Solid Phase Extraction and Simultaneous Chromatographic Quantification of some Non-steroidal Anti-inflammatory Drug Residues; an Application in Pharmaceutical Industrial Wastewater Effluent

Abstract Two sensitive and selective methods were developed for the simultaneous determination of four commonly used non-steroidal anti-inflammatory drugs (NSAIDs), namely; paracetamol (PCM), diclofenac sodium (DCF), ibuprofen (IBP), and indomethacin (IND) in wastewater effluents. The first method used HPLC for the determination of the studied drugs using a mobile phase consisting of phosphate buffer (pH 3.0) and acetonitrile at a flow rate of 1 mL/min. in gradient elution mode and detection at 220 nm. The separation process was performed on BDS Hypersil Cyano column (250 x 4.6 mm, 5 µm). The second method was a TLC-densitometric one which was performed using n-Hexane: ethyl acetate: acetic acid in the ratio (6:3.5:0.5) as a developing system. The proposed chromatographic methods were successfully applied for the selective determination of the four studied drugs in simulated and real pharmaceutical wastewater samples after their solid-phase extraction

Optimization and validation of the analytical methods to detect common illicit drugs in sewage / 中国药科大学学报

@#The waste water-based epidemiology is an important technique to fight against drug abuse by analyzing the concentration of illicit drugs in urban sewage, which can monitor the abuse of drugs.An SPE-UPLC-MS/MS method was developed for the analysis of 12 common drugs and their metabolites involving amphetamine and morphine.It was shown that the best result was achieved when hydrochloric acid/ acetonitrile (5∶95) was added to acidify the sample during the concentration process, guaranteeing the anti-across contamination of the analysis of organic nitrogen basic trace components, and improve the stability, specificity, and accuracy of the method.The optimized method meets the analytical requirements of complex sewage samples, and has been successfully applied to the assessment of urban drug abuse through sewage analysis.

Cohort study of changes in expression of three serum cytokines in patients with advanced non-small cell lung cancer after intensity-modulated radiotherapy combined with chemotherapy / 中华放射肿瘤学杂志

Objective:To investigate the changes of the expression levels of serum proliferating cell nuclear antigen (PCNA), tumor-specific growth factor (TSGF), soluble E-cadherin (SE-CAD) and the relationship with clinical prognosis of advanced non-small cell lung cancer (NSCLC) patients treated with intensity-modulated radiotherapy combined with chemotherapy.Methods:Eighty-four patients (29 cases of Ⅲ A, 30 Ⅲ B and 25 Ⅳ) with advanced NSCLC treated in our hospital from January 2016 to January 2018 were selected, and all patients were given with intensity-modulated radiotherapy combined with chemotherapy. The expression levels of serum PCNA, TSGF, and SE-CAD were compared among different TNM stages and before and after treatment. The serum PCNA, TSGF, SE-CAD levels were compared among patients with different clinical efficacy. The relationship between serum PCNA, TSGF and SE-CAD levels and clinical efficacy was assessed by Logistic regression analysis. The survival analysis was performed with Kaplan- Meier method. Results:The expression levels of serum PCNA, TSGF and SE-CAD before treatment in stage Ⅳ patients were significantly higher than those in stage Ⅲ B and Ⅲ A patients (584.11±60.25 pg/ml vs. 531.06±51.37 pg/ml and 477.54±46.49 pg/ml, 96.13±7.54 U/ml vs. 8.52±5.91 U/ml and 82.41±5.0 U/ml, 3.02±0.26 ng/ml vs. 2.87±0.22 ng/ml and 2.71±0.15 ng/ml, all P<0.05), and the serum levels of three cytokines in Ⅲ B stage patients were significantly higher than those in their Ⅲ A stage counterparts (all P<0.05). After treatment, the serum levels of PCNA, TSGF and SE-CAD were significantly lower than those before treatment (396.11±50.23 pg/ml vs. 528.37±75.09 pg/ml, 74.81±4.72 U/ml vs. 88.68±6.13 U/ml, 1.92±0.24 ng/ml vs.2.86±0.31 ng/ml, all P<0.05). At 18 months after treatment, the serum levels of PCNA, TSGF and SE-CAD in surviving patients were significantly lower than those of dead patients (332.51±54.32 pg/ml vs. 444.92±60.07 pg/ml, 70.59±6.20 U/ml vs. 78.05±8.44 U/ml, 1.71±0.24 ng/ml vs. 2.08±0.27 ng/ml, all P<0.05). The serum levels of PCNA, TSGF and SE-CAD were significantly associated with clinical prognosis (all P<0.05). Among 84 NSCLC patients, the objective response rate after treatment was 29%(24/84). The survival curves in patients with high expression levels of serum PCNA, TSGF and SE-CAD were significantly lower than those in the low-expression group (all P<0.05). Conclusion:Serum PCNA, TSGF and SE-CAD are highly expressed in patients with advanced NSCLC, which are closely correlated with clinical staging and prognosis and contribute to predicting survival status.

