with good sensitivity and affinity ability has been rapidly developed in the field of probe sensing. The efficient and accurate quantification of lactoferrin (Lac) and iron ions (Fe3+) in human serum and milk samples by the probe sensing method can provide useful clues for human health and early diagnosis of anemia. In this paper, contractile hairpin DNA-mediated dual-mode probes of Fe3O4/Ag-ZIF8/graphitic quantum dot (Fe3O4/Ag-ZIF8/GQD) NPs were prepared to realize the simultaneous quantification of Lac by surface-enhanced Raman scattering (SERS) and Fe3+ by fluorescence (FL). In the presence of targets, these dual-mode probes would be triggered by the recognition of aptamer and release GQDs to produce FL response. Meanwhile, the complementary DNA began to shrink and form a new hairpin structure on the surface of Fe3O4/Ag, which produced hot spots and generated a good SERS response. Thus, the proposed dual-mode analytical strategy possessed excellent selectivity, sensitivity, and accuracy due to the dual-mode switchable signals from "off" to "on" in SERS mode and from "on" to "off" in FL mode. Under the optimized conditions, a good linear range was obtained in the range of 0.5-100.0 µg/L for Lac and 0.01-5.0 µmol/L for Fe3+ and with detection limits of 0.14 µg/L and 3.8 nmol/L, respectively. Finally, the contractile hairpin DNA-mediated SERS-FL dual-mode probes were successfully applied in the simultaneous quantification of iron ion and Lac in human serum and milk samples.

All-in-One Preparation Strategy Integrated in a Miniaturized Device for Fast Analyses of Biomarkers in Biofluids by Surface Enhanced Raman Scattering.

Complex and tedious sample preparation processes have greatly limited rapid analyses of biological samples. In this work, an all-in-one sample preparation strategy based on a miniaturized gas membrane separation/oven ring enrichment (GMS/ORE) device was developed for efficient surface enhanced Raman scattering (SERS) analyses of trace biomarkers in biofluid samples. This strategy integrating gasification separation, liquid trapping, derivatization SERS activation, and coffee-ring enrichment could highly promote the efficiency of sample preparation. Meanwhile, the edges of membranes modified by the hydrophobic-infusing slippery liquid-induced uniform "coffee-ring" effect could significantly improve the sensitivity and stability for SERS quantification. By adapting proper derivatization approaches to the miniaturized GMS/ORE pretreatment, the matrix effects in samples could be prominently eliminated, and clear SERS responses could be obtained for the selective analyses of target biomarkers. The miniaturized GMS/ORE device was practically applied for SERS analyses of trace biomarkers in biofluids, including hydrogen sulfide in saliva samples, creatinine in serum samples, and sarcosine, creatinine, and dimethyl disulfide in urine samples. Accurate quantification of all biomarkers was achieved with recoveries of 89.5%-120.0%, and the contents found by GMS/ORE-SERS matched well with those found by corresponding chromatographic methods with relative errors from -8.6% to 9.3%. The miniaturized GMS/ORE device with multiple parallel processing units could simultaneously treat eight samples in one run with a total analysis time of 40 min. Such an efficient all-in-one strategy integrated on a miniaturized device possesses great potential for fast on-site/point-of-care detection in analytical science and clinical medicine.

Mid-infrared broadband circular polarizer based on Weyl semimetals.

As a three-dimensional topological phase of matter, Weyl semimetals possess extremely large gyrotropic optical response in the mid-infrared region, leading to the strong chiral anomaly. This study proposes a circular polarizer design with a double-WSM-layer structure. It is theoretically shown that the proposed polarizer possesses a high circular polarization efficiency and high average transmittance in the wavelength region from 9 µm to 15 µm at incidence angles up to 50°. The modified 4 × 4 matrix method is used to calculate the circularly polarized transmittance of Weyl semimetals in thin-film or multilayer structures. The temperature dependence on the transmittance is also examined to demonstrate the flexibility of the proposed polarizer in a varying temperature environment. This study reveals the technological prospect that Weyl semimetals are promising candidates for high-performance circular polarizers in infrared spectroscopy and polarimetry.

ß-Ketoenamine-linked covalent organic framework absorbent for online micro-solid phase extraction of trace levels bisphenols in plastic samples.

Covalent organic frameworks with tunable porous crystallinity and outstanding stability have exhibited fascinating pretreatment performance as ideal extraction media. Herein, the ß-ketoenamine-linked TpPa-1 synthesized by 1,3,5-triformylphloroglucinol and paraphenylenediamine was employed as the absorbent for online micro-solid phase extraction of trace bisphenols combined with high-performance liquid chromatography detection. A series of characterizations indicated that the TpPa-1 possessed large surface areas, high stability, and hydrophobicity. The main experimental parameters affecting the extraction efficiency were optimized in detail. Compared with four commercial sorbents, the TpPa-1 exhibited superior enrichment capacity for extracting bisphenols. Under the optimum conditions, the established method demonstrated a wide linear range and high sensitivity with the limit of detection ranging from 0.05-0.06 µg/L. Furthermore, the developed method was successfully applied to determine bisphenols in plastic samples. Bisphenol A was actually detected in a transparent box with a concentration of 0.31 µg/g, and the recoveries of the four bisphenols in the plastic samples were 80.5-116% with the relative standard deviation less than 9.2%. Such performance was attributed to recognition affinity, including the π-π affinity, hydrophobic effect, and hydrogen bond. These results demonstrated that TpPa-1 possessed great potential to be an excellent pretreatment medium for online separation and analysis of trace analytes in complex samples.

Sagittal Cephalometric Evaluation Without Point Nasion: Sagittal G-Triangle Analysis.

ABSTRACT: This study aims to introduce a new sagittal cephalometric measurement, the sagittal G-triangle analysis, to accurately and reproducibly assess the sagittal jaw relationship. Sagittal G-triangle analysis, which consists of angles AXK and BXK, is based on an equilateral triangle (Bo-X-K) constructed using 5 cephalometric landmarks (Ba, Bo, Po, Or, and G). To test the diagnostic efficiency of this analysis, pretreatment cephalometric radiographs of 120 female and 120 male Chinese patients were randomly selected. For each enlisted subject, angles SNA and SNB as well as angles AXK and BXK were measured and recorded. On the basis of the SNA and SNB results, subjects were categorized into 6 groups: maxillary retrognathism, normal maxilla, maxillary prognathism, mandibular retrognathism, normal mandible, and mandibular prognathism. The diagnostic efficiency of angles AXK and BXK were evaluated using various statistical tests. A high correlation was detected between angles SNA and AXK as well as between angles SNB and BXK. Female patients with angle AXK between -2.255° and 2.860° and male patients with angle AXK between -2.615° and 2.120° were considered to have a normal maxilla position. Female patients with angle BXK between -2.61° and 2.93° and male patients with angle BXK between -2.275° and 0.610° were considered to have a normal mandible position. In conclusion, sagittal G-triangle analysis could be used as an alternative method for the evaluation of the sagittal position of the maxilla and mandible in cephalometric analysis.

Co-assembled Monolayers as Hole-Selective Contact for High-Performance Inverted Perovskite Solar Cells with Optimized Recombination Loss and Long-Term Stability.

Self-assembled monolayers (SAMs) have been widely employed as an effective way to modify interfaces of electronic/optoelectronic devices. To achieve a good control of the growth and molecular functionality of SAMs, we develop a co-assembled monolayer (co-SAM) for obtaining efficient hole selection and suppressed recombination at the hole-selective interface in inverted perovskite solar cells (PSCs). By engineering the position of methoxy substituents, an aligned energy level and favorable dipole moment can be obtained in our newly synthesized SAM, ((2,7-dimethoxy-9H-carbazol-9-yl) methyl) phosphonic acid (DC-PA). An alkyl ammonium containing SAM is co-assembled to further optimize the surface functionalization and interaction with perovskite layer on top. A champion device with an excellent power conversion efficiency (PCE) of 23.59 % and improved device stability are achieved. This work demonstrates the advantage of using co-SAM in improving performance and stability of PSCs.

Simultaneous and Accurate Quantification of Multiple Antibiotics in Aquatic Samples by Surface-Enhanced Raman Scattering Using a Ti3C2Tx/DNA/Ag Membrane Substrate.

Rapid and accurate analysis of multiple targets in complex samples is still a big challenge in the fast detection field. Herein, we developed a rapid and accurate strategy for simultaneous quantification of trace multiple antibiotic residues in complex aquatic samples by surface-enhanced Raman scattering (SERS) using a Ti3C2Tx/DNA/Ag membrane substrate. This membrane substrate was proven to have good uniformity, reproducibility, stability, and SERS activity by a series of characterizations. Also, this substrate combined excellent electromagnetic enhancement and chemical enhancement effects, which endowed it with good sensitivity and selectivity during SERS analysis. It achieved the integration of multitarget separation, enrichment, and in situ detection, which significantly improved the selectivity, sensitivity, accuracy, and detection throughput by membrane substrate coupling with SERS for real-sample analysis. Finally, this rapid SERS analysis strategy was successfully applied to the simultaneous quantification of trace nitrofurantoin (NFT) and ofloxacin (OFX) in aquatic samples. It was observed that trace NFT and OFX were actually detected and simultaneously quantified to be 8.0-13.7 and 42.6-49.1 µg/kg in aquatic samples, respectively, with good recoveries of 88.0-107% and relative standard deviations of 0.3-5.5%. The results were verified by a traditional high-performance liquid chromatography method with relative errors of -9.8 to 5.3%. This strategy provided a methodological reference for accurate SERS quantification of multiple targets in complex samples.

Synthesis of sea urchin-shaped Au nanocrystals by double-strand diblock oligonucleotides for surface-enhanced Raman scattering and catalytic application.

It is of great significance to construct specially designed gold nanocrystals (AuNCs) with precisely controllable size and morphology to achieve an excellent physicochemical performance. In this work, sea urchin-shaped AuNCs with tunable plasmonic property were successfully synthesized by the hybridized double-strand poly adenine (dsPolyA) DNA-directed self-assembly technique. Hybridized dsPolyA as the directing template had suitable rigidity and upright conformation, which benefited the controllable formation of these anisotropic multi-branched AuNCs with the assistance of surfactant. The effects of essential conditions influencing the synthesis and precise morphology control were investigated in detail. COMSOL simulation was used to evaluate their electromagnetic field distribution according to their morphologies, and the result suggested that sea urchin-shaped AuNCs had abundant 'hot spots' for surface-enhanced Raman scattering (SERS) detection due to their regular nanoprotuberance structure. Finally, sea urchin-shaped AuNCs with excellent SERS and catalytic performance were applied for the quantitative analysis of food colorant and catalytic degradation of potential pollutants. The SERS enhancement factor of sea urchin-shaped AuNCs was up to 5.27 × 106, and the catalytic degradation rate for 4-NP by these AuNCs was up to -0.13min-1.

Advanced materials on sample preparation for safety analysis of aquatic products.

Safety analysis of aquatic products has been a challenge in recent years due to the serious matrix interference, complex characteristics, and ultra-low content of analytes. Introducing advanced materials to sample preparation technique can greatly improve the extraction, enrichment, and separation for further qualification and quantification of target analytes by coupling with consequent analytical technologies. Based on this scope, this review is mainly introducing advanced materials on the sample preparation for safety analysis of aquatic products in the past decade. After introducing the importance of the corresponding advanced materials, advanced materials are used for the sample preparation and in the improvement of safety analysis result of aquatic products. Advanced materials for sample preparation of aquatic products were reviewed including carbon materials, metal organic frameworks, covalent organic frameworks, molecularly/ions imprinted polymers, etc. Then, applications of the advanced materials for the analysis of specific fishery analytes (antibiotics, anesthetic, preservatives, etc.) were briefly introduced. Conclusions and perspectives on advanced materials for sample preparation and safety analysis of aquatic products were also presented.

Rapid and accurate determination of trace volatile sulfur compounds in human halitosis by an adaptable active sampling system coupling with gas chromatography.

Halitosis with the main components of trace volatile sulfur compounds widely affects the quality of life. In this study, an adaptable active sampling system with two sample-collection modes of direct injection and solid-phase microextraction was developed for the rapid and precise determination of trace volatile sulfur compounds in human halitosis coupled with gas chromatography-flame photometric detection. The active sampling system was well designed and produced for efficiently sampling and precisely determining trace volatile targets in halitosis under the optimized sampling and detection conditions. The analytical method established was successfully applied for the determination of trace targets in halitosis. The limits of detection of H2 S, CH3 SH, and CH3 SCH3 by direct injection were 0.0140-23.0 µg/L with good recoveries ranging from 82.2 to 118% and satisfactory relative standard deviations of 0.4-9.5% (n = 3), respectively. The limit of detections of CH3 SH and CH3 SCH3 by solid-phase microextraction were 2.03 and 0.186 × 10-3  µg/L with good recoveries ranging from 98.3 to 108% and relative standard deviations of 5.9-9.0% (n = 3). Trace volatile targets in positive real samples could be actually found and quantified by combination of direct injection and solid-phase microextraction. This method was reliable and efficient for the determination of trace volatile sulfur compounds in halitosis.

Preparation and characterization of molecularly imprinted polymers based on ß-cyclodextrin-stabilized Pickering emulsion polymerization for selective recognition of erythromycin from river water and milk.

Molecularly imprinted polymers were prepared via ß-cyclodextrin-stabilized oil-in-water Pickering emulsion polymerization for selective recognition and adsorption of erythromycin. The synthesized molecularly imprinted polymers were spherical in shape, with diameters ranging from 20 to 40 µm. The molecularly imprinted polymers showed high adsorption capacity (87.08 mg/g) and adsorption isotherm data fitted well with Langmuir model. Adsorption kinetics study demonstrated that the molecularly imprinted polymers acted in a fast adsorption kinetic pattern and the adsorption features of molecularly imprinted polymers followed a pseudo-first-order model. Adsorption selectivity analysis revealed that molecularly imprinted polymers had a much better specificity for erythromycin than that for spiramycin or amoxicillin, and the relative selectivity coefficient values on the bases of spiramycin and amoxicillin were 3.97 and 3.86, respectively. The Molecularly imprinted polymers also showed a satisfactory reusability after four times of regeneration. In addition, molecularly imprinted polymers exhibited good adsorption capacities for erythromycin under complicated environment, that is, river water and milk. These results proved that the as-prepared molecularly imprinted polymers is a potent absorbent for selective recognition of erythromycin, and therefore it may be a promising candidate for practical applications, such as wastewater treatment and detection of erythromycin residues in food.

Multi-region saliency-aware learning for cross-domain placenta image segmentation.

We propose a multi-region saliency-aware learning (MSL) method for cross-domain placenta image segmentation. Unlike most existing image-level transfer learning methods that fail to preserve the semantics of paired regions, our MSL incorporates the attention mechanism and a saliency constraint into the adversarial translation process, which can realize multi-region mappings in the semantic level. Specifically, the built-in attention module serves to detect the most discriminative semantic regions that the generator should focus on. Then we use the attention consistency as another guidance for retaining semantics after translation. Furthermore, we exploit the specially designed saliency-consistent constraint to enforce the semantic consistency by requiring the saliency regions unchanged. We conduct experiments using two real-world placenta datasets we have collected. We examine the efficacy of this approach in (1) segmentation and (2) prediction of the placental diagnoses of fetal and maternal inflammatory response (FIR, MIR). Experimental results show the superiority of the proposed approach over the state of the art.

A covalently cross-linked microporous polymer based micro-solid phase extraction for online analysis of trace pesticide residues in citrus fruits.

Covalently cross-linked microporous polymers are a new class of highly cross-linked porous network materials with large surface area and potential superiority in sample pretreatment. In this work, a covalently cross-linked microporous polymer was well designed and synthesized by condensation of acylhydrazines in terephthalic dihydrazide with aldehyde groups in 1,3,5-benzenetricarboxaldehyde. The adsorption mechanism was explored and discussed based on π-π stacking interaction and steric effect. Then, a covalently cross-linked microporous polymer was employed as the adsorbent of online micro-solid-phase extraction coupled with high-performance liquid chromatography for the enrichment and analysis of trace pesticide residues in citrus fruits. The method was successfully applied to the online analysis of sugar orange and Huangdigan samples with the detection limits of 0.10-0.30 µg/kg. It was satisfactory that chlorpifos and triazophos in real sugar orange and Huangdigan samples could be actually found and quantified at concentrations of 0.20 and 0.51 mg/kg, respectively. The recoveries of sugar orange and Huangdigan samples were in the range of 70.0-103 and 74.0-119% with relative standard deviations of 0.4-9.7 and 0.5-9.2% (n = 3), respectively. The proposed method was accurate, reliable, and convenient for the online simultaneous analysis of trace pesticide residues in citrus fruits.

Miniaturized Thermal-Assisted Purge-and-Trap Technique Coupling with Surface-Enhanced Raman Scattering for Trace Analysis of Complex Samples.

It still remains a great challenge for quantification of trace analytes in complex samples by surface-enhanced Raman scattering (SERS) technique due to potential matrix influence or weak SERS responses of analytes. In this work, a miniaturized thermal-assisted purge-and-trap (MTAPT) device was designed and developed to eliminate matrix influence coupled with derivatization method before SERS analysis. The design of MTAPT chamber was optimized based on quantitative calculation of its dead volume by computational fluid dynamics simulation. The small straight chamber was selected as an optimized design with a recovery of 96.1% for formaldehyde. The practical feasibility of MTAPT was validated based on four real analytical applications including phenthiol in industrial water, formaldehyde in flour, sulfion in wastewater, and methanol in industrial alcohol. The results showed that SERS responses of all analytes dramatically increased by eliminating sample matrices after MTAPT process. Phenthiol, formaldehyde, sulfion, and methanol in real samples could be accurately quantified with recoveries of 80.9-110.0%, and the analytical results were validated by corresponding standard methods. The time consumption of MTAPT-SERS for real sample analysis including sample preparation and determination was within 16 min. It is highly expected that the combination of MTAPT technique with portable SERS instrument can greatly expand the range of SERS analysis. The proposed MTAPT-SERS method has high potential for on-site analysis of complex samples.

Resonance perfect absorption by exciting hyperbolic phonon polaritons in 1D hBN gratings.

Natural materials with hyperbolic responses can confine light with well-defined propagation directions inside the micro/nanostructure. Here we theoretically demonstrate that strong resonance absorption can be achieved in one-dimensional gratings made of hexagonal boron nitride (hBN) due to hyperbolic phonon polaritons. The radiative properties of both trapezoidal and square resonators are calculated using anisotropic rigorous coupled-wave analysis. The resonance wavelengths can be theoretically predicted and are shown to follow the anomalous or traditional scaling laws depending on the hyperbolicity. These findings may benefit the applications including photodetection, color filters, and optomechanics.

An intrinsic internal standard substrate of Au@PS-b-P4VP for rapid quantification by surface enhanced Raman scattering.

