Recoveries In Range Research Articles

Negligible In Vitro Recovery of Macromolecules from Microdialysis Using 100 kDa Probes and Dextran in Perfusion Fluid

Microdialysis is applied in neurointensive care to monitor cerebral glucose metabolism. If recoverable, macromolecules may also serve as biomarkers in brain disease and provide clues to their passage across the blood–brain barrier. Our study aimed to investigate the in vitro recovery of human micro- and macromolecules using microdialysis catheters and perfusion fluids approved for clinical use. In vitro microdialysis of a bulk solution containing physiological or supraphysiological concentrations of glucose, lactate, pyruvate, human IgG, serum albumin, and hemoglobin was performed using two different catheters and perfusion fluids. One had a membrane cut-off of 20 kDa and was used with a standard CNS perfusion fluid, and the other had a membrane cut-off of 100 kDa and was perfused with the same solution supplemented with dextran. The flow rate was 0.3 µl/min. We used both push and push–pull methods. Dialysate samples were collected at 2-h intervals for 6 h and analyzed for relative recovery of each substance. The mean relative recovery of glucose, pyruvate, and lactate was > 90% in all but two sets of experiments. In contrast, the relative recovery of human IgG, serum albumin, and hemoglobin from both bulk solutions was below the lower limit of quantification (LLOQ). Using a push–pull method, recovery of human IgG, serum albumin, and hemoglobin from a bulk solution with supraphysiological concentrations were above LLOQ but with low relative recovery (range 0.9%–1.6%). In summary, exchanging the microdialysis setup from a 20 kDa catheter with a standard perfusion fluid for a 100 kDa catheter with a perfusion solution containing dextran did not affect the relative recovery of glucose and its metabolites. However, it did not result in any useful recovery of the investigated macromolecules at physiological levels, either with or without a push–pull pump system.

Reverse total shoulder arthroplasty for primary osteoarthritis with restricted preoperative forward elevation demonstrates similar outcomes but faster range of motion recovery compared to anatomic total shoulder arthroplasty

BackgroundReverse total shoulder arthroplasty (RSA) has been increasingly utilized for a variety of shoulder pathologies that are difficult to treat with anatomical shoulder arthroplasty (TSA). Few studies have compared the outcomes of TSA versus RSA in patients with cuff intact GHOA and poor preoperative forward elevation. This study aimed to determine whether there is a difference in functional outcomes and postoperative ROM between TSA and RSA in these patients. MethodsThis retrospective cohort study included 116 patients who underwent RSA or TSA between 2013 and 2022 for the treatment of rotator cuff intact primary osteoarthritis with restricted preoperative forward flexion (FF) and a minimum 1-year follow-up. Each arthroplasty group was divided into two subgroups: patients with preoperative FF between 91 and 120 degrees or FF lower than or equal to 90 degrees. Patients' clinical outcomes, including active range of motion (ROM), American Shoulder and Elbow Surgeons (ASES) score, Visual analog scale (VAS) for pain, and Subjective Shoulder Value (SSV) were collected. Clinical and radiographic complications were evaluated. ResultsThere was no significant difference between RSA and TSA in terms of sex (58.3% male vs 62.2% male, p=0.692), or follow-up duration (20.1 months vs 17.7 months, p=0.230). However, the RSA cohort was significantly older (72.0± 8.2 vs 65.4 ± 10.6, p=0.012) and weaker in FF and ER before surgery (p<0.001). There was no difference between RSA (57 patients) and TSA (59 patients) in VAS pain score (1.2 ± 2.3 vs 1.3 ± 2.3, p=0.925), SSV score (90 ± 15 vs 90 ± 15, p=0.859) or ASES score (78.4 ± 20.5 vs 82.1 ± 23.2, p=0.476). Postoperative active ROM was statistically similar between RSA and TSA cohorts in FF (145 ± 26 vs 146 ± 23, p= 0.728), and ER (39 ± 15 vs 41 ± 15, p= 0.584). However, IR was lower in the RSA cohort (p <0.001). This was also true in each subgroup. RSA led to faster postoperative FF and ER achievement at 3 months (p<0.001). There was no statistically significant difference in complication rates between cohorts. ConclusionThis study demonstrates that patients with GHOA who have a structurally intact rotator cuff but limited preoperative forward elevation can achieve predictable clinical improvement in pain, range of motion, and function after either TSA or RSA. Reverse arthroplasty may be a reliable treatment option in patients at risk for developing rotator cuff failure.

