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1.
Anal Chem ; 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38979946

RESUMO

Calibration by Proxy (CbPx) is a matrix-matched calibration method that utilizes multiple internal standard species to build a calibration curve. The technique requires only two solutions: solution 1 containing a sample solution and a suite of internal standards at known concentrations, and solution 2 identical to solution 1, plus an aliquot of a standard containing all analytes and the internal standards at the same concentration. The calibration curve is prepared by plotting the signal measured for each internal standard in solution 1 divided by the signal arising due to the aliquot of internal standard added to solution 2 on the y-axis. In this ratio, the sensitivity for each element cancels, because the sample matrix is equal between the solutions. Therefore, the y-axis value measured for a specific internal standard is identical to the value that would be measured for any other element present at the same concentrations in the two solutions. Hence, each internal standard serves as a proxy for analyte values. The concentrations of internal standards in solution 1 are plotted on the x-axis, and these correspond to any analytes present in solution 1 at the same concentration. CbPx is applied to the analysis of five certified reference materials by inductively coupled plasma optical emission spectrometry (ICP-OES). Percent recoveries for analytes range from 89 to 106%, with relative standard deviations on the order of 1%. A recommended working range for the method is developed through both theoretical simulation and experimental results and then exhibited through the analysis of off-the-shelf vitamin tablets.

2.
Anal Bioanal Chem ; 413(5): 1293-1302, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33388844

RESUMO

The extrapolation approach, traditionally used with standard additions (SA), is compared with the alternative strategies of interpolation, reversed-axis, and normalization. The interpolation approach is based on employing twice the analytical signal recorded for the sample (ysam) to determine an unknown analyte concentration. In the reversed-axis strategy, x- and y-axes are swapped when building the SA calibration plot to facilitate uncertainty estimation. A new strategy, based on signal normalization using ysam, is also described and compared to the other approaches. Results from 3 instrumental methods, 396 sample replicates, 16 analytes, and 2 certified reference materials are included in this study. For most applications, all four SA approaches provide statistically similar trueness and precision. However, extrapolation and reversed-axis provide more consistent values (within narrower ranges) than the other strategies when employing inductively coupled plasma optical emission spectrometry (ICP OES). On the other hand, normalization provides better trueness for the less robust method of microwave-induced plasma OES (MIP OES), as it is capable of minimizing systematic errors associated with different points of the calibration curve. Normalization is particularly useful for quickly processing data, without the need for inspecting each individual calibration plot to identify outlying points. Reversed-axis and normalization are the most adequate approaches for SA applications involving MIP OES and ICP-based methods. In addition to providing similar accuracies to the traditional extrapolation approach, these strategies present the advantage of a simple uncertainty estimation, which can be easily calculated using commonly available software such as Microsoft Excel and R.

3.
Environ Sci Technol ; 54(22): 14152-14160, 2020 11 17.
Artigo em Inglês | MEDLINE | ID: mdl-33138370

RESUMO

Few schools and child care facilities test for Pb in their drinking water. Reviewing the United States Environmental Protection Agency Lead and Copper rule data can contribute to guiding future legislation on Pb testing. This work aims to (i) identify variations in Pb levels in North Carolina school and child care drinking water by building age, (ii) evaluate the effect of corrosion control measures on reducing these levels, and (iii) evaluate the adequacy of Pb reporting limits according to modern instrumentation. To achieve these objectives, information on 26,608 water samples collected in 206 North Carolina child centers between 1991 and 2019 has been analyzed. Lead concentrations were above a recently proposed 5 µg/L trigger level in 12.3%, 10.4%, 7.5%, and 0.9% of samples from pre-1987, 1987-1990, 1991-2013, and post-2013 buildings, respectively. Thus, recently proposed legislation requiring testing only for pre-1987 (or pre-1991) buildings will fail to identify all centers at risk. The odds that a greater than 5 µg/L Pb level is detected has been decreasing over the years, with a faster decreasing rate for buildings reporting corrosion control. Over 15% of samples report a method detection limit of 5 µg/L. For accurate results, future legislation should require sub-µg/L detection limits, which are easily achievable with commonly available instrumentation.


