Maximum Relative Standard Deviation Research Articles

Graphene oxide-based stationary phase synthesis and separation of drug molecules for liquid chromatography (HPLC) analysis

A new graphene oxide-based liquid chromatography stationary phase was synthesized, characterized, and used for the first time in the separation of paracetamol and caffeine in pharmaceutical preparations under reversed phase conditions. For this purpose, graphene oxide was synthesized using the modified Hummers method, and Si-GO stationary phase was obtained by immobilizing graphene oxide on aminopropyl silica. The obtained graphene oxide, Si–GO and aminopropyl silica materials were characterized by XRD, SEM, TEM and FTIR analysis. Different mobile phases were used to separate drug molecules in order to determine the mechanism of interaction between drug molecules and the stationary phase. Once the appropriate solvent system was determined, optimum chromatographic parameters such as mobile phase composition (methanol percentage in water), flow rate and column temperature were determined. The linearity of the method was in the range of 0.989–0.997. The maximum relative standard deviation (% RSD) value was calculated as 0.54. Mean recoveries for paracetamol and caffeine were 98%–99%, respectively, and LOD and LOQ were 6 × 10−3 to 6.5 × 10−3 mg/L and 2 × 10−2 to 2.2 × 10−2 mg/L, respectively. The results showed that the new graphene oxide-based stationary phase could be used for the separation of paracetamol and caffeine in pharmaceutical preparations.

Increasing protein identifications in bottom-up proteomics of T. castaneum − Exploiting synergies of protein biochemistry and bioinformatics

Depending on the respective research question, LC-MS/MS based bottom-up proteomics poses challenges from the initial biological sample all the way to data evaluation. The focus of this study was to investigate the influence of sample preparation techniques and data analysis parameters on protein identification in Tribolium castaneum by applying free software proteomics platform Max Quant.Multidimensional protein extraction strategies in combination with electrophoretic or chromatographic off-line protein pre-fractionation were applied to enhance the spectrum of isolated proteins from T. castaneum and reduce the effect of co-elution and ion suppression effects during nano-LC-MS/MS measurements of peptides. For comprehensive data analysis, MaxQuant was used for protein identification and R for data evaluation. A wide range of parameters were evaluated to gain reproducible, reliable, and significant protein identifications.A simple phosphate buffer, pH 8, containing protease and phosphatase inhibitor cocktail and application of gentle extraction conditions were used as a first extraction step for T.castaneum proteins. Furthermore, a two-dimensional extraction procedure in combination with electrophoretic pre-fractionation of extracted proteins and subsequent in-gel digest resulted in almost 100 % increase of identified proteins when compared to chromatographic fractionation as well as one-pot-analysis. The additionally identified proteins could be assigned to new molecular functions or cell compartments, emphasizing the positive effect of extended sample preparation in bottom-up proteomics. Besides the number of peptides during post-processing, MaxQuant’s Match between Runs exhibited a crucial effect on the number of identified proteins. A maximum relative standard deviation of 2 % must be considered for the data analysis.Our work with Tribolium castaneum larvae demonstrates that sometimes – depending on matrix and research question − more complex and time-consuming sample preparation can be advantageous for isolation and identification of additional proteins in bottom-up proteomics.

Systematically amino acid analysis: Advancements in extinction coefficient determination for therapeutic proteins

Biologicals developers often face challenges in accurately determining the extinction coefficient (EC) measurement. We have successfully improved the precision and robustness of the widely recognized amino acid analysis method for EC determination, through a stepwise optimization process. Extensive analyses based on 114 observations, covering eight proteins over three years were performed, with a maximum relative standard deviation of 1.5% among multiple analysts, and a maximum deviation of 2.8% from the theoretical EC across the eight given proteins examined.

Monocular vision-based dynamic calibration method for determining the sensitivities of low-frequency tri-axial vibration sensors.

Low-frequency vibrations exist widely in the natural environment and in human activities. Low-frequency tri-axial vibration sensors are enormously applied in the fields of seismic monitoring, building structure health monitoring, aerospace navigating, etc. Their sensitivity calibration accuracy directly determines whether their applications can work reliably. Although the laser interferometry recommended by the International Standardization Organization (ISO) is commonly used to achieve the vibration calibration, it suffers from the shortages of low-frequency range, high cost, low efficiency, and limited applicable environment. In this study, a novel monocular vision-based dynamic calibration method is proposed, which determines the whole sensitivities of tri-axial sensors by the monocular vision method to accurately measure the spatial input excitation. This method improves the calibration performance by eliminating the installation error and enhancing calibration efficiency via decreasing reinstallations. The experimental results compared with the laser interferometry demonstrate that the investigated method can obtain similar calibration accuracy in the range of 0.16-2 Hz with more efficiency. The corresponding maximum relative deviations of X-, Y-, and Z-axial sensitivities were approximately 2.5%, 1.8%, and 0.4%. In addition, the maximum relative standard deviation of the investigated method was only about 0.3% in this range.

Novel Digital SERS-Microfluidic Chip for Rapid and Accurate Quantification of Microorganisms.

In this work, we present a simple and novel digital surface-enhanced Raman spectroscopy (SERS)-microfluidic chip designed for the rapid and accurate quantitative detection of microorganisms. The chip employs a high-density inverted pyramid microcavity (IPM) array to separate and isolate microbial samples. The presence or absence of target microorganisms is determined by scanning the IPM array using SERS and identifying the characteristic Raman bands. This approach allows for the "digitization" of the SERS response of each IPM, enabling quantification through the application of mathematical statistical techniques. Significantly, precise quantitative detection of yeast was achieved within a concentration range of 106-109 cells/mL, with the maximum relative standard deviation from the concentration calibrated by the cultivation method being 5.6%. This innovative approach efficiently addresses the issue of irregularities in SERS quantitative detection, which arises due to fluctuations in SERS intensity and poor reproducibility. We strongly believe that this digital SERS-microfluidic chip holds immense potential for diverse applications in the rapid detection of various microorganisms, including pathogenic bacteria and viruses.

A simple and rapid method for evaluating the disintegration performance of compound fertilizer

ABSTRACT Rapid determination of the dissolution behavior of a compound fertilizer is difficult in agricultural industry. In this work, we describe a simple and rapid method for quantifying the disintegration properties of compound fertilizer for the indirect evaluation of their dissolution. The effects of screen mesh, disintegration time, temperature, fertilizer-water ratio, stacking mode and particle size on fertilizer disintegration test were studied. Under standardized conditions, the maximum and minimum relative standard deviation (RSD) were 12.7% and 0.9%, respectively. The mean deviations of the measured data were > 4%, standard deviations > 4.6%, and interquartile ranges > 6.7%. The feasibility, accuracy, error tolerance, and consistency of this lift disintegration method meet industrial requirements and can be utilized for the rapid determination of the solubility of compound fertilizers.

A multi-laser hybrid absorption sensor for simultaneous measurement of NH3, NO, and temperature in denitrification flue gas

The real-time monitoring of NH3, NO, and flue gas temperatures is critical to controlling NOx emissions from coal-fired power plants, reducing ammonia slip, and realizing accurate ammonia injection. However, few previous studies have utilized laser absorption sensors to measure these three indicators simultaneously. In this paper, a multi-laser hybrid sensor is designed based on tunable diode laser absorption spectroscopy (TDLAS) for simultaneous measurement of NH3, NO, and flue gas temperature. The sensor uses a distributed feedback (DFB) laser to target the NH3 and the H2O lines, and a quantum cascade laser (QCL) is used to target the NO line. In the measurements of NH3 and NO using calibration-free wavelength-modulated spectroscopy (CF-WMS), we employ a method to obtain the laser wavelength response by fitting the demodulated signal of a standard gas. Additionally, temperature measurements are obtained using the time-division multiplexing (TDM) strategy and direct absorption spectroscopy (DAS) techniques with the help of the absorption spectrum of H2O. Under static conditions, the relative accuracy of NH3 and NO detected by the sensor is 4.2% and 2%, respectively, and the maximum relative standard deviation of temperature is 1.3%. When tested under flowing conditions, the sensor can accurately capture NH3, NO, and temperature changes. The relative accuracy of NH3 and NO is 4.7% and 2.2%, and the relative standard deviation of temperature is 0.9%. The sensor has great potential in optimizing denitrification processes in thermal power plants.

Development of a fast GC-response factor method to quantify total FAMEs in biodiesel from various fatty acid sources

Biodiesel is a renewable energy source that can be employed as an alternative fuel to fossil diesel. Monitoring samples in terms of fatty acid methyl esters (FAMEs) content using gas chromatography (GC) is a useful way to evaluate the quality of biodiesel produced. Fast GC can be used to reduce the time of analysis and consequently the costs, even though the equipment required for this may be expensive. Therefore, we developed and validated a Fast GC-response factor (Fast-GCRF) methodology using a low-priced nonpolar column, flame ionization detection (FID) and a standard chromatograph usually destined for conventional GC separations. The method was validated and applied to the quantification of FAMEs produced from various raw materials (soybean, cottonseed, canola, coconut, palm, sesame, sunflower, castor, corn, macauba, almond, peanut, chia seeds, residual frying oils, and chicken fat), being both selective and robust even when subjected to changes in sample preparation. The Fast GCRF method presented respective maximum relative standard deviation (RSD) values for instrumental precision, repeatability, and intermediate precision of 2.3 %, 3.6 %, and 2.8 %. When compared to conventional GC methodologies, accurate results with high degrees of agreement were obtained using the Fast-GCRF method, within an at least four times shorter analysis time.

Micro gas chromatographic column with copper benzene-1,3,5-tricarboxylate modified by multilayer fluorinated graphene as a stationary phase

A composite material was synthesized at room temperature by performing modification of the copper benzene-1,3,5-tricarboxylate (HKUST-1) metal-organic framework material by multilayer fluorinated graphene (FG). The FG-HKUST-1 composite was used as a stationary phase for a micro gas chromatography column (μGCC) fabricated using micro-electro-mechanical system (MEMS) technology. The separation results showed that the μGCC with the FG-HKUST-1 composite stationary phase achieved a baseline separation of C1-C4 in 8 min. The retention factors for C2-C4 were 2.13, 7.14, and 12.04, respectively. The maximum relative standard deviation (RSD) of the retention times was 0.14 %. The difference in the retention time between methane and ethane was 1.11 min, with a resolution of 9.2 for methane and ethane. The retention factor of ethane and the resolution of methane and ethane were increased by 166 % and 114 %. Therefore, this μGCC is promising for separating light hydrocarbons with widely differing concentrations.

A reaction-based carbazole-dicyanovinyl conjugated colorimetric and ratiometric fluorescent probe for selective detection of cyanide ions

In the present work, 4-(9′-hexylcarbazol-3′-yl)benzylidenemalononitrile 5 (probe L) was tested as a colorimetric and ratiometric fluorescent probe in dimethyl sulfoxide (DMSO) medium towards anions, cations and neutral molecules. The sensing properties of probe L were investigated by using UV–Vis absorption and fluorescence spectroscopy techniques. Probe L showed selectivity and sensitivity towards cyanide ions (CN–) in the presence of analytes used. Upon the addition of CN–, intramolecular charge transfer (ICT) band at 425 nm in UV spectrum disappeared. In addition, ICT emission intensity at 593 nm decreased and ligand-centred (LC) emission intensity at 480 nm increased. These findings indicate that nucleophilic conjugate addition of CN– to the dicyanovinyl group of probe L successfully occurs, hence forming a new adduct between probe L and CN–. In this adduct, π-conjugation was partially blocked, and the ICT transfer was hindered. Adduct formation was proved by Job’s plot, 1H NMR and FT-IR analysis. Probe L showed very low limit of detection (LOD) value of 1.467 nM towards CN–. Probe L was also applied to the CN– detection in real-world water samples by the spike and recovery method. The maximum relative standard deviation (RSD) value was 4.24, indicating this method works successfully. Therefore, probe L could find a potential use in detection of CN– in liquid media.

The solvent- and surface-dependent adsorption of the lipopeptide antibiotic daptomycin: The general necessity of adsorption tests

The impact of poor or non-reproducible analyte recoveries due to non-specific drug adsorption on various analytical assays is often underestimated. Even internationally approved guidelines for pharmaceutical analysis such as the EMA guideline on bioanalytical method validation, the ICH guideline M10 on bioanalytical method validation and study sample analysis or the FDA bioanalytical method validation guidance do not adequately encourage more detailed investigations. Furthermore, other areas of research in which the concentration of active pharmaceutical compounds plays a crucial role, for example screening for minimal inhibitory concentrations of bacterial isolates, are potentially affected as well. The aim of this study was to demonstrate the general necessity of drug adsorption tests, using the lipopeptide antibiotic daptomycin as an example. A wide range of typical materials used in processing samples in pharmaceutical and biological analysis, as well as various solvents and biological matrices were included in the experiments. A fully validated LC-MS/MS method was applied for the determination of daptomycin concentrations, which were subsequently used to calculate the recovery. Recovery results (n = 3) ranged from 0.00% to 102.12% with a maximum relative standard deviation of 12.78%. These findings demonstrate that recovery can vary greatly depending on the solvent and the contact material, indicating the need to be optimized and, if applicable, validated. Hence, high reproducibility can only be achieved if all materials (and their manufacturers) used in a method are specified, not just those used in steps considered critical.

An adaptive law based online system identification of cropped delta unmanned aerial vehicles from flight tests

Online system identification of an aircraft has multifaceted advantages, such as real-time health monitoring, fault detection and reconfiguration of control, to name a few. Researchers have utilized variants of the equation error method, which involves non-gradient-based computation to carry out online system identification, due to its feasibility for real-time implementation. However, it was found to be underperforming while handling high angles of attack as well as time-varying bias parameters. In the current manuscript, an attempt has been made to alleviate the aforementioned limitation by proposing a novel online system identification technique based on adaptive law and its applicability is demonstrated by using compatible flight data sets, acquired from two cropped delta wing unmanned aerial vehicles, pertaining to linear, moderately nonlinear, and near stall flight regimes. It is observed that the proposed method is able to predict unknown aerodynamic derivatives, irrespective of flight envelopes, if dynamic modes are adequately excited. Confidence in the estimated aerodynamic parameters is assured with the two-sigma error bound. It is noticed that the maximum relative standard deviation in the estimates obtained with the proposed method is less than the recursive least squares method and higher than the sequential least squares-recursive Fourier transform method in the linear flight regime. Simulated responses using the estimates obtained from aforementioned methods are compared with measured flight data, and it is witnessed that the simulated nondimensional lift coefficient with the proposed method has a relative offset of less than 34.2% w.r.t measured value in near-stall flight regimes, which is least among all three methods.

Atrazine and its degradation products in drinking water source and supply: Risk assessment for environmental and human health in Campinas, Brazil

Atrazine is a broad-spectrum herbicide widely used worldwide to control grassy and broadleaf weeds. Atrazine's popularity is attributable to its cost-effectiveness and reliable performance. Relatedly, it is also an important micropollutant with a potential negative impact on biodiversity and human health. Atrazine has long been regularly detected in several environmental compartments, and its widespread use has resulted in ubiquitous and unpreventable contamination. Among pesticides sold in Brazil, atrazine has remained among the top-ranked active ingredients for the last several years. Thus, this study aimed to evaluate the occurrence of atrazine and three degradation products (hydroxyatrazine, desisopropylatrazine, and desethylatrazine) in surface water (Capivari and Atibaia rivers) and treated water, monthly sampling from two drinking water treatment plants in Campinas (São Paulo, Brazil). An analytical method using solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to determine target compounds simultaneously. The method presented instrument quantification limits from 0.5 to 4.0 ng mL−1 and recovery values from 80 to 112%, with a maximum relative standard deviation of 6%. All analytes had a detection frequency of 100% from 2 to 2744 ng L−1. Statistical analysis showed no analyte removal after conventional water treatment. Also, the Capivari River showed greater analyte concentration than the Atibaia River. Performed risk assessments according to current Brazilian standards showed no human and environmental health risks. However, other risk assessment approaches may indicate potential risks, advocating for further research and ongoing surveillance.

A Compact High-Stability Nanosecond Pulse Test System Using Corona-Stabilized Switch and Coaxial Resistance Divider

Due to the lack of a standard nanosecond high-voltage pulse generator for sensor calibration, a high-stability nanosecond high-voltage pulse test system was developed in terms of circuit analysis, structural design, and performance test. By establishing the equivalent circuit model of the nanosecond pulse generator, the circuit component parameters of the five-stage Marx loop and the one-stage compression steepening unit were simulated. The influence of the action performance of the steepening gap on the characteristics of output nanosecond pulse was analyzed. The nanosecond pulse test system was established through the structural design of the nanosecond pulse-generating circuit, the development of a high-performance corona-stabilized switch, and the measurement of a fast-response resistance divider made of metal oxide thin-film resistors. The nanosecond pulse test system has the capability to output a double exponential nanosecond pulse voltages in the amplitude range of 10–60 kV with a rise time of 2.3 ± 0.5 ns and a half-peak time of 23 ± 5 ns. In addition, the output pulse voltage has a high consistency and stability in the full amplitude range. The maximum relative standard deviation of the peak value is 1.517%, and the relative standard uncertainty is less than 5‰.

Quantitative determination of polychlorinated biphenyls in chicken based on QuEChERS extraction and GC-MS/MS detection

Polychlorinated biphenyls (PCBs), a class of synthetic organic compounds consisting of chlorine atoms on two coupled biphenyl rings, have been declared class A carcinogens by the World Health Organization. Here, we report a new method for the determination of PCBs content in chicken. The method employs QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction, followed by gas chromatography and tandem mass spectrometry (GC-MS/MS) detection for the identification and quantification of seven indicative PCBs (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, PCB180). The PCBs were extracted by acetone with an Association of Official Analytical Chemists (AOAC) extraction kit, followed by a clean-up step using primary secondary amine, octadecyl silica, florisil, and anhydrous magnesium sulfate. PCBs in the extracts were subsequently quantified by GC-MS/MS. The method was validated, and the correlation coefficients of the curves were found to be higher than 0.99. The limits of detection for the seven indicative PCBs ranged from 0.1 to 0.5 ng/g, and the limits of quantification were 0.3–1.5 ng/g. Satisfactory recovery rates ranged from 96% to 115%, with a maximum relative standard deviation of 9%. For simple pretreatment and accurate detection, this method is quick and efficient in detecting batches of seven indicative PCBs in chicken.

Aromatic hydrocarbons extracted by headspace and microextraction methods in water-soluble fractions from crude oil, fuels and lubricants.

Two extraction protocols were developed for the determination of mono- and poly-aromatic hydrocarbons in water-soluble fractions from gasoline, diesel, crude, mineral insulating, and lubricant oils. Development of the procedures was based on clean miniaturized strategies, such as headspace extraction and vortex-assisted dispersive liquid micro-extraction, together with quantification by gas chromatography-mass spectrometry. The mono-aromatic hydrocarbons were extracted using the headspace extraction method. The linear range obtained was 10-500µgL-1, with r2 > 0.99. Based on the parameters of the analytical curves, detection and quantification limits of 2.56-3.20 and 7.76-9.71µgL-1 were estimated. In addition, the method showed adequate recoveries of 69.4-83.5%, with a satisfactory precision of 4.7-17.1% (n = 5). Micro-extraction was applied for the poly-aromatics and the most favorable variables were sample volume (5.00mL) in sodium chloride medium (1%, w/v), trichloromethane as extractor solvent (75µL), acetone as disperser (925µL) and vortexing for 1min. Under these conditions, analytical curves of 0.15-4.00µgL-1 were obtained and limits of determination and quantification were 0.03-0.15 and 0.09-0.46µg L-1, respectively. Recovery values of 87.6-124.5% and a maximum relative standard deviation of 18.9% (n = 5) verify satisfactory accuracy and precision. This led to the achievement of enrichment factors for poly-aromatic hydrocarbons of 41-89 times. Finally, the methods were employed in samples of water-soluble fractions for the determination of analytes. The values followed the order: gasoline > diesel > crude > lubricant > mineral insulating oil. These results indicate an increase in lighter fractions, followed by poly-aromatics in more refined products.