Modeling Framework for Cost Optimization of Process-Scale Desalination Systems with Mineral Scaling and Precipitation.

Cost-optimization models are powerful tools for evaluating emerging water treatment processes. However, to date, optimization models do not incorporate detailed chemical reaction phenomena, limiting the assessment of pretreatment and mineral scaling. Moreover, novel approaches for high-salinity and high-recovery desalination are typically proposed without direct quantification of pretreatment needs or mineral scaling. This work addresses a critical gap in the literature by presenting a modeling framework that includes complex water chemistry predictions with process-scale optimization. We use this approach to conduct a technoeconomic assessment on a conceptual high-recovery treatment train that includes chemical pretreatment (i.e., soda ash softening and recarbonation) and membrane-based desalination (i.e., standard and high-pressure reverse osmosis). We demonstrate how to develop and integrate accurate multidimensional surrogate models for predicting precipitation, pH, and mineral scaling tendencies. Our findings show that cost-optimal results balance the costs of pretreatment with reverse osmosis system design. Optimizing across a range of water recoveries (i.e., 50-90%) reveals multiple cost-optimal schemas that vary the chemical dosing in pretreatment and the design and operation of reverse osmosis. Our results reveal that pretreatment costs can be more than double the cost of the primary desalination process at high recoveries due to the extensive pretreatment required to control scaling. This work emphasizes the importance of and provides a framework for including chemistry and mineral scaling predictions in the evaluation of emerging technologies in high-recovery desalination.

Design of sonochemical assisted synthesis of Zr-MOF/g-C3N4-modified electrode for ultrasensitive detection of antipsychotic drug chlorpromazine from biological samples.

Therapid fabrication is describedof binary electrocatalyst based on a highly porous metal-organic framework with zirconium metal core (Zr-MOF) decorated over the graphitic carbon nitride (g-C3N4) nanosheets via facile ultrasonication method. It is used for the robust determination of antipsychotic drug chlorpromazine (CLP) from environmental samples. The electrochemical behaviour of 2D Zr-MOF@g-C3N4 was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies. The crystalline and porous nature of the composite was characterized by XRD and SEM analysis. The functional groups and surface characteristics were investigated by FT-IR, Raman and XPS. The major electrochemical properties of the Zr-MOF@g-C3N4 composite towards CLP detection were analyzed by CV, chronocoulometric (CC), chronoamperometric (CA) and differential pulse voltammetry (DPV) techniques. The composite exhibits a low detection limit (LOD) of 2.45nM with a linear range of 0.02 to 2.99µM and attractive sensitivity for CLP. The sensor system shows higher selectivity towards the possible interferences of CLP drug and exhibits betterrepeatability and stability. Finally, the fabricated sensor system shows a high recovery range varying from 96.2 to 98.9% towards the real samples. The proposed electrochemical probe might be a promising alternative to the prevailing diagnostic tools for the detection of CLP.

A highly sensitive electrochemical sensing probe incorporating classical Berthelot's reaction and glassy carbon electrode for measuring ultra-trace levels of ammonia/ NH4+ in water

In quantifying NH3 and/or NH4+ ions, the wavelength-based spectrochemical methods involving formation of colored products of the Berthelot’s or Nessler reactions might be challenging due to auto-self absorbance, spectral overlap, and background scattering noise. Thus, the current study reports a renewable glassy carbon electrode (GCE) sensing probe combined with Berthelot’s reaction (indophenol formation) and adsorptive square - wave-anodic stripping voltammetry (Ads SWSV) at pH = 10 for detection of NH3 and/or NH4+ in water. The redox characteristics and the high surface coverage of the oxidation product of indophenol on the sensing platform suggested its use for NH3 and/or NH4+ detection. The electrochemical sensing probe for NH4+ displayed good linear relationship between 5.56 nM and 55.6 μM of NH4+ with limits of detection (LOD) and quantitation (LOQ) of 4.83 × 10-9 and 1.47 × 10-8 M, and sensing probe sensitivity of 1.27μA/μM−1 cm−2,respectively. The probe was applied for measuring NH3/NH4+in fresh and seawater samples, and the results were validated using standard ion chromatography (IC) and micro spectrophotometry assays. The assembled probe was also tolerably selective against interfering of other contaminants in a comparable potential window. Additionally, the probe has exceptional selectivity, long-term stability, and repeatability, and has good capacity to detect NH3 and/or NH4+ ions with high accuracy (recovery range = 97.14 ± 4.12–102.9 ± 4.7) in environmental water samples. The calculated Student texp and Fexp values (n = 5) were less than the tabulated ttab (2.78) and Ftab (6.39) at 95 % probability (P = 0.05, n = 5). The study offer high reliability towards NH3 and/or NH4+ detection in complex environments.

A modified QuEChERS-based UPLC-MS/MS method for rapid determination of multiple antibiotics and sedative residues in freshwater fish

Antibiotics and sedatives are used in freshwater fish culture and transportation, and residue in freshwater fish pose potential risks to human health. Therefore, a throughput method was developed to detect antibiotic and sedative residues in fish, simultaneously quantifying 68 antibiotics and 9 sedatives in freshwater fish using a modified QuEChERS extraction method and UPLC-MS/MS. Matrix-matched calibrations demonstrated good correlation coefficients (R2 > 0.995), with a recovery range of 66.2–118.5%. The intra-day and inter-day relative standard deviation (RSD) were below 9.7% and 12.8%, respectively. The limits of detection (LOD) and quantification (LOQ) were 0.08–1.46 μg/kg and 0.25–4.86 μg/kg, respectively. 68.8% of analytes had weak matrix effects, and 13.0% had moderate matrix effects. In addition, diazepam and many types of antibiotics were detected in30 freshwater fish. The validation parameters were in agreement with the acceptable criteria of the Codex guidelines. The method was effective in analyzing antibiotic and sedative residues in freshwater fish.

Rapid, Simple and Low-Cost Analytical Method Development for Quantification of Eltrombopag Olamine in Tablet Dosage by UV Spectroscopy Method.

Eltrombopag Olamine is a drug used to treat thrombocytopenia, a disorder where blood platelet counts get lower and severe aplastic anemia. It serves as a thrombopoietin receptor agonist, which give rise to platelet production in the bone marrow. The objective of this study is to develop a simple, specific, accurate, precise and economical Ultraviolet spectroscopy method to estimate the amount of Eltrombopag Olamine in bulk and tablet dosage form. The developed method was performed using methanol for identification and physicochemical characterization of the drug. The validation parameters like linearity, precision, accuracy, robustness limits of detection and quantitation, and specificity were assessed as per ICH Q2 (R2). The maximum absorbance wavelength (λmax) of the drug was found at 247 nm in methanol. The linearity was found in the concentration range of 2-14 μg/ml with regression equation y = 0.0619x - 0.0123 and r² = 0.999. The standard addition method was used to determine the accuracy of the developed method. The result was found in the % recovery range of 98-99%. The precision was done on λmax with respect to the parameters such as repeatability, intraday, and interday. The method was found to be precise as the % RSD value was found to be <2%. The detection limit value (LOD) and quantitation limit value (LOQ) were 0.0524 μg/ml and 0.1588 μg/ml, respectively. The developed method is simple, economical, accurate and selective. The developed method was adaptable for the estimation of Eltrombopag Olamine analysis in pharmaceutical dosage form and routine quality control laboratory.

Randomized controlled trial of compressive cryotherapy versus standard cryotherapy after total knee arthroplasty: pain, swelling, range of motion and functional recovery

BackgroundAfter total knee arthroplasty (TKA), patients have limited knee range of motion (ROM), trophic changes and pain. Cryotherapy and compression are recommended in the literature, but no study has shown that cryotherapy and compression combined leads to better results than cryotherapy alone. The primary objective was to compare knee ROM after 21 days of rehabilitation post-TKA between patients who underwent rehabilitation with compressive cryotherapy with those who had cryotherapy alone. The secondary objectives were to compare other trophic, pain and functional outcomes.MethodsForty patients were randomized into two groups: Standard Cryotherapy (SC = 20, median age 77 years), which applied cold packs along with their rehabilitation; and Compressive Cryotherapy (CC = 20, median age 76 years), which received cold compression. Knee joint’s passive and active ROM (primary outcome) were measured with a goniometer. Knee’s circumference, fluctuation test, pain at rest and during activity, 6-minute walking test (6MWT) and KOOS questionnaire were secondary outcomes. The groups were compared on D1 (baseline) and D21 of rehabilitation. A survival analysis has compared the groups on D1, D8, D15, D21.ResultsAll subjects had a significant improvement in all the parameters on D21 relative to D1 (p < .05), except for pain at rest (p = .065 for CC and p = .052 for SC). On D21, the CC group had a significantly larger improvement in the joint effusion (p = .002), pain during activity (p = .005), 6MWT (p = .018) and KOOS (p = .004) than the SC group. Based on the survival analysis, the CC group had significantly faster improvement in the joint ROM (p = .011 for flexion and p = .038 for extension) and knee circumference (p = .013) than the SC group.ConclusionsBoth cryotherapy methods improved joint ROM, trophic changes, pain and function. Adding dynamic compression to a cryotherapy protocol provided further benefits: a significantly faster improvement in passive knee flexion ROM, a greater reduction of swelling, and pain during activity. Similarly, walking distance and KOOS questionnaire were significantly better for CC.Trials registrationThe study was registered in the ClinicalTrials.gov database on 14/09/2023 (identifier: NCT06037824).

High-pressure batch reverse osmosis (RO) for zero liquid discharge (ZLD) in a Cr(III) electroplating process

A batch RO system was designed and built for high-pressure (120 bar) operation. The system was developed for a ZLD application involving treatment of metal plating wastewater from a Cr(III) electroplating process at a major industrial plant. Hybrid semi-batch/batch operation enabled a compact design to be achieved. To maximize water recovery without exceeding a set peak pressure, a method for controlling the switch point between semi-batch and batch phases was developed. The system was tested with feed representative of rinse water from the electroplating process. A range of feed concentrations (at 10–20× dilution of the plating bath), feed flows (0.21–0.46 m3/h), water fluxes (6–14 LMH) and water recoveries (87–95.7 %) were investigated. The system successfully recovered Cr(III) and restored its concentration to that of the electrolyte bath, thus meeting the requirements for reuse in the electroplating process. Rejection of most species was >99.8 %, sufficient for reuse of the permeate as rinse. However, rejection of boric acid was only 69–80 % such that a second RO pass may be needed to remove boric acid. Specific Energy Consumption was <2.25 kWh per m3 of treated rinse water, representing a 50-fold saving compared to the current method of treatment and disposal at the industrial plant.

Differential degradation dynamics of λ-cyhalothrin in mineral and peat soils: a comparative study under laboratory condition

Dissipation kinetics of λ-cyhalothrin in mineral and peat soils of Semongok (mineral soil) and Sibu (peat soil) farms was investigated in a laboratory incubation experiment under different temperature and moisture conditions at normal and double application dosages. The soil was spiked with λ-cyhalothrin at 5 and 25 µg/g soil, respectively. The soil moisture content was adjusted to 20, 40, and 60% of field capacity and then incubated in three climatic chambers at 15, 25, and 35 °C. Samples were collected at 0, 7, 21, 42, 70, and 105 days and analysed by Gas Chromatography-Electron Capture Detector (GC-ECD). Pesticides from the soil were extracted via a facile-modified QuEChERS method. Recovery studies of λ-cyhalothrin in mineral and peat soils were carried out at 0.05, 0.1, 0.5 and 1.0 µg/g fortification levels. The percentage of recovered amount was in the range of 81.4–95.0% and 81.3–86.5% for mineral and peat soils, respectively which falls within the acceptable recovery range of 70.0–120.0%. Factors i.e., soil carbon content, moisture, temperature, and applied dosage that render the degradation of λ-cyhalothrin in mineral and peat soils were evaluated. Findings showed that faster λ-cyhalothrin degradation took place in soil that contained low organic carbon content (< 12%), low soil moisture (≤ 20%) and incubated under higher temperatures (≤ 35 °C). Degradation of λ-cyhalothrin was described by first-order kinetics in both mineral and peat soils at various conditions. Half-lives of λ-cyhalothrin in mineral soil were shorter compared to peat soil. This is due to its lower carbon content and lower soil organic matter availability. This study provides significant information to the agriculture industry and farmers on the important factors such as soil properties, environmental conditions and application dosage that will influence the fate of pesticides in soil.Graphical abstract

On-Off-On Fluorometric Detection of Hg(II) and L-Cysteine Using Red Emissive Nitrogen-Doped Carbon Dots for Environmental and Clinical Sample Analysis.

This research introduces a novel fluorescence sensor 'on-off-on' employing nitrogen-doped carbon dots (N-CDs) with an 'on-off-on' mechanism for the selective and sensitive detection of Hg(II) and L-cysteine (L-Cys). N-CDs was synthesized using citric acid as the carbon precursor and urea as the nitrogen source in dimethylformamide (DMF) solvent, resulting in red emissive characteristics under UV light. Comprehensive spectroscopic analyses, including UV-Vis, fluorescence, FT-IR, XRD, XPS, Raman, and Zeta potential techniques, validated the structural and optical characteristics of the synthesized N-CDs. The maximum excitation and emission of N-CDs were observed at 548 and 622nm, respectively. The quantum yield of N-CDs was calculated to be 16.1%. The fluorescence of N-CDs effectively quenches upon the addition of Hg(II) due to the strong coordination between Hg(II) and the surface functionalities of N-CDs. Conversely, upon the subsequent addition of L-Cys, the fluorescence of N-CDs was restored. This restoration can be attributed to the stronger affinity of the -SH group in L-Cys towards Hg(II) relative to the surface functionalities of N-CDs. This dual-mode response enabled the detection of Hg(II) and L-Cys with impressive detection limits of 15.1 nM and 8.0 nM, respectively. This sensor methodology effectively detects Hg(II) in lake water samples and L-Cys levels in human urine, with a recovery range between 99 and 101%. Furthermore, the N-CDs demonstrated excellent stability, high sensitivity, and selectivity, making them a promising fluorescence on-off-on probe for both environmental monitoring of Hg(II) and clinical diagnostics of L-Cys.

Smartphone-Controlled Aptasensor for Voltammetric Detection of Patulin in Apple Juice.

Patulin (PAT) is a mycotoxin that adversely affects the health of humans and animals. PAT can be particularly found in products such as apples and apple juice and can cause many health problems if consumed. Therefore, accurate and sensitive determination of PAT is very important for food quality and human and animal health. A voltammetric aptasensor was introduced in this study for PAT determination while measuring the changes at redox probe signal. The limit of detection (LOD) was found to be 0.18 pg/mL in the range of 1-104 pg/mL of PAT in buffer medium under optimum experimental conditions. The selectivity of the PAT aptasensor against ochratoxin A, fumonisin B1 and deoxynivalenol mycotoxins was examined and it was found that the aptasensor was very selective to PAT. PAT determination was performed in an apple juice medium for the first time by using a smartphone-integrated portable device, and accordingly, an LOD of 0.47 pg/mL was achieved in diluted apple juice medium. A recovery range of 91.24-93.47% was obtained for PAT detection.

Synchronous activation of praseodymium vanadate/graphitic carbon nitride nanocomposite: A promising electrode material for detection of flavonoid– Quercetin

Flavonoids or phenolic compounds are part of the daily intake of every human being. Though they are positive traders for metabolism, excessive intakes bring about detrimental impacts on human health. Herein, the anti-cancer capacitive nature quercetin (Qc) was electrochemically detected through the rare earth metal-based sphere like praseodymium vanadate (PrVO4) entrapped graphitic carbon nitride (g-CN) as electrode modifiers. The nanocomposite was prepared by the one-pot hydrothermal method and characterized by phase compositional and morphology-based techniques. The existing synergistic nature between the PrV@g-CN (praseodymium vanadate@graphitic carbon nitride) makes them have an enhanced electrochemical response towards the Qc than the individual material. The obtained cyclic voltammogram and differential pulse voltammogram profile show one major oxidation peak which is attributed to the conversion of quercetin to quercetin-o-quinone. The PrV@g-CN/GCE (GCE- glassy carbon electrode) shows a good electrochemical active surface area (A = 110 cm2) and linear range between 0.05 and 252.00 μM with a LOD (limit of detection) of 0.002 µM. Moreover, the PrV@g-CN/GCE exhibits good current retention (94.76 %) around 14 days and appreciable repeatability (RSD- 0.5 %) and reproducibility (RSD- 1.3 %) towards the Qc. The real-time implementation of the proposed sensor exhibits a good recovery range towards the black tea (95.00–98.10 %) and green tea (97.80–99.60 %).

A continuum damage coupled unified viscoplastic model for simulating the mechanical behaviour of a ductile cast iron under isothermal low-cycle fatigue, fatigue-creep and creep loading

A novel continuum damage coupled unified viscoplastic model is used for simulating the stress–strain responses of SiMo 4.06 cast iron under Low-Cycle Fatigue (LCF), fatigue-creep and creep loading for temperatures up to 650 °C. The advanced constitutive model that is developed within the framework of the Chaboche model allows the simulation of various effects including strain rate sensitivity, cyclic hardening and softening, static recovery and strain range dependency. The hyperbolic sine flow rule and the static recovery of kinematic hardening rule are proposed in order to effectively simulate both stress relaxation and creep strains. The isotropic damage variable is introduced into the constitutive equations to represent the effects of material degradation. Three main damage mechanisms are considered: fatigue, creep and ductile damage. In addition, the model is further modified to take into account the progressive microdefects closure effect. Finally, the prediction capability of the proposed model is illustrated for the experimental data obtained from the various uniaxial material tests. A good correlation was achieved between the simulated and the experimental results.

A copper metal-organic framework-based electrochemical sensor for identification of glutathione in pharmaceutical samples.

The construction of a new electrochemical sensing platform based on a copper metal-organic framework (Cu-MOF) heterostructure is described in this paper. Drop-casting Cu-MOF suspension onto the electrode surface primed the sensor for glutathione detection. The composition and morphology of the Cu-MOF heterostructure were investigated using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FT-IR), and UV-visible spectroscopy. The Cu-MOF heterostructure can identify glutathione (GSH) with an enhanced sensitivity of 0.0437 μA μM-1 at the detection limit (LOD; 0.1 ± 0.005 μM) and a large dynamic range of 0.1-20 μM. Boosting the conductivity and surface area enhances electron transport and promotes redox processes. The constructed sensors were also adequately selective against interference from other contaminants in a similar potential window. Furthermore, the Cu-MOF heterostructure has outstanding selectivity, long-term stability, and repeatability, and the given sensors have demonstrated their capacity to detect GSH with high accuracy (recovery range = 98.2-100.8%) in pharmaceutical samples.

Electrochemical sensing of sodium ions present in bovine serum using 4-tert-butylcalix[4]arene as a receptor.

The concentration of sodium ions can cause severe imbalances (high pressure on blood vessels, swelling of the muscular tissues, and misfunctioning of the whole nervous system) to the human body when its limits are uncontrolled. Thus, it is necessary to determine the amount of sodium ions present in the blood. Electrochemical sensing is an efficient methodology for detecting lower concentrations of ions even with fewer samples. Calixarenes are one of the supramolecules with a distinctive structure that has a predominant ability to complex with alkali metals. Thus, calixarenes are widely used in the detection of sodium (Na+) ions. Herein, 4-tert-butylcalix[4]arene, the simplest and cheapest calixarene, is used to deduce sodium ion concentration by electrochemical sensing approach. The sensitivity of the 4-tert-butylcalix[4]arene/GCE was 0.35269 μA M-1 and the limit of detection was 0.1 ± 0.06 μM, the lowest range of detection reported for sodium ions through differential pulse voltammetry, which is an accurate analysis. This is because calixarenes can interact with sodium ions efficiently through the hydrophilic OH groups at the lower rim of the calixarene structure. The interaction of Na+ ions with phenolic OH was confirmed by proton NMR titration against NaOH. 4-tert-Butylcalix[4]arene/GCE is adequately selective against various interfering metal ions, and it can also detect sodium ions with high accuracy (recovery range = 99.25-100.01%) in bovine serums.

Cu2+-doped zeolitic imidazolate frameworks and gold nanoparticle (AuNPs@ZIF-8/Cu) nanocomposites enable label-free and highly sensitive electrochemical detection of oral cancer-related biomarkers.

It is of great significance to accurately and sensitively detect oral cancer-related biomarkers (ORAOV 1) for the early diagnosis of oral cancer. Present here is a novel electrochemical biosensor based on Cu2+-doped zeolitic imidazolate frameworks and gold nanoparticle (AuNPs@ZIF-8/Cu) nanocomposites and a one-step strand displacement reaction for label-free, simple and sensitive detection of ORAOV 1 in saliva. It is worth noting that AuNPs@ZIF-8/Cu nanocomposites show large electrochemically effective surface area, good electrical conductivity and electrocatalytic activity due to the synergistic effect of metal nanoparticles (MNPs) and ZIF-8. Consequently, the newly developed electrochemical sensor displays a wide linear range of 0.1-104 pM and a low limit of detection (LOD) of 63 fM. Meanwhile, the electrochemical biosensor can distinguish single base mismatch. The relative standard deviation (RSD) of intra-assays and inter-assays is 1.46% and 1.76%, respectively, and the peak current values decline by 9.20% with a RSD value of 1.35% after being stored at 4 °C for 7 days, suggesting that the newly designed electrochemical sensor exhibits good selectivity, reproducibility and stability to detect ORAOV 1. More importantly, this novel electrochemical sensor is found to be applicable for detecting ORAOV 1 in human saliva samples with a satisfactory result. The RSD values range from 1.15% to 1.77%, and the recoveries range from 95.46% to 112.98%.

A rapid and sensitive ultra-performance liquid chromatography-tandem mass spectrometry method for determination of phytohormones in the medicinal plant saffron.

Saffron (Crocus sativus L.) is a valuable Chinese herb with high medicinal value. Saffron pistils are used as medicine, so increasing the number of flowers can increase the yield. Plant hormones have essential roles in the growth and development of saffron, as well as the response to biotic and abiotic stresses (especially in floral initiation), which may directly affect the number of flowers. Quantitative analysis of plant hormones provides a basis for more efficient research on their synthesis, transportation, metabolism, and action. However, starch (which interferes with extraction) is present in high levels, and hormone levels are extremely low, in saffron corms, thereby hampering accurate determination of plant-hormone levels in saffron. Herein, we screened an efficient and convenient pre-treatment method for plant materials containing abundant amounts of starch. Also, we proposed an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the quantification of abscisic acid (ABA) and auxin (IAA). Then, the method was applied for the detection of hormone-content differences between flowering and non-flowering top buds, as well as between lateral and top buds. Our method showed high sensitivity, reproducibility, and reliability. Specifically, good linearity in the range 2-100 ng ml-1 was achieved in the determination of ABA and IAA, and the correlation coefficient (R2) was >0.9982. The relative standard deviation was 2.956-14.51% (intraday) and 9.57-18.99% (interday), and the recovery range was 89.04-101.1% (n = 9). The matrix effect was 80.38-90.50% (n = 3). The method was thoroughly assessed employing various "green" chemistry evaluation tools: Blue Applicability Grade Index (BAGI), Complementary Green Analytical Procedure Index (Complex GAPI) and Red Green Blue 12 Algorithm (RGB12). These tools revealed the good greenness, analytical performance, applicability, and overall sustainability alignment of our method. Quantitative results showed that, compared with saffron with a flowering phenotype cultivated at 25 °C, the contents of IAA and ABA in the terminal buds of saffron cultivated at 16 °C decreased significantly. When cultivated at 25 °C, the IAA and ABA contents in the terminal buds of saffron were 1.54- and 4.84-times higher than those in the lateral buds, respectively. A simple, rapid, and accurate UPLC-MS/MS method was established to determine IAA and ABA contents. Using this method, a connection between the contents of IAA and ABA and the flowering phenotype was observed in the quantification results. Our data lay a foundation for studying the flowering mechanism of saffron.

Determination of 21 organophosphate esters and their metabolites in drinking water by automatic solid phase extraction-liquid chromatography-tandem mass spectrometry

To establish a method for simultaneous determination of 21 organophosphate esters(OPEs) and their metabolites in drinking water by automatic solid phase extraction-liquid chromatography-tandem mass spectrometry. The drinking water was purified by automatic solid phase extraction with HLB column, eluted by methanol, determined by liquid chromatography tandem mass spectrometry with ACQUITY UPLC BEH(100 mm×2.1mm, 1.7 μm) column, and quantified by internal standard method. The optimized method could simultaneously detect 21 organophosphate esters and their metabolites in drinking water. The detection limit was 0.01-0.24 ng/L, the quantitation limit was 0.03-0.77 ng/L. The recovery range was 57.6%-121.2% and the relative standard deviation is 1.2%-11.1% when the concentration was 0.8-20 ng/L. Senventeen tap water and 30 packaged drinking water collected by the supermarket were measured. The ΣOPEs range was 16.8-177 ng/L, and the Σdi-OPEs range was 0.328-16.3ng/L, indicating the exposure risk of organophosphates and their metabolites in water. The pretreatment of the method is simple, automatic and sensitive, and is suitable for simultaneous high-throughput determination of organophosphate esters and their metabolites in large quantities of drinking water.

Multi-pesticide residue screening, identification, and quantification analysis in various fruits and vegetables by UHPLC-Q Exactive HRMS.

A general strategy for qualitative screening and quantitative analysis of 403 pesticides in various fruits and vegetables was developed using ultrahigh-performance liquid chromatography (UHPLC) in conjunction with a Thermo Q Exactive Focus high-resolution mass spectrometer, relying on an executable compound database comprised of the exacted mass of precursor ions, retention times, and fragment ions. Taking advantage of the powerful separation capacity of UHPLC, an Orbitrap analyzer with high sensitivity in full scan mode and elevated mass resolution of product ions in the MS/MS mode, eight pairs of isomers and fifty-seven groups of isobaric compounds were selectively identified. The method was then systematically assessed and validated for eight fruits and vegetables, in terms of screening detection limit (SDL), matrix effects, recovery, and precision over 400 pesticides. The results showed that the SDLs of 68.0-84.4% for the pesticides were less than or equal to 10 μg kg-1 in the representative matrices, recoveries in the range of 60-120% accounting for 48.6-84.4% of all the targets at three lower fortified levels of 5, 20, and 50 μg kg-1 with a precision of less than 20% while the range of overall average recoveries for the majority of the pesticides were from 82.4% to 105.1% in the as-selected matrices with RSDs between 3.9% and 7.7%. Using this method, screening data from a survey of pesticide residues in 68 practical samples across 32 different matrix types provides scientific data for the inspection and supervision of pesticide residue safety of fruits and vegetables.