Extracción e identificación de lípidos polares de las microalgas Nannochloropsis oceanica y Desmodesmus asymmetricus / Extraction and identification of polar lipids from microalgae Nannochloropsis oceanica and Desmodesmus asymmetricus / Extração e identificação os lipídios polares das microalgas Nannochloropsis ocean ca e Desmodesmus asymmetricus

Resumen Los lípidos polares de las microalgas sor de gran interés debido a su aplicación como ingredientes naturales novedosos para las industrias cosmética, nutricional y farmacéutica. Por ello, el presente trabajo buscó determinar el efecto de los principales factores en la extracción e identificación de los lípidos polares de las microalgas Nannochloropsis oceanica y Desmodesmus asymmetricus, mediante el diseño de superficie de respuesta de Box-Behnken y el diseño factorial completo, respectivamente. Estas cepas del Banco de Germoplasma de Organismos Acuáticos (BGOA - IMARPE) fueron cultivadas en un invernadero, en biorreactores de 30 litros, centrifugadas y liofilizadas. Los lípidos fueron extraídos con cloroformo-metanol, fraccionados y analizados con un espectrómetro de masas Waters Xevo G2-XS QTOF. La maximización de la extracción de los lípidos totales determinó un valor óptimo de la relación masa-solvente de 25mg/3 mL, una proporción 1:1 de cloroformo-metanol, aproximadamente, y un tiempo del baño de ultrasonido entre 10 y 30 min. Los principales lípidos polares identificados para N. oceanica fueron lisofosfatidilcolina (LPC), diacilgliceril-N,N,N-trimetilhomoserina (DGTS), digalactosil diacilglicerol (DGDG) y monogalactosil diacilglicerol (MGDG) y para D. asymmetricus fueron sulfoquinovosil diacilglicerol (SQDG), LDGTS, DGTS, DGDG y MGDG.

Abstract The microalgae polar lipids are of great interest due to their application as novel natural ingredients for the cosmetic, nutritional, and pharmaceutical industry. For this reason, the present work sought to determine the effect of the main factors in the extraction and identification of polar lipids from the microalgae Nannochloropsis oceanica and Desmodesmus asymmetricus, using Box-Behnken response surface methodology design and full factorial design, respectively. These strains from the Germplasm Bank of Aquatic Organisms (BGOA - IMARPE) were grown in a greenhouse, in 30 L bioreactors, centrifuged and lyophilized. The lipids were extracted with chloroform-methanol, fractionated and analyzed with the Waters Xevo G2-XS QTOF mass spectrometer. The maximization of total lipid extraction determined an optimal value of the mass-solvent ratio of 25 mg / 3 mL, an approximate ratio of chloroform-methanol 1:1 and an ultrasound bath time between 10 and 30 min. The main polar lipids identified for the N. oceanica microalgae were lysophophatidylcholine (LPC), diacylglyceryl-N,N,N-trimethylhomoserine (DGTS), digalactosyldiacylglycerol (DGDG), and monogalactosyldiacylglycerol (MGDG) and for D. asymmetricus were sulfoquinovosyl diacylglycerol (SQDG), LDGTS, DGTS, DGDG, and MGDG.

Resumo Os lipídios polares das microalgas possuem grande interesse em sua aplicação como novos ingredientes naturais na indústria cosmética, nutricional e farmacêutica. A presente pesquisa procura determinar o efeito dos principais fatores na extração e identificação dos lipídios polares das microalgas Nannochloropsis oceanica e Desmodesmus asymmetricus, por meio do um experimento de Box-Behnken e um experimento fatorial completo, respectivamente. As cepas do Banco do Germoplasma do Organismos Aquáticos (BGOA - IMARPE), foram cultivadas em casa de vegetação, em biorreatores do 30 L, centrifugadas e liofilizadas. Os lipídios foram extraídos com clorofórmio-metanol, fracionados e analisados com o espectrómetro do massa Waters Xevo G2-XS QTOF. A maximização da extração lipídica determinou um valor ótimo da razão massa-solvente de 25 mg / 3 mL, uma proporção aproximadamente clorofórmio-metanol de 1:1 e no tempo do banho de ultrassom entre 10 e 30 minutos. Os principais lipídios polares identificados para das microalgas N. oceanica foram lisofosfatidilcolina (LPC), diacilgliceril-N,N,N-trimetil-homoserina (DGTS), digalactosil diacilglicerol (DGDG) e monogalactosil diacilglicerol (MGDG), e para D. asymmetricus foram sulfoquinovosil diacilglicerol (SQDG), LDGTS, DGTS, DGDG e MGDG.

Consulta do Registo de Saúde Eletrónico ­ Análise ética de um caso clínico / Electronic Health Registry Query - Ethical Case Study / Consulta electrónica de registros de salud - Estudio de caso ético

Introducción: La bioética surgió de la necesidad de regular un código de conducta ética que evitara las prácticas médicas abusivas llevadas a cabo durante varios siglos. El Procedimiento Deliberativo (PD), aplicado a la medicina, ayuda a tomar decisiones éticas de forma objetiva (equilibrada, podenrada) y justa. Con la presentación de este caso clínico se pretende, como ejemplo, demostrar la importancia de aplicar el PD en la práctica clínica en medicina general y familiar (MGF). Caso clínico: Un hombre de 58 años que, después de un antígeno prostático específico alterado, fue derivado a una consulta de urología. Un mes después de la biopsia de próstata, asiste a la consulta de MGF con la confianza de que el resultado sería negativo. Sin su autorización, el médico de familia (MF) accedió al registro electrónico de salud y descubrió que el paciente tenía un adenocarcinoma de próstata, aunque no habia sido re-evaluado por Urologia. Se eligió el problema ético más importante y se definió el curso de acción óptimo que cumplía los criterios de legalidad, publicidad y temporalidad. Conclusión: La decisión del médico siempre debe beneficiar el paciente. El PD permite tomar decisiones estructuradas, por lo cual debe aplicarse en el contexto de la MGF frente a problemas éticos

Introduction: Bioethics emerged from the need to implement an ethical code of conduct that would avoid abusive clinical practice carried for centuries. The Deliberative Procedure (DP) applied to medicine helps in making ethical decisions in a well-reasoned and fair manner. This clinical case report is intended to exemplify the importance of applying the deliberative process in clinical practice in general practice/family medicine (GP/FM). Clinical case: Male, 58 years old referenced to urology office visit after positive Prostate-Specific Antigen (PSA) test. A month after prostatic biopsy he went to the medical consultation with his Family Doctor, believing the result was negative. His family doctor assessed his health electronic record without his authorization, and verified the result of the biopsy was a prostatic adenocarcinoma, without new urology appointment. It was elected the most important ethic problem and defined the action curse that accomplish the legality, publicity and temporary criteria. Conclusions: Whatever the physician decides, it should always be for the benefit of the wearer. DP allows structured decision making so it should be applied in the context of GP/FM in the face of ethical problems.

Introdução: A bioética surgiu da necessidade de regulamentar um código de conduta ética que evitasse as práticas médicas abusivas realizadas durante vários séculos. O Procedimento Deliberativo (PD) aplicado à medicina, ajuda na tomada de decisões éticas de forma ponderada e justa. Com a apresentação deste caso clínico pretende-se exemplificar a importância da aplicação do PD na prática clínica em Medicina Geral e Familiar (MGF). Apresentação do caso: Homem de 58 anos que no seguimento de um antígeno específico da próstata (PSA) alterado foi referenciado à consulta de urologia. Um mês após biópsia prostática recorre à consulta de MGF confiante de que o resultado seria negativo. Sem a sua autorização, o Médico de Família (MF) acedeu ao Registo de Saúde Eletrónico e verificou que o doente apresentava um adenocarcinoma da próstata, embora não tivesse ainda consulta de reavaliação de urologia. Foi eleito o problema ético mais importante e definido o curso de ação ótimo que cumpria os critérios de legalidade, publicidade e temporalidade. Conclusões: Qualquer que seja a decisão do médico, deve ser sempre em benefício da pessoa. O PD permite uma tomada de decisão estruturada pelo que deve ser aplicado no contexto de MGF perante a ocorrência de problemas éticos.

Simultaneous determination of illicit drugs and their metabolites in wastewater by SPE-UPLC-MS/MS / 中国药科大学学报

@#A quantitative analysis method based on solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS) for simultaneous determination of illicit drugs and their metabolites in wastewater was established. Samples filtered at pH of 2 and spiked with internal standard were loaded to Oasis Prime MCX cartridges for solid-phase extraction. The samples were washed with 4 mL of methanol and eluted with 4 mL of 5% ammonia in acetonitrile before reconstituting with 0.1% formic acid/water solution. ZORBAX Eclipse Plus C18 column was used for chromatography, and gradient elution was performed with 0.1% formic acid/water solution and acetonitrile as mobile phase. The samples were then detected by electrospray ionization (ESI) in positive ion mode, and multiple reaction monitoring mode (MRM) was adopted for quantitative analysis. All analytes had a good linear relationship (r ≥ 0.993 2) within the range of their respective standard curve; the limit of quantification was 1 ng/L (except amphetamine at 2.5 ng/L); the extraction recovery ranged from 82.13% to 99.96%; and the intra- and inter-day precisions were less than 9.43%. The method is accurate, reliable and reproducible, and is suitable for the quantitative determination of illicit drugs and their metabolites in wastewater and can provide an analytical method for real-time monitoring of drug abuse.

Determination of Polycyclic Aromatic Hydrocarbons in Human Blood Samples Using Solid Phase Extraction and Gas Chromatography Mass Spectrometry- A Review

Abstract@#Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants with toxic effects and adverse health impacts on general population. Several methods of extraction had been applied to extract PAHs from human blood samples such as solid phase extraction (SPE). The SPE represents one of the most common techniques for extraction and clean-up procedures as it needs low quantity of solvents with less manual efforts. Similarly, various analytical instruments like gas chromatography coupled to mass spectrometry (GC-MS) was used to measure the PAHs levels. Gas chromatography is a simple, fast, and very efficient method for solvents and small organic molecules. This review provides an overview of the measured concentrations of PAHs in human blood samples through the application of SPE and GCMS during the last ten years. While these studies used various solvents, their application of SPE method and GC-MS revealed rewarding results about the determination of PAHs levels in the human samples.

Clinical value of serum phospholipase A2 in the screening and diagnosis of benign prostatic hyperplasia / 国际检验医学杂志

Objective To investigate the clinical value of serum lipoprotein associated phospholipase A 2 (Lp-PLA2)as a biomarker for benign prostatic hyperplasia(BPH).Methods A total of 65 serum samples of BPH patients were selected as BPH group,64 serum samples of healthy male as control group.The serum lev-el of Lp-PLA2,total prostate specific antigen(tPSA)and free prostate specific antigen(fPSA)in both groups were detected,and the specificity and sensitivity of Lp-PLA2,F/T ratio and combine both were analyzed by ROC curve.Results The serum level of Lp-PLA2,tPSA and fPSA in BPH group were significantly higher than those in control group,the different were significant(P<0.05).ROC curve analyze shown that the area under the curve(AUC)of Lp-PLA2 was 0.763,95% confidence interval(CI)was 0.680-0.833;AUC of F/T ratio was 0.715,95% CI 0.633 -0.795;AUC of Lp-PLA2 combined with F/T ratio was 0.832,95% CI 0.756-0.892.Conclusion The serum level of Lp-PLA2 could be used as a potential diagnostic marker for BPH,and the diagnostic value of Lp-PLA2 combined with F/T ratio was better than ther single indicator. Key words:benign prostatic hyperplasia; lipoprotein associated phospholipase A 2; total prostate spe-cific antigen; free prostate specific antigen; F/T ratio

Release of Bisphenol A From Polycarbonate and Polyethylene Terephthalate Drinking Water Bottles Under Different Storage Conditions and Its Associated Health Risk

@#Introduction: Bisphenol A (BPA) is a controversial plastics ingredient used mainly in the production of polycarbonate plastics (PC) and epoxy resins that widely used nowadays in food and drink packaging. Even though BPA is not involved in polyethylene terephthalate (PET) manufacturing, recent study had reported the present of BPA in PET water bottle. This study was conducted to investigate effects storage conditions on release of BPA from PC and PET bottled water as well as to assess health risks associated with consumption. Methods: Solid phase extraction (SPE) was used to extract the samples, followed by analysis using ultra high performance liquid chromatography with fluorescence detector (UHPLC-FLD). The possibility of developing chronic non-carcinogenic health risk among consumers of bottled water was evaluated using hazard quotient (HQ). Results: Results showed that BPA migrated from PC and PET water bottles at concentrations ranging from 9.13 to 257.67 ng/L and 11.53 ng/L to 269.87 ng/L respectively. Concentrations of BPA were higher in PET bottled water compared to PC bottled water across all storage conditions. Higher storage temperature and longer storage duration increased BPA concentrations in PC and PET bottled water. Concentrations of BPA in bottled water which were kept in a car and were exposed to sunlight were higher than control samples which were stored indoor at room temperature. Conclusion: No significant chronic non-carcinogenic health risks were calculated for daily ingestion of BPA-contaminated bottled water; calculated HQ was less than one.

Study of the sensitivity and specificity on near-infrared spectroscopy in diagnosis of depression / 中华行为医学与脑科学杂志

Objective To explore the sensitivity and specificity of near-infrared spectroscopy ( NIRS) in the diagnosis of depression. Methods From March 2013 to August 2013,62 patients with de-pression and 70 normal controls were collected from Peking University Sixth Hospital. Optical Tomography System (52 channels) was used to collect the NIRS data during the Verbal Fluency Test (VFT),and the number of words produced during VFT task was recorded. The wave analysis was performed by a professional psychiatrist. Results There was statistical difference in the number of words produced during VFT task be-tween the patients with depression (8.65±0.49)and control group(10.19±0.43) ( t=2.385, P<0.05). Through the wave analysis of NIRS to test patients with depression,the results demonstrated that the sensitivi-ty was 66.1% and the specificity was 91.4%. Conclusion The results of NIRS test display high specificity in the diagnosis of depression,which can be used as an objective index for clinical auxiliary diagnosis.

Detection of xylazine and 2,6-xylidine in blood and urine by SPE-HPLC/MS/MS / 中国法医学杂志

Objective To develop an HPLC-MS/MS method for simultaneous determination of xylazine and 2,6-xylidine in body fluid samples.Methods The samples were extracted by HLB SPE,separated by Waters Atlantis dC18 chromatographiccolumn,and then detected in the MRM scan ion mode under positive ionization condition.Results The recoveryrates of this method were between 70.5％ and 79.8％ with the range of RSD rfrom8.2％ to 10.5％.The limits of detection ofxylazine and 2,6-xylidine in blood and urine samples were 0.4 and 0.3 ng/mL,and the limits of quantitation were 1.2 and 1.0 ng/mL,respectively.Conclusion This method is of high sensitivity,good specificity and good reproducibility,and thus could besuitable for accurate quantification of xylazine in blood and urine samples.

Simultaneous determination of cordycepin and 2'-deoxyadenosine in Cordyceps genus by online SPE-HPLC / 中国中药杂志

An online SPE-HPLC method for simultaneous determination of cordycepin (3'-deoxyadenosine) and 2'-deoxyadenosine in Cordyceps genus (C. sinensis,C. militaris,Hirsutella sinensis and C. sobolifera) was developed. The samples were enriched on a ZORBAX SB-AQ (4.6 mm×12.5 mm,5 μm) column with isocratic elution by 9% methanol solution. The separation of analytes was performed on a ZORBAX SB-AQ (4.6 mm×150 mm,5 μm) column with gradient elution by 0.1% formic acid solution and methanol (91∶9). The flow rate was 1.0 mL•min⁻¹. Column temperature was 40 ℃ and detection wavelength was 260 nm. This method has been applied for analysis of different Cordyceps genus. The 2'-deoxyadenosine was detected in C. sinensis,Hirsutella sinensis and C. sobolifera. The cordycepin was detected in C. militaris. In summary,the cordycepin chromatographic peak from C. sinensis in some past reports may be the 2'-deoxyadenosine chromatographic peak or the mixture peak of 2'-deoxyadenosine and cordycepin in which 2'-deoxyadenosine content was higher than cordycepin. The developed method is suitable for analysis of cordycepin and 2'-deoxyadenosine in Cordyceps genus.

Highly sensitive assay for the determination of therapeutic peptide desmopressin in human plasma by UPLC–MS/MS / 药物分析学报

An analytical method based on ultra-performance liquid chromatography with positive ion electrospray ionization (ESI) coupled with tandem mass spectrometry (UPLC–MS/MS) was developed and validated for the determination of therapeutic peptide desmopressin in human plasma. A desmopressin stable labeled isotope (desmopressin d8) was used as an internal standard. Analyte and the internal standard were extracted from 200 μL of human plasma via solid-phase extraction technique using Oasis WCX cartridges. The chromatographic separation was achieved on an Aquity UPLC HSS T3 column by using a gradient mixture of methanol and 1 mM ammonium formate buffer as the mobile phase. The calibration curve obtained was linear (r2≥0.99) over the concentration range of 1.01–200 pg/mL. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. The results of the intra- and inter-day precision and accuracy studies were well within the acceptable limits. The proposed method was successfully applied to pharmacokinetic studies in humans.

A DFT study on Dichloro {(E)-4-dimethylamino-N'-[(pyridin-2-yl) methylideneK N] benzohydrazide-k0}M2+ (M = Zn, Cu, Ni, Fe, Mn, Ca and Co) complexes: Effect of the metal over association energy and complex geometry / Un estudio DFT en complejos Dicloro {(E)-4-dimetilamino-N'-[(piridin-2-il) metilideno-K N] benzohidrazida-K0} M2+ (M = Zn, Cu, Ni, Fe, Mn, Ca y Co): efecto del metal sobre la energía de asociación y la geometría del complejo / Um estudo DFT nos complexos Dicloro {(E)-4-dimetilamino-N'-[(piridin-2-il) metilideno -K N] benzohidrazida-K0} M2+ (M = Zn, Cu, Ni, Fe, Mn, Ca y Co): efeito do metal sobre a energia de associação e a geometria do complexo

The molecular geometry of (E)-4-dimethylamino-N'-[(pyridin-2yl)methylidene-kN]benzohydrazide (C15H16N4O) complexed with M²+ (M=Zn, Cu, Ni, Fe, Mn, Ca and Co) ions was calculated, using density functional theory (B3LYP) with 6-31G(d, p) basis set. Vibrational frequencies were computed in order to verify the absence of imaginary vibrational frequencies, fact that confirms the global minimum in geometry optimization. Molecular geometry parameters (bond lengths and angles) for Cu²+ and Zn²+ complexes were compared with crystallographic data previously reported, showing good correlation. Binding energies for all complexes were computed at the B3LYP/6-31G++(d, p) level of theory. These calculations indicate that Cu-L is the lowest favorable complex, Cu²+ corresponds to the smallest cation on the present study. On the other hand, Ca-L, one of the less favorable complex, corresponds to the largest cation analyzed in the present study. Molecular orbital analysis was carried out showing variations in ΔE HOMO-LUMO values as a function of the metallic ion employed.

La geometría molecular de la (E)-4-dimetilamino-N'-[(piridin-2-il) metilideno-kN] benzohidrazida (C15H16N4O) acomplejada con iones M²+ (M=Zn, Cu, Ni, Fe, Mn, Ca y Co) se calculó usando la teoría funcional de densidad (B3LYP) empleando un conjunto de bases 6-31G(d, p). Las frecuencias vibracionales fueron calculadas con el propósito de comprobar la ausencia de frecuencias vibracionales imaginarias, hecho que confirma el mínimo global en la optