Composition of breast milk from mothers of premature and full-term infants and its influence in Z-Scores for infant physical growth.

BACKGROUND: Breast milk contains various crucial nutrients and biologically active substances and is ideal for newborns. This study aimed to analyze the composition of breast milk from mothers of premature and full-term infants and its influences on the growth of infants. METHODS: Infant-mother dyads examined at our Hospital (March 2016 to May 2017) were included. Milk was collected at 0-1 month, 2-3 months, and 5-6 months and analyzed using a MIRIS human milk analyzer. Z-scores of weight-for-length (WLZ), weight-for-age (WAZ), and length-for-age (LAZ) were calculated. RESULTS: This study included full-term (> 37 weeks of gestation, n = 177) and premature (< 37 weeks, n = 94) infant-mother dyads. The premature infants showed higher ΔWAZ, ΔLAZ, and ΔWLZ from infancy to toddlerhood for the physical growth speed, compared with term infants (P < 0.001). All proteins and true protein components of breast milk decreased with infants' age (P < 0.001). For premature and full-term infants, differences in ΔWAZ and ΔLAZ from birth to infancy and the difference in ΔLAZ, WAZ, and LAZ in toddlerhood were positively associated with non-protein nitrogen (NPN) (all P < 0.05), while the Z-score differences in ΔWLZ from birth to infancy were negatively associated with NPN (all P < 0.05). For premature babies, from birth to infancy stage, ΔWAZ was positively correlated with NPN and carbohydrates while negatively correlated with dry matter (all P < 0.05), and ΔLAZ correlated with NPN (ß = 0.428, P = 0.005). CONCLUSION: Breastfeeding helped premature infants compensatory growth when compared to term infants. Whileduring early infancy stage ΔWLZ gain was negatively associated with increased amounts of NPN in breast milk. This might mean although NPN increase the Z-scores of weight-for-age and length-for-age, with no rise in adipose tissue mass.

Molecularly imprinted ratiometric fluorescence sensor for visual detection of 17ß-estradiol in milk: A generalized strategy toward imprinted ratiometric fluorescence construction.

17ß-Estradiol (E2) is the typical endocrine disruptor of steroidal estrogens and is widely used in animal husbandry and dairy processing. In the environment, even lower concentrations of E2 can cause endocrine dysfunction in organisms. Herein, we have developed a novel molecularly imprinted ratiometric fluorescent sensor based on SiO2-coated CdTe quantum dots (CdTe@SiO2) and 7-hydroxycoumarin with a post-imprint mixing strategy. The sensor selectively detected E2 in aqueous environments due to its two fluorescent signals with a self-correction function. The sensor has been successfully used for spiking a wide range of real water and milk samples. The results showed that the sensor exhibited good linearity over the concentration range 0.011-50 µg/L, obtaining satisfactory recoveries of 92.4-110.6% with precisions (RSD) < 2.5%. Moreover, this sensor obtained an ultra-low detection limit of 3.3 ng/L and a higher imprinting factor of 13.66. By using estriol (E3), as a supporting model, it was confirmed that a simple and economical ratiometric fluorescent construction strategy was provided for other hydrophobic substances.

A novel urease-assisted ratiometric fluorescence sensing platform based on pH-modulated copper-quenched near-infrared carbon dots and methyl red-quenched red carbon dots for selective urea monitoring.

A novel and sensitive fluorescence ratiometric method is developed for urea detection based  on the pH-sensitive response of two fluorescent carbon dot (CD) systems: R-CDs/methyl red (MR) and NIR-CDs/Cu2+. The sensing mechanism involves breaking down urea using the enzyme urease, releasing ammonia and increasing pH. At higher pH, the fluorescence of NIR-CDs is quenched due to the enhanced interaction with Cu2+, while the fluorescence of R-CDs is restored as the acidic MR converts to its basic form, removing the inner filter effect. The ratiometric signal (F608/F750) of the R-CDs/MR and NIR-CDs/Cu2+ intensities changed in response to the pH induced by urea hydrolysis, enabling selective and sensitive urea detection. Detailed spectroscopic and morphological investigations confirmed the fluorescence probe design and elucidated the sensing mechanism. The method exhibited excellent sensitivity (0.00028 mM LOD) and linearity range (0.001 - 8.0 mM) for urea detection, with successful application in milk samples for monitoring adulteration, demonstrating negligible interference and high recovery levels (96.5% to 101.0%). This ratiometric fluorescence approach offers a robust strategy for selective urea sensing in complicated matrices.

Chloramphenicol-imprinted polychitosan bounded with carbon dots as fluorescent sensor, dispersive sorbent, and drug carrier.

Chitosan, an abundant natural polysaccharide, was conjugated with carbon dots (CDs) and self-polymerized with chloramphenicol (CAP) templates to synthesize CD-incorporated and molecularly CAP-imprinted polychitosan (CD-MIC). The CD-MIC was used for fluorescent sensing, dispersive sorption, and dosage release of CAP at different pH levels. The sphere of action mechanism, approved by emission and excitation fluorescence, UV-Vis absorption, and fluorescence lifetime measurements, regulated the fluorescence static quenching. By the Perrin model, the quenching extent was linearly correlated to CAP within 0.17 - 33.2 µM (LOD = 37 nM) at pH 7.0. With an imprinting factor of 3.1, the CD-MIC was more selective for CAP than CD, although it was less sensitive to CAP. The recoveries of 5.0 µM CAP from milk matrix were 95% (RSD = 2.3%) for CD-MIC probes and 62% (RSD = 4.5%) for CD. The Langmuir and pseudo-second-order models preferably described the isothermal and kinetic sorptions of CAP into the imprinted cavities in CD-MICs, respectively. The Weber - Morris kinetic model showed three stages involved in intraparticle diffusion, which was pH-dependent and gradually arduous at the later stage, and showed external diffusion partly engaged in the diffusion mechanism. The 20 - 70% of CAP formulated in CAP-embedded CD-MICs were released in 8 - 48 h. The release percentage was lower at pH 7.0 than at pH 5.0 and 9.0, but the equilibrium time was shorter. At pH 7.0, the release percentage reached 45% at 10 min and slowly increased to 51% at 24 h.

Hydroxylated hierarchical flower-like COF for solid-phase extraction of adrenergic receptor agonists in milk.

A new detection platform based on a hydroxylated covalent organic framework (COF) integrated with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was constructed and used for detecting adrenergic receptor agonists (ARAs) residues in milk. The hydroxylated COF was prepared by polymerization of tris(4-aminophenyl)amine and 1,3,5-tris(4-formyl-3-hydroxyphenyl)benzene and applied to solid-phase extraction (SPE) of ARAs. This hydroxylated COF was featured with hierarchical flower-like morphology, easy preparation, and copious active adsorption sites. The adsorption model fittings and molecular simulation were applied to explore the potential adsorption mechanism. This detection platform was suitable for detecting four α2- and five ß2-ARAs residues in milk. The linear ranges of the ARAs were from 0.25 to 50 µg·kg-1; the intra-day and the inter-day repeatability were in the range 2.9-7.9% and 2.0-10.1%, respectively. This work demonstrates this hydroxylated COF has great potential as SPE cartridge packing, and provides a new way to determine ARAs residues in milk.

Label-free colorimetric sensor for Pb2+ determination using catalytic activity of MnO2 nanoflowers and elongated aptamer.

In this study, a label-free aptasensor utilizing colorimetric properties was developed to detect Pb2+ with high sensitivity. The approach involved applying modified aptamer which enhanced the oxidase-mimicking activity of MnO2 nanoflowers. This innovative method provides an efficient means for monitoring Pb2+ ions without requiring any labeling techniques. The fundamental principle of this aptasensor is based on the adsorption of a modified aptamer onto MnO2 nanoflowers' surface, which in turn increases their affinity for chromogenic substrates and enhances their catalytic activity. The proposed aptasensor exploits the high sensitivity due to the extension of the aptamer sequence length by terminal deoxynucleotidyl transferase (TdT). Under optimum experimental conditions, the developed colorimetric aptasensor indicated a linear detection range from 4 to 80 nM with a limit of detection (LOD) of 1.4 nM. Moreover, the aptasensor successfully monitored Pb2+ in the drinking water, milk and human serum samples. Henceforth, the colorimetric aptasensor exhibited in this study possesses several benefits such as uncomplicated operation, cost-effectiveness, label-free detection and remarkable sensitivity. Thus rendering it a suitable option for analyzing intricate samples.

All-solid-state chip utilizing molecular imprinted polymer for erythromycin detection in milk samples: Printed circuit board-based potentiometric system.

Detection of erythromycin (ERY) residues in commercial milk samples is crucial for the safety assessment. Herein, a printed circuit board was patterned as a feasible miniaturized potentiometric sensor for ERY determination in dairy samples. The proposed chip design fits to a 3.5-mm female audio plug to facilitate the potential measurements of working electrode versus reference one in this all-solid-state system. The sensor utilizes molecular imprinted polymer (MIP) for the selective recognition of the studied drug in such challenging matrix. The electrode stability is achieved through the addition of poly (3,4-ethylenedioxythiophene) nano-dispersion on its surface. The proposed device detects down to 6.6 × 10-8 M ERY with a slope of 51 mV/decade in the 1 × 10-7-1 × 10-3 M range. The results display high accuracy (99.9% ± 2.6) with satisfactory relative standard deviation for repeatability (1.6%) and reproducibility (5.0%). The effect of common antibiotic classes, namely, amphenicols, beta-lactams, fluoroquinolones, sulfonamides, and tetracyclines, can be neglected as evidenced by their calculated binding capacities towards the proposed MIP. The calculated selectivity coefficients also show a good electrode performance in the presence of naturally present inorganic ions allowing its application to different milk samples.

Self-ratiometric fluorescence approach based on plant extract-assisted synthesized silver nanoparticles for the determination of vanillin.

The current study designed and applied a novel self-ratiometric fluorescent nanosensor composed of green-synthesized silver nanoparticles (Ag-NPs) to determine vanillin in adult and infant foods and human plasma. A straightforward microwave-assisted approach is proposed for synthesizing Ag-NPs in less than 1 min using a reducing agent, tailed pepper seed extract. The synthesized Ag-NPs had a strong fluorescence with an intense emission band at 360 nm and a shoulder peak at 430 nm when excited at 265 nm. Upon interaction with vanillin, the fluorescence peak of Ag-NPs at 360 nm decreases in a concentration-dependent manner while being shifted to a longer wavelength, 385 nm. Meanwhile, the shoulder fluorescence peak at 430 nm is only slightly affected by vanillin addition. Thus, a new Ag-NP self-ratiometric probe was designed and validated for vanillin determination using the peak at 385 nm and the shoulder peak at 430 as two built-in reference peaks. The optimized system accurately measured vanillin with a detection limit of 9.0 ng/mL and a linear range of 0.05-8.0 µg/mL without needing pre-derivatization or high-cost instrumentation. The method successfully measured vanillin in adult and infant milk formula, biscuits, and human plasma samples with high percentage recoveries (95.3-104.6%) and excellent precision (relative SD; ≤3.85%).

LED-Based Desktop Analyzer for Fat Content Determination in Milk.

In dairy, there is a growing request for laboratory analysis of the main nutrients in milk. High throughput of analysis, low cost, and portability are becoming critical factors to provide the necessary level of control in milk collection, processing, and sale. A portable desktop analyzer, including three light-emitting diodes (LEDs) in the visible light region, has been constructed and tested for the determination of fat content in homogenized and raw cow's milk. The method is based on the concentration dependencies of light scattering by milk fat globules at three different wavelengths. Univariate and multivariate models were built and compared. The red channel has shown the best performance in prediction. However, the joint use of all three LED signals led to an improvement in the calibration model. The obtained preliminary results have shown that the developed LED-based technique can be sufficiently accurate for the analysis of milk fat content. The ways of its further development and improvement have been discussed.

Aptamer-AuNP-conjugated carboxymethyl chitosan-functionalized graphene oxide for colorimetric identification of Salmonella typhimurium.

A novel aptamer-AuNP-conjugated carboxymethyl chitosan-functionalized graphene oxide (CMC/GO@Apt-Au NP) probe was for the first time developed for the determination of Salmonella typhimurium (S. typhimurium). Owing to the conformational change of the aptamers in the presence of S. typhimurium, the Au NPs, which were pre-adsorbed on the aptamers through van der Waals forces, were released into the solution phase and induced the color change of the solution. As a result, S. typhimurium ranging from 102 to 107 CFU/mL was successfully identified using the designed assay with a limit of detection (LOD) of 10 CFU/mL. This low detection level allowed the sensitive recognition of S. typhimurium in milk samples within 40 min without sample pretreatment, a conclusion that agreed well with the traditional plate counting method. The developed method not only provides a rapid way for the determination of S. typhimurium with simplicity and sensitivity but also shows potential universality in the quantification of other pathogenic microorganisms.

Sulfonic acid-functionalized covalent organic frameworks as the coating for stir bar sorptive extraction of fluoroquinolones in milk samples.

Sulfonic acid-functionalized covalent organic frameworks (COF-SO3) as a coating of stir bar sorptive extraction (SBSE) for capturing three fluoroquinolones from milk have been developed. The COF-SO3 material was characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. Milk without any typical treatments like protein precipitation and defatting was only diluted five times with water for test. Combined with high-performance liquid chromatography (HPLC), a SBSE-HPLC method was established for detecting fluoroquinolones in milk samples. The corresponding wide linear ranges (4.00-500.0 µg L-1), low detection limits (1.20-2.62 µg L-1), good test repeatability (RSD < 5.2%), and acceptable enrichment factors (56.2-61.5) were implemented for three fluoroquinolones. The analytical method was applied to determine trace targets and provided satisfactory results. Furthermore, the research displayed satisfied reproducibility for bar-to-bar (RSD < 6.5%) and batch-to-batch (RSD < 8.6%) tests.

Fabrication of highly fluorinated porphyrin-based covalent organic frameworks decorated Fe3O4 nanospheres for magnetic solid phase extraction of fluoroquinolones.

A highly fluorinated porphyrin-based covalent organic frameworks magnetic adsorbent (FPy-COF@PDA@Fe3O4) was fabricated by using polydopamine (PDA) grafting Fe3O4 nanospheres as magnetic core and FPy-COF as shell for magnetic solid phase extraction (MSPE) of fluoroquinolones (FQs). FPy-COF was constructed by using 5,15-bis(4-aminophenyl)-10,20-bis(perfluorophenyl)porphyrin and 4,4'-biphenyldicarboxaldehyde as two building blocks. PDA as a bridge grafting on the surface of Fe3O4 nanospheres facilitated the growth of FPy-COF. The morphology and structure of FPy-COF@PDA@Fe3O4 adsorbent were characterized in detail. The prepared magnetic adsorbent exhibited good extraction capability to amphiphilic FQs due to their superior chemical affinities such as fluorophilic interaction and hydrogen-bond interaction from nitrogen-rich skeleton. Under the optimized conditions, the MSPE method combined with high performance liquid chromatography with ultraviolet detection (HPLC-UV) was developed to sensitively quantify trace level of six FQs in milk samples. The developed MSPE-HPLC method showed good linearity with wide concentration range, precision, and low limits of detection (S/N = 3) for six FQs as low as 2.3 ngꞏmL-1 in milk. The extraction recoveries of different spiked concentrations were in the range 77.8-110.4% for milk samples with RSD less than 9.7%.

Construction of a magnetic covalent organic framework for magnetic solid-phase extraction of AFM1 and AFM2 in milk prior to quantification by LC-MS/MS.

A magnetic covalent organic framework (M-COF) was designed and selected as sorbent for magnetic solid-phase extraction (MSPE) of AFM1 and AFM2 in milk, followed by LC-MS/MS analysis. The application of 2,5-Dihydroxy-1,4-benzenedicarboxaldehyde (Dt) and 4',5'-bis(4-aminophenyl)-[1,1':2',1″-terphenyl]-4,4″-diamine (BAPTPDA) as monomers endows M-COF excellent properties for adsorbing AFM1 and AFM2. The morphology, structure, stability, and magnetism of the Fe3O4@COF(BAPTPDA-Dt) were characterized by various techniques including scanning electron microscopy, transmission electron microscopy, FTIR, thermogravimetric analysis, and vibrating sample magnetometer. The Fe3O4 microspheres were covered by COF shells. Fe3O4@COF exhibited excellent magnetism and stability. Some parameters that may influence the adsorption efficiency of MSPE were also optimized, making the extraction process more effective, time-saving (about 3 min), and less organic-reagent-consuming (only 4 mL of acetonitrile required). It is noteworthy that the Fe3O4@COF(BAPTPDA-Dt) can be reutilized more than 8 times. The AFM1 and AFM2 were determined by LC-MS/MS. The LODs for AFM1 and AFM2 were in the range 0.0069 to 0.0078 µg kg-1. A wide linearity range (0.01-100 µg kg-1) with coefficients of determination (R2) ranging from 0.9998 to 0.9999 was obtained. The recoveries at four spiked concentrations (0.05, 0.5, 5, and 50 µg kg-1) in the milk matrix ranged from 85.2 to 106.5%. The intraday RSDs and the interday RSDs were in the range 1.74-4.58% and 2.65-6.69%, respectively. The matrix effect (9.3% for AFM1 and 6.7% for AFM2) was also significantly lower than that observed in other work . Overall, the established method has provided a powerful tool for rapid pretreatment and sensitive determination of AFM1 and AFM2 in milk with negligible matrix effect, presenting important value in toxicant determination.

Macronutrient analysis of human milk and factors associated with its composition in mothers of preterm infants ≤ 32 weeks.

We conducted an exploratory longitudinal study to evaluate the macronutrient composition of human milk in mothers delivering very preterm infants ≤ 32 weeks over the first 4 weeks of lactation and the association of human milk composition with maternal and neonatal factors A total of 213 human milk samples collected in the morning between 8 am and 12 pm from 60 eligible mothers were analyzed on 7 (n = 60), 14 (n = 60), 21 (n = 52), and 28 (n = 41) days of lactation by infrared transmission spectroscopy. The true protein content decreased significantly over 4 weeks (mean difference (95% confidence interval)) (MD (95% CI)) week 1 and week 4 = 0.2 g (0.037 to 0.363, P = 0.009)). On the contrary, the mean fat and calorie content showed significant increase over time (MD (95% CI)) = - 1.03 g (- 1.719 to - 0.343, P = 0.001) and - 9.0 kcal/dl (- 15.170 to - 2.830, P = 0.001), respectively). There was no difference in the carbohydrate content of human milk over 4 weeks. Macronutrient composition was independent of maternal parity, mode of delivery, pre-pregnancy body mass index, umbilical artery Doppler flows, previous breast feeding experience, neonatal centile status, gestation, and infant's weight at birth. Multiple regression analysis of human milk composition with mother's dietary components showed no significant association. CONCLUSION : We conclude that in mothers who deliver very preterm infants ≤ 32 weeks, true protein content decreased, fat and calorie content increased, and carbohydrate content remained stable in human milk during first 4 weeks of lactation. Human milk macronutrient composition was independent of various maternal and neonatal factors including maternal body mass index and dietary intake. TRIAL REGISTRATION : CTRI/2017/02/007895 What is Known: • Preterm human milk has high temporal and inter-individual variation in the macronutrient composition. What is New: • In mothers who deliver very preterm infants < 32 weeks, true protein content decreases, fat and calorie content increases, and carbohydrate content remains stable in human milk during first 4 weeks of lactation. • Human milk macronutrient composition is independent of various maternal and neonatal factors including maternal body mass index and dietary intake.

Preparation of yellow-emitting carbon dots and their bifunctional detection of tetracyclines and Al3+ in food and living cells.

A novel bifunctional carbon dot (CD)-based sensing platform was constructed for detection of tetracyclines (TCs) and Al3+. The fluorescence CDs were fabricated by hydrothermal method using phenylenediamine (p-PD) and ethylenebis(oxyethylenenitrilo) tetraacetic acid (EGTA) as precursors. The obtained prepared CDs show bright yellow fluorescence (y-CDs, EX = 400 nm and Em = 556 nm), high fluorescence quantum yield (QY = 21.55 ± 0.06%), and preferable optical stability. TCs can directly quench the fluorescence of y-CDs based on static quenching characteristics and a small internal filtration effect (IEF). By adding Al3+ to the y-CDs + TCs system, the fluorescence is partly recovered because TCs escape from the surface of the y-CDs and form a more stable chelate with Al3+. The sensing platform displays good selectivity and high sensitivity to TCs and Al3+ with low detection limits of 0.057-0.23 µM and 0.091 µM, respectively. Importantly, this sensing platform has enabled the detection of TCs and Al3+ in milk samples with satisfactory recoveries and RSDs, confirming the reliability and feasibility of this method. Combining with low toxicity and preferable biocompatibility, the y-CDs are extended to cellular imaging and detection of CTC and Al3+ in A549 cells.

Lateral flow immunoassay for 5-hydroxyflunixin based on near-infrared fluorescence molecule as an alternative label to gold nanoparticles.

A high-affinity monoclonal antibody (mAb) has been prepared and separately a gold nanoparticle (AuNP)-based and a near-infrared (NIR) fluorescence-based lateral flow immunoassay (LFA) developed for determination of 5-hydroxyflunixin residue in raw milk. The AuNP and IRDye® 800CW were used to label anti-5-hydroxyflunixin mAb to form the AuNP-mAb and NIR dye-mAb conjugates, respectively. Quantitative determination of 5-hydroxyflunixin was achieved by imaging the optical or fluorescence intensity of the AuNP-mAb and NIR dye-mAb captured on the test line. As a result, the detection limits of the AuNP-based LFA and NIR dye-based LFA were 0.82 and 0.073 ng/mL in raw milk, respectively. The considerable improvement on assay sensitivity of the NIR-based LFA can be attributed to the lower background and less antibody consumption per test than that of the AuNP-based LFA. The spiking experiment by the NIR-based LFA yielded 85.7-112.6% recovery with a relative standard deviation below 14%, indicating that it has satisfactory assay accuracy and precision. Furthermore, the analytical results of actual samples by the NIR dye-based LFA were consistent with that by instrumental analysis. Therefore, these results demonstrated that the NIR dye is an ideal alternative label to the conventional AuNP for the development of LFA for veterinary drugs in animal-origin food. Graphical abstract.

Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin based on SERS substrates composited of Au nanoparticles supported on twice-oxidized graphene oxide.

A surface-enhanced Raman spectroscopy (SERS) substrate consisting of Au nanoparticles supported on twice-oxidized graphene oxide (ro-GO) for the determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was prepared. The Raman shift at △v = 779, 993, and 1203 cm-1 was collected on the excitation condition of λ = 785 nm for the qualitative identification of 2,3,7,8-TCDD in milk. The peak at △v = 1203 cm-1 was selected as the characteristic peak for quantitation. The quantitation calculation was realized in the concentration range 10 to 100 ng mL-1 with a limit of detection of 3.24 ng mL-1 in milk samples. The average recoveries of 2,3,7,8-TCDD in milk were 60.6-68.6% with relative standard deviations less than 6.4%. The long-term stability of the substrates was approximately 180 days at 4 °C. Further, the SERS method for the determination of 2,3,7,8-TCDD in milk samples based on the optimized hybrid SERS substrate and corresponding pre-treatment procedure is proposed. Graphical abstract Schematic representation of surface-enhanced Raman spectroscopy (SERS) determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in milk samples by Au nanoparticles supported on twice-oxidized graphene oxide (ro-GO/AuNP) as a substrate.

Net-like mesoporous carbon nanocomposites for magnetic solid-phase extraction of sulfonamides prior to their quantitation by UPLC-HRMS.

A net-like mesoporous carbon nanocomposite (MCN) was hydrothermally prepared by using filter paper as the raw material. The MCN contains magnetic nanoparticles of type Fe3O4 which result from the addition of Fe(NO3)3·9H2O during synthesis. The MCN was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectra, Brunauer-Emmett-Teller methods and vibrating sample magnetometry. The MCN is shown to be a viable material for magnetic solid-phase extraction of trace sulfonamides (SAs) including sulfadiazine, sulfapyridine, sulfamerazine, sulfamethazine, sulfamethizole, sulfamethoxypridazine, sulfachloropyridazine and sulfadimethoxine. Following desorption with acetone containing 0.5% ammonia, the SAs were quantified by UPLC with high-resolution mass spectrometric detection. With sulfamethazine as an example, the adsorption equilibrium configurations and the major interaction mechanism between SAs and the MCN were calculated by using density functional theory. Under the optimal conditions, the calibration plots are linear in the 0.05-10 ng·mL-1 SA concentration ranges. The limits of detection are between 7.2 and 13.6 ng·L-1. The recoveries from spiked samples ranged from 79 to 107%, with relative standard deviations of <9.9%. Graphical abstractSchematic representation of nanocomposite preparation, adsorption mechanism of sulfonamide and magnetic solid-phase extraction (MSPE) for sulfadiazine (SDZ), sulfapyridine (SPD), sulfamerazine (SMR), sulfamethazine (SMZ), sulfamethizole (SMT), sulfamethoxypridazine (SMP), sulfachloropyridazine (SCP) and sulfadimethoxine (SDMX). Quantification was accomplished by UPLC with high-resolution mass spectrometric detection.

Ultrasonication-facilitated synthesis of functionalized graphene oxide for ultrasound-assisted magnetic dispersive solid-phase extraction of amoxicillin, ampicillin, and penicillin G.

A simplistic approach is presented for the synthesis of ultrasonically fabricated graphene oxide functionalized with polyaniline and N-[3-(Trimethoxysilyl)propyl]ethylenediamine. The synthesized nanocomposite was then employed for the facile, green, ultrasound-assisted, magnetic dispersive solid-phase extraction of amoxicillin, ampicillin, and penicillin G in milk samples and infant formula prior to high-performance liquid chromatography-ultraviolet determination. The designed nanocomposites were comprehensively characterized using field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. In order to achieve the best extraction efficiencies, the influential parameters including pH, amount of magnetic sorbent, type and volume of elution solvent, extraction time, sample volume, and desorption time were assessed. At the optimum conditions, linear ranges of 2.5-1000 (µg L-1) for ampicillin and penicillin G and a linear range of 2.5-750 (µg L-1) were obtained for amoxicillin at optimum conditions. Moreover, the limits of detection (S/N = 3) of 0.5, 0.8, and 0.9 (µg L-1) were obtained for amoxicillin, ampicillin, and penicillin G, respectively. The precision (relative standard deviations (%)) values of 3.1, 2.6, and 2.5 at the concentration of 50 µg L-1 for seven replicates were obtained for ampicillin, amoxicillin, and penicillin G, respectively. The efficiencies of ≤ 96% and relative standard deviations of less than 3.1% were also obtained thereby confirming the high potential of the synthesized nanocomposites for simultaneous preconcentration and separation of the ß-lactam antibiotics in complex matrixes. Graphical Abstract.

Fluorometric determination of fipronil by integrating the advantages of molecularly imprinted silica and carbon quantum dots.

A fluorometric method is described for the determination of fipronil, a frequently-used insecticide. It exploits the blue fluorescence of carbon quantum dots (CQDs) and the selectivity of molecularly imprinted silica (MIS). The MIS was prepared via the sol-gel method by using fipronil as the template, 3-aminopropyltriethoxysilane as functional monomer, and tetraethoxysilane as cross-linker in the presence of CQDs. The blue fluorescence of the CQD@MIS, with excitation/emission peaks at 340/422 nm, is quenched by fipronil. The assay works in the 0. 70 pM to 47 µM fipronil concentration range, and the limit of detection is 19 pM. The method was successfully applied to the quantitation of fipronil in spiked eggs, milk, and tap water. Recoveries between 83.8 and 114.0% were achieved. The corresponding relative standard deviations (RSD) are less than 6.67%. Graphical abstractSchematic representation of a high sensitivite and selectivite fluorescence nanoprobe constructed by combining the excellent fluorescence property of carbon quantum dots and the predicted selectivity of molecularly imprinted silica. It was applied to analyze fipronil in egg, milk and tap water, respectively.