Reliable quantification by surface enhanced Raman scattering (SERS) highly depends on the development of a reproducible substrate with excellent anti-interference capability. In this work, an intrinsic internal standard (IS) SERS substrate based on a diblock copolymer, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP), as a template was developed by a modified block copolymer lithography (BCL) technique of reserving the diblock copolymer template. This substrate generated a stable vibration peak at 1066 cm-1 attributed to poly(4-vinylpyridine) (P4VP) which could be used as an intrinsic IS for precise SERS quantification. A series of characterization results showed that the diblock copolymer template endowed this substrate with homogeneous distribution of Au nanoparticles, excellent stability and reproducibility. A minor relative standard deviation (RSDs) of SERS responses at 1066 cm-1 was measured and calculated to be 4.3% from ten different substrates in the same batch, which suggested good substrate-to-substrate reproducibility of this substrate. Finally, this intrinsic IS substrate was successfully applied for the rapid quantification of a trace banned dye, chrysoidine, in food samples with complicated matrices by SERS. It was proved that chrysoidine could be found and quantified to be 0.50 and 0.41 mg L-1 in a positive dried bean curd stick and chilli powder sample respectively with good recoveries by this substrate coupled with SERS. The development of intrinsic IS substrates would benefit rapid and accurate quantification of trace targets in complex samples coupled with SERS analysis.

Rapid determination of trace semicarbazide in flour products by high-performance liquid chromatography based on a nucleophilic substitution reaction.

Semicarbazide, a toxic food contaminant, widely exists in food products and it originates from the thermal degradation of a food additive of azodicarbonamide or a metabolite of nitrofurazone abused in meat specimens. Many previous methods for semicarbazide determination usually required expensive instruments, difficult-to-prepare monoclonal antibodies, and a long operation time. In this study, a high-performance liquid chromatography method was developed for the rapid determination of trace semicarbazide coupling with a nucleophilic substitution reaction firstly using 4-nitrobenzoyl chloride as derivatization reagent. The derivatization reaction was mild at room temperature for 1 min in neutral solution. Then, semicarbazide derivative was separated and quantified by high-performance liquid chromatography with ultraviolet detection under optimal separation conditions at λmax = 261 nm. The proposed method offered the detection limit of 1.8 µg/L and was successfully applied for the rapid determination of trace semicarbazide in flour products. Semicarbazide in positive real samples could be actually found and quantified in the range of 0.47-7.53 mg/kg. The recoveries were 76.6-119% with relative standard deviations of 0.5-9.1% (n = 3). This developed method was rapid, reliable, and convenient for the determination of trace semicarbazide in food.

Acrylamide-functionalized graphene micro-solid-phase extraction coupled to high-performance liquid chromatography for the online analysis of trace monoamine acidic metabolites in biological samples.

Monoamine acidic metabolites in biological samples are essential biomarkers for the diagnosis of neurological disorders. In this work, acrylamide-functionalized graphene adsorbent was successfully synthesized by a chemical functionalization method and was packed in a homemade polyether ether ketone micro column as a micro-solid-phase extraction unit. This micro-solid-phase extraction unit was directly coupled to high-performance liquid chromatography to form an online system for the separation and analysis of three monoamine acidic metabolites including homovanillic acid, 5-hydroxyindole-3-acetic acid, and 3,4-dihydroxyphenylacetic acid in human urine and plasma. The online system showed high stability, permeability, and adsorption capacity toward target metabolites. The saturated extraction amount of this online system was 213.1, 107.0, and 153.4 ng for homovanillic acid, 5-hydroxyindole-3-acetic acid, and 3,4-dihydroxyphenylacetic acid, respectively. Excellent detection limits were achieved in the range of 0.08-0.25 µg/L with good linearity and reproducibility. It was interesting that three targets in urine and plasma could be actually quantified to be 0.94-3.93 µg/L in plasma and 7.15-19.38 µg/L in urine. Good recoveries were achieved as 84.8-101.4% for urine and 77.8-95.1% for plasma with the intra- and interday relative standard deviations less than 9.3 and 10.3%, respectively. This method shows great potential for online analysis of trace monoamine acidic metabolites in biological samples.