Assuntos
Água Potável , Poluentes Químicos da Água , Criança , Cuidado da Criança , Humanos , Chumbo/análise , North Carolina , Instituições Acadêmicas , Estados Unidos , Poluentes Químicos da Água/análise , Abastecimento de Água
4.
J Mol Recognit ; 31(10): e2731, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-29862590

RESUMO

Bent DNA, or DNA that is locally more flexible, is a recognition motif for many DNA binding proteins. These DNA conformational properties can thus influence many cellular processes, such as replication, transcription, and DNA repair. The importance of these DNA conformational properties is juxtaposed to the experimental difficulty to accurately determine small bends, locally more flexible DNA, or a combination of both (bends with increased flexibility). In essence, many current bulk methods use average quantities, such as the average end-to-end distance, to extract DNA conformational properties; they cannot access the additional information that is contained in the end-to-end distance distributions. We developed a method that exploits this additional information to determine DNA conformational parameters. The method is based on matching end-to-end distance distributions obtained experimentally by atomic force microscopy imaging to distributions obtained from simulations. We applied this method to investigate cisplatin GG biadducts. We found that cisplatin induces a bend angle of 36° and softens the DNA locally around the bend.


Assuntos
Cisplatino/farmacologia , DNA/química , Microscopia de Força Atômica/métodos , Proteínas de Ligação a DNA , Conformação de Ácido Nucleico/efeitos dos fármacos
5.
Anal Chem ; 87(4): 2321-7, 2015 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-25599250

RESUMO

Standard dilution analysis (SDA) is a novel calibration method that may be applied to most instrumental techniques that will accept liquid samples and are capable of monitoring two wavelengths simultaneously. It combines the traditional methods of standard additions and internal standards. Therefore, it simultaneously corrects for matrix effects and for fluctuations due to changes in sample size, orientation, or instrumental parameters. SDA requires only 200 s per sample with inductively coupled plasma optical emission spectrometry (ICP OES). Neither the preparation of a series of standard solutions nor the construction of a universal calibration graph is required. The analysis is performed by combining two solutions in a single container: the first containing 50% sample and 50% standard mixture; the second containing 50% sample and 50% solvent. Data are collected in real time as the first solution is diluted by the second one. The results are used to prepare a plot of the analyte-to-internal standard signal ratio on the y-axis versus the inverse of the internal standard concentration on the x-axis. The analyte concentration in the sample is determined from the ratio of the slope and intercept of that plot. The method has been applied to the determination of FD&C dye Blue No. 1 in mouthwash by molecular absorption spectrometry and to the determination of eight metals in mouthwash, wine, cola, nitric acid, and water by ICP OES. Both the accuracy and precision for SDA are better than those observed for the external calibration, standard additions, and internal standard methods using ICP OES.

6.
Int J Hyperthermia ; 30(5): 312-23, 2014 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-25144821

RESUMO

PURPOSE: Silver nanoparticles (Ag NP) can generate heat upon exposure to infrared light. The in vitro response of breast cell lines to Ag NP, both with and without nanoparticle-induced heating was evaluated. MATERIALS AND METHODS: Ag NP heat generation, intracellular silver concentration, and cell viability of MDA-MB-231, MCF7, and MCF 10A breast cells with Ag NP alone, or after exposure to 0.79 or 2.94 W/cm2 of 800 nm light were evaluated. RESULTS: The concentration of Ag NP to induce sufficient heat for cell death, upon exposure to 800 nm light, was 5-250 µg/mL. Clonogenics assay indicates a cytotoxic response of MCF7 (45% decrease) and MDA-MB-231 (80% decrease) cells to 10 µg/mL, whereas MCF 10A had a 25% increase. Without Ag NP, MDA-MB-231 cells were more susceptible to hyperthermia, compared to MCF7 and MCF 10A cells. Clonogenics assay of Ag NP-induced photothermal ablation demonstrated that MCF 10A cells have the highest survival fraction. MCF7 cells had more silver in the cytoplasm, MDA-MB-231 cells had more in the nuclei, and MCF 10A cells had equivalent concentrations in the cytoplasm and nuclei. CONCLUSIONS: Ag NP are effective photothermal agents. A secondary benefit is the differential response of breast cancer cells to Ag NP-induced hyperthermia, due to increased intracellular silver content, compared to non-tumorigenic breast epithelial cells.


Assuntos
Hipertermia Induzida , Raios Infravermelhos , Nanopartículas Metálicas , Fototerapia , Prata/farmacologia , Neoplasias da Mama/terapia , Linhagem Celular Tumoral , Núcleo Celular/metabolismo , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Citoplasma/metabolismo , Humanos
7.
Animals (Basel) ; 14(1)2023 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-38200862

RESUMO

Shoulder sores predominantly arise in breeding sows and often result in untimely culling. Reported prevalence rates vary significantly, spanning between 5% and 50% depending upon the type of crate flooring inside a farm, the animal's body condition, or an existing injury that causes lameness. These lesions represent not only a welfare concern but also have an economic impact due to the labor needed for treatment and medication. The objective of this study was to evaluate the use of computer vision techniques in detecting and determining the size of shoulder lesions. A Microsoft Kinect V2 camera captured the top-down depth and RGB images of sows in farrowing crates. The RGB images were collected at a resolution of 1920 × 1080. To ensure the best view of the lesions, images were selected with sows lying on their right and left sides with all legs extended. A total of 824 RGB images from 70 sows with lesions at various stages of development were identified and annotated. Three deep learning-based object detection models, YOLOv5, YOLOv8, and Faster-RCNN, pre-trained with the COCO and ImageNet datasets, were implemented to localize the lesion area. YOLOv5 was the best predictor as it was able to detect lesions with an mAP@0.5 of 0.92. To estimate the lesion area, lesion pixel segmentation was carried out on the localized region using traditional image processing techniques like Otsu's binarization and adaptive thresholding alongside DL-based segmentation models based on U-Net architecture. In conclusion, this study demonstrates the potential of computer vision techniques in effectively detecting and assessing the size of shoulder lesions in breeding sows, providing a promising avenue for improving sow welfare and reducing economic losses.

8.
Anal Chim Acta ; 1190: 339258, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34857134

RESUMO

Several species are simultaneously used for internal standardization to improve accuracy in inductively coupled plasma optical emission spectrometry (ICP-OES). In multi-internal standard calibration (MISC), signal ratios between the analyte and each of several internal standard species are used for calibration. A single calibration solution is required, and the MISC graph is built with intensity ratios calculated with analytical signals recorded for the sample (IA,sam) on the y-axis, while those recorded for the calibration standard (IA,std) are plot on the x-axis (i.e. IA,sam/IIS(i)vs. IA,std/IIS(i), where IIS(i) represents the signal intensity for a given internal standard species). Nine analytes (As, Cd, Cr, Cu, Fe, Mg, Mn, Pb and Zn), and two sets of internal standard species (i.e. Bi, Ge, In, Rh, Sc, Te, Tl and Y in solution, or eighteen emission lines from plasma naturally occurring Ar) were evaluated in this proof-of-concept study. The MISC method's efficiency was evaluated by analyte addition and recovery experiments and by analyzing two certified reference materials. Figures of merit for MISC (limit of detection, repeatability and trueness) were comparable to those obtained for the traditional external standard calibration (EC) and internal standard (IS) methods. Different from IS, MISC requires no time-consuming study to identify an ideal internal standard species, and signal biases are minimized by an averaged, more encompassing internal standardization effect.


Assuntos
Calibragem , Padrões de Referência , Análise Espectral
9.
Spectrochim Acta A Mol Biomol Spectrosc ; 283: 121737, 2022 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-35964351

RESUMO

Raman spectroscopy (RS) was used to identify and quantify different nitrogen species in fertilizers. This is a fast and inexpensive method that requires no extensive sample preparation. Urea and nitrate were determined at 1000 and 1045 cm-1, respectively. Calibration plots obtained for these analytes showed adequate linearity, with regression coefficients (r) of 0.9989 and 0.9976, respectively. Ammonium was determined by difference after total N determination by high-resolution continuum source flame molecular absorption spectrometry (HR-CS FMAS), which provided a calibration plot with r = 0.9960. The inline coupling of RS and HR-CS FMAS allowed for a fast sequential determination of ammonium, nitrate, and urea, with limits of detection of 0.03 mg/L ammonium, 0.03 mg/L nitrate, and 0.01 mg/L urea. Relative standard deviations were ≤ 11 %, and the external standard calibration method provided accurate results for all analytes determined in certified reference materials, raw materials, and commercial samples of fertilizers. For comparison purposes, all samples were also analyzed by traditional Kjeldahl method. The RS HR-CS FMAS method was further validated by addition and recovery experiments, which provided recoveries in the 93 - 113 % range.


Assuntos
Compostos de Amônio , Fertilizantes , Fertilizantes/análise , Nitratos , Nitrogênio/análise , Compostos Orgânicos , Espectrofotometria Atômica/métodos , Análise Espectral Raman , Ureia
10.
Anal Chem ; 83(7): 2526-31, 2011 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-21370824

RESUMO

Tungsten coil atomic emission spectrometry is an ideal technique for field applications because of its simplicity, low cost, low power requirement, and independence from cooling systems. A new, portable, compact design is reported here. The tungsten coil is extracted from an inexpensive 24 V, 250 W commercial light bulb. The coil is housed in a small, aluminum cell. The emission signal exits from a small aperture in the cell, while the bulk of the blackbody emission from the tungsten coil is blocked. The resulting spectra exhibit extremely low background signals. The atomization cell, a single lens, and a hand-held charge coupled device (CCD) spectrometer are fixed on a 1 × 6 × 30 cm ceramic base. The resulting system is robust and easily transported. A programmable, miniature 400 W solid-state constant current power supply controls the temperature of the coil. Fifteen elements are determined with the system (Ba, Cs, Li, Rb, Cr, Sr, Eu, Yb, Mn, Fe, Cu, Mg, V, Al, and Ga). The precision ranges from 4.3% to 8.4% relative standard deviation for repetitive measurements of the same solution. Detection limits are in the 0.04 to 1500 µg/L range. Accuracy is tested using standard reference materials for polluted water, peach leaves, and tomato leaves. For those elements present above the detection limit, recoveries range from 72% to 147%.

11.
Talanta ; 223(Pt 2): 121665, 2021 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-33298255

RESUMO

Supervised and unsupervised machine learning methods are used to evaluate matrix effects caused by carbon and easily ionizable elements (EIEs) on analytical signals of inductively coupled plasma optical emission spectrometry (ICP OES). A simple experimental approach was used to produce a series of synthetic solutions with varying levels of matrix complexity. Analytical lines (n = 29), with total line energies (Esum) in the 5.0-15.5 eV range, and non-analyte signals (n = 24) were simultaneously monitored throughout the study. Labeled (supervised learning) and unlabeled (unsupervised learning) data on normalized non-analyte signals (from plasma species) were used to train machine learning models to characterize matrix effect severity and predict analyte recoveries. Dimension reduction techniques, including principal component analysis, uniform manifold approximation and projection and t-distributed stochastic neighborhood embedding, were able to provide visual and quantitative representations that correlated well with observed matrix effects on low-energy atomic and high-energy ionic emission lines. Predictive models, including partial least squares regression and generalized linear models fit with the elastic net penalty, were tuned to estimate analyte recovery error when using the external standard calibration method (EC). The best predictive results were found for high-energy ionic analytical lines, e.g. Zn II 202.548 nm (Esum = 15.5 eV), with accuracy and R2 of 0.970 and 0.856, respectively. Two certified reference materials (CRMs) were used for method validation. The strategy described here may be used for flagging compromising matrix effects, and complement method validation based on addition/recovery experiments and CRMs analyses. Because the data analysis workflows feature signals from plasma-based species, there is potential for developing instrument software capable of alerting users in real time (i.e. before data processing) of inaccurate results when using EC.

12.
Environ Res ; 110(1): 83-8, 2010 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-19818439

RESUMO

BACKGROUND: Immigrant farmworkers are a population at risk for numerous environmental and occupational exposures. The metals arsenic, lead, mercury, and cadmium are known neurotoxins to which workers can be exposed both in the US and in their country of origin. Because farmworkers are exposed to neurotoxic pesticides, they may be at risk for adverse health effects from the combined exposure. OBJECTIVES: To examine the relationship between exposure to metals, as measured in urine, with personal and work-related characteristics of Mexican migrant and seasonal farmworkers in the US. METHODS: We analyzed data on metals found in urine of 258 farmworkers recruited from 44 camps in eastern North Carolina in 2007. Geometric means and 95% confidence intervals (CI) were used to compare data with data from the National Health and Nutrition Examination Survey (NHANES). We used multivariate regression models fitted for each metal to estimate the association of creatinine-corrected urinary metals and worker characteristics related to environmental and occupational exposures. RESULTS: Geometric mean urinary metals concentrations (mug/g creatinine) exceeded NHANES reference values for arsenic (13.23 [CI 11.11, 15.35] vs. 8.55 [CI 7.23, 9.86]) and lead (1.26 [CI 1.08, 1.43] vs. 0.63 [CI 0.60, 0.66]). Age, being from the central region of Mexico, and pack years of cigarette smoking were significant predictors of metals exposure; being a current smoker and years worked in US agriculture were not. CONCLUSIONS: This first study to examine indicators of worker body burdens of metals shows that workers have body burdens related to exposures other than work in the US. Further research should address their risk for adverse health outcomes due to combined exposures to neurotoxins in pesticides.


Assuntos
Agricultura , Poluentes Ambientais/urina , Metais Pesados/urina , Exposição Ocupacional/análise , Adolescente , Adulto , Agricultura/estatística & dados numéricos , Carga Corporal (Radioterapia) , Feminino , Humanos , Masculino , México/etnologia , Análise Multivariada , North Carolina , Análise de Regressão , Inquéritos e Questionários , Adulto Jovem
13.
Anal Chim Acta ; 1062: 37-46, 2019 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-30947994

RESUMO

An unsupervised data-driven methodology is used to quantify matrix effects caused by carbon and easily ionizable elements (EIEs) in inductively coupled plasma optical emission spectrometry (ICP OES). Background signals from nine plasma naturally-occurring species of Ar, H and O are used with principal component analysis (PCA) and affinity propagation (AP) clustering to evaluate the effects of complex matrices on ionic emission lines of Cd, Co, Cr and Pb. Matrix effect severity is then quantified based on Euclidean distance in principal component space from an average calibration curve point. The method has been applied to spiked solutions of Mediterranean Sea and Dead Sea water samples, and a significant correlation (- 0.997) was found between Euclidean distance and analyte recoveries. For sea water analysis, accurate results are found using external standard calibration (EC) when Euclidean distance < 1 for a given sample, and/or when that sample point groups with the calibration curve after affinity propagation clustering. Thus, by applying the PCA-AP strategy, one needs to perform no addition/recovery experiment to evaluate EC applicability. In addition, it can be carried out on the fly, as the background species used to monitor plasma changes are simultaneously recorded with the analytical signals, and a specific algorithm can be added to the instrument control software to flag instances in which EC may be ineffective. This is a proof-of-concept study, and additional work is required to evaluate the method's applicability to a larger number of analytes and sample matrices. However, the PCA-AP method described here for ICP OES can be used to quantify matrix effects, allowing for informed decisions regarding calibration. It requires no additional sample preparation and can be easily implemented in routine analyses of such complex-matrix samples as sea water.

14.
J Trace Elem Med Biol ; 54: 62-68, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31109622

RESUMO

BACKGROUND: Platinum-based anticancer drugs are relatively successful chemotherapeutic agents, which can cause significant elemental changes in key organs and are known for undesirable side effects, such as nephrotoxicity (damage to the kidneys). OBJECTIVES AND METHODS: Inductively coupled plasma mass spectrometry (ICP-MS) and traditional statistical tools such as two-sample Student's t-test and Pearson's correlation analysis are used to evaluate the effects of different investigational Pt-based anticancer drugs on the elemental constitution of kidneys and liver of mice. Principal component analysis is used to uncover relationships in element concentration and potential correlations between those and clinical effects. Random forest importance is used to identify elements most associated with the drug's maximum tolerated doses (MTDs). RESULTS: Strong negative correlations between Pt and both Cu (-0.814) and Zn (-0.784) in kidneys were observed for one of the Pt-acridine anticancer agents evaluated (Drug C). Strong positive correlations were observed between Cu in both kidneys (0.834) and liver (0.756) with Zn in liver for the same compound. Cisplatin administration correlates to higher concentrations of Ca, Cu, Rb and Zn in liver. Calcium and Mo in kidneys and Pt and Zn in liver are the features most associated with MTDs. CONCLUSIONS: The results indicate that the Pt-based agents investigated are major modulators of ion homeostasis in excretory organs, which most likely contributes to their systemic toxicity and limits their efficacy. A better understanding of subtle patterns and correlations among elements in key organs may provide deeper insights into the mechanisms of action and ultimately contribute for better, safer drugs. To achieve this goal, researchers involved in cancer drug development may leverage the high sensitivity and high sample throughput of ICP-MS, and the capabilities of modern statistical tools to extract relevant information from a large dataset.


Assuntos
Antineoplásicos/farmacologia , Rim/efeitos dos fármacos , Rim/metabolismo , Fígado/efeitos dos fármacos , Fígado/metabolismo , Oligoelementos/análise , Animais , Cálcio/análise , Cobre/análise , Espectrometria de Massas , Camundongos , Análise de Componente Principal , Rubídio/análise , Zinco/análise
15.
Talanta ; 205: 120160, 2019 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-31450451

RESUMO

Simple data processing and unattended calibration are achieved in automated standard dilution analysis (aSDA) using two internal standards and an inline lab-made mixing chamber furnished from a common plastic syringe. Only two calibration solutions are required per sample, which minimizes reagent consumption and waste generation. Solution 1 contains 50% sample and 50% of a standard containing the analytes and internal standard 1 (IS1). Solution 2 has 50% sample and 50% of a blank containing internal standard 2 (IS2). The concentration of analyte in the sample is calculated from (i) the slope and intercept of an analyte vs. IS1 plot, (ii) the concentration of analyte in the standard added to Solution 1, and (iii) the intercept of a second plot with IS1vs. IS2. The aSDA method was used to determine Cd, Co, Cr, Cu, Pb and Zn in tap and creek water, beer, cola soft drink, mouthwash, cough syrup and cachaça by ICP OES. Addition/recovery experiments involving these same samples and other challenging matrices (i.e. 40% v/v HNO3, and 1% m/v Na, Ca or C) were performed to evaluate the method's accuracy. The results were compared with values obtained with external standard calibration (EC), internal standardization (IS) and standard additions (SA). Considering all samples and analytes evaluated, aSDA provided the best accuracy, with an average absolute error (ε‾=|analytepercentrecovery-100|) of 4% (EC, IS and SA had 13%, 9% and 7% errors, respectively). The aSDA strategy is a simple and inexpensive alternative to traditional methods. It has great potential for broad implementation with existing ICP OES instrumentation, as it requires little modification to systems already in place in routine laboratories.

16.
Ann Surg Oncol ; 15(8): 2137-45, 2008 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-18493824

RESUMO

BACKGROUND: Cytoreductive surgery with intraperitoneal hyperthermic chemoperfusion (IPHC) has evolved into a promising approach for peritoneal surface malignancy. A large body of literature suggests that oxaliplatin has excellent cytotoxicity against colorectal cancer. Therefore, we undertook a phase I evaluation of IPHC with oxaliplatin for peritoneal dissemination from colorectal and appendiceal cancers to establish the dose-limiting toxicity (DLT) and the maximum tolerated dose (MTD). METHODS: Cohorts of three patients underwent cytoreductive surgery followed by a 2-h IPHC with escalating doses of oxaliplatin at a target outflow temperature of 40 degrees C. The initial peritoneal oxaliplatin dose was 200 mg/M(2) with increases planned in 50 mg/M(2 )increments. Plasma and perfusate samples were collected during the IPHC and evaluated using emission spectrometry techniques. Normal tissue and tumor samples were collected before and after the IPHC for analysis. DLT was defined as a grade 3 toxicity lasting 5 days. RESULTS: Fifteen patients were enrolled at two dose levels. Peritoneal fluid areas under the curve (AUCs) were above those of plasma. Additionally, intratumoral oxaliplatin was similar to that of surrounding normal tissue. Dose-limiting toxicities at 250 mg/M(2 )were observed in two of three patients enrolled in this study. CONCLUSION: We found that IPHC with 200 mg/M(2 )of oxaliplatin is well tolerated and is the MTD for a 2-h chemoperfusion. Higher doses are not feasible with this perfusion protocol given the significant toxicities associated with 250 mg/M(2 )oxaliplatin. Based on the data from this phase I study, we propose to conduct further studies with oxaliplatin delivered at 200 mg/M(2).


Assuntos
Antineoplásicos/administração & dosagem , Neoplasias do Apêndice/terapia , Neoplasias Colorretais/terapia , Compostos Organoplatínicos/administração & dosagem , Neoplasias Peritoneais/terapia , Adulto , Idoso , Antineoplásicos/farmacocinética , Neoplasias do Apêndice/patologia , Neoplasias do Apêndice/cirurgia , Quimioterapia do Câncer por Perfusão Regional , Neoplasias Colorretais/patologia , Neoplasias Colorretais/cirurgia , Terapia Combinada , Feminino , Humanos , Hipertermia Induzida/métodos , Infusões Parenterais , Masculino , Dose Máxima Tolerável , Pessoa de Meia-Idade , Compostos Organoplatínicos/farmacocinética , Oxaliplatina , Neoplasias Peritoneais/secundário , Neoplasias Peritoneais/cirurgia , Resultado do Tratamento
17.
Adv Carbohydr Chem Biochem ; 75: 215-316, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30509401

RESUMO

Investigations of methodologies aimed on improving the stereoselective synthesis of sialosides and the efficient assembly of sialic acid glycoconjugates has been the mission of dedicated research groups from the late 1960s. This review presents major accomplishments in the field, with the emphasis on significant breakthroughs and influential synthetic strategies of the last decade.


Assuntos
Glicosídeos/síntese química , Ácido N-Acetilneuramínico/química , Configuração de Carboidratos , Glicosídeos/química
19.
Anal Chim Acta ; 909: 24-9, 2016 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-26851081

RESUMO

In this work, standard dilution analysis (SDA) is combined with microwave-induced plasma optical emission spectrometry (MIP OES) to determine seven elements in coffee, green tea, energy drink, beer, whiskey and cachaça (Brazilian hard liquor). No sample preparation other than simple dilution in HNO3 1% v v(-1) is required. Due to relatively low plasma temperatures, matrix effects may compromise accuracies in MIP OES analyzes of complex samples. The method of standard additions (SA) offers enhanced accuracies, but is time-consuming and labor intensive. SDA offers a simpler, faster approach, with improved accuracies for complex matrices. In this work, SDA's efficiency is evaluated by spike experiments, and the results are compared to the traditional methods of external calibration (EC), internal standard (IS), and standard additions (SA). SDA is comparable to the traditional calibration methods, and it provides superior accuracies for applications involving ethanol-containing beverage samples. The SDA-MIP OES procedure is effective. Using only two calibration solutions, it may be easily automated for accurate and high sample throughput routine applications.


Assuntos
Bebidas/análise , Micro-Ondas , Espectrofotometria Atômica/métodos , Técnicas de Diluição do Indicador , Gases em Plasma , Espectrofotometria Atômica/normas
20.
Talanta ; 161: 826-829, 2016 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-27769489

RESUMO

This work describes a procedure using the recently proposed standard dilution analysis (SDA) calibration method for the determination of As, Cr and Ni in concentrated HNO3 and HCl by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). Because of the low contaminant levels, and consequently low limits of detection required for these reagents (commonly used in trace element analysis and the semiconductor industry), samples were minimally diluted. The analysis of concentrated acids can result in matrix/transport effects, which may compromise accuracy in ICP-MS determinations. High-chlorine content samples are also challenging for As and Cr determination due to the formation of polyatomic species such as 40Ar35Cl+ and 35Cl16OH+, which overlap the only As isotope, 75As+, and the main Cr isotope, 52Cr+, respectively. The combination of SDA and ICP-MS/MS was evaluated to overcome matrix, transport and spectral interferences in order to increase accuracy, precision and sample throughput. The performance of SDA was compared with the traditional methods of external standard calibration (EC), internal standardization (IS), and standard additions (SA). The limits of detection for SDA were calculated as 6, 10, and 30ngL-1 for As, Cr, and Ni, respectively. Recoveries for spike experiments using the new method were in the 90-114% range for all analytes. The procedure described here provides similar or even better analytical performance in comparison with EC, IS and SA.

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