Influence of the Soil Composition on the Determination of 2,4-D and Fipronil in Environmental Samples by SLE-LC-MS/MS

The main objective of this work was to develop and validate an analytical method using solid-liquid extraction and liquid chromatography coupled with mass spectrometry in tandem (LC-MS/MS) for the simultaneous determination of the herbicide 2-(2,4-dichlorophenoxy)acetic acid (2,4-D) and the insecticide fipronil and its degradation products, fipronil sulfone and fipronil sulfide in different types of soil from Brazil (Oxisol and Entisol). Solid-liquid extraction was performed in two cycles using 20 mL of dichloromethane per cycle and sonication. The extraction efficiency of 2,4-D was more influenced by soil composition than the other compounds. The limits of quantification of the method were between 0.015 and 0.75 mg kg-1 and recovery values from 61 to 118%, with a maximum relative standard deviation (RSD) value of 4%. The method was further applied to over 500 real soil and sediment samples. 2,4-D and fipronil concentrations varied from 0.03 to 1145 µg kg-1 and 1.1 to 282 µg kg-1, respectively.

Stress Online Monitoring Method Based on Multifrequency SH0 Guided Wave Information Fusion

This article proposes a stress monitoring technique based on multifrequency SH0 guided wave information fusion. Its nondispersive acoustoelastic characteristic facilitates joint analysis in the whole frequency band. Moreover, the typical representation of broadband multifrequency signal is equivalent to realizing multiple measurements simultaneously, effectively improving the measurement efficiency and reliability. First, a generalized multifrequency comprehensive measurement model is established, which combines with specific data analysis and postprocessing criteria to construct a new stress characterization method. Then, the acoustoelastic effect of SH0 guided wave is investigated. Next, the wideband shear piezoelectric transducer based on the out-of-plane d15 mode is designed. The frequency-domain finite-element method (FDFEM) is applied to optimize the SH0 guided wave excitation and reception interval. Finally, the laboratory experiments of 6061-T6 aluminum plates with a thickness of 1 mm are conducted to verify the proposed strategy. The fitting result of multifrequency component fusion is better than that of any single-frequency algorithm. The actual measurements from the same batch are carried out through the calibration results. The maximum error does not exceed 2.5 MPa and the maximum relative standard deviation (RSD) is 7% in the range of 15–85 MPa, demonstrating good measurement accuracy and consistency.

New Quantum-Dot-Based Fluorescent Immunosensor for Cancer Biomarker Detection

Cancer antigen 15-3 (CA 15-3) is a biomarker for breast cancer used to monitor response to treatments and disease recurrence. The present work demonstrates the preparation and application of a fluorescent biosensor for ultrasensitive detection of the cancer antigen CA 15-3 protein tumor marker using mercaptopropionic-acid-functionalized cadmium telluride (CdTe@MPA) quantum dots (QDs) conjugated with CA 15-3 antibodies. First, the QDs were synthesized by the hydrothermal route, resulting in spherical nanoparticles up to 3.50 nm in diameter. Subsequently, the QD conjugates were characterized by Fourier transform infrared spectroscopy (FTIR), UV absorption, and fluorescence. The interaction between the conjugates and the protein was studied by fluorescence spectroscopy in buffer and in 10-fold diluted commercial human serum. Calibration in spiked serum samples gave a detection limit of 0.027 U/mL, 1000-fold lower than the clinical limit for CA 15-3 (25 U/mL to 30 U/mL), indicating that this is an ultrasensitive technique. In addition, a rapid response was obtained within 10 min. The biosensor was selective in the presence of the interfering serum proteins BSA, CEA, and CA-125, with a maximum interference of 2% for BSA. The percent recovery was close to 100% with maximum relative standard deviation (RSD%) values of 1.56. Overall, the developed CA 15-3 biosensor provides a simple and sensitive method for ultrasensitive monitoring of breast cancer, as well as the ability to detect other molecules of interest in human serum matrices.

Chromatographic Separation of Aromatic Amine Isomers: A Solved Issue by a New Amphiphilic Pillar[6]arene Stationary Phase.

In this work, the fabrication, synthesis, and characterization of a new stationary phase based on an amphiphilic pillar[6]arene (P6A-C10-2NH2) for gas chromatographic analyses are reported. The gas chromatography (GC) column prepared with P6A-C10-2NH2 stationary phase exhibited a medium polarity, an efficiency of 3219 plates/m, and unmatched resolving capabilities toward chloroaniline, bromoaniline, iodoaniline, and toluidine isomers. Furthermore, the P6A-C10-2NH2 column showed excellent repeatability with maximum relative standard deviations equal to 0.02, 0.07, and 2.56% for run-to-run, day-to-day, and column-to-column, respectively, demonstrating a great potential as a new stationary phase in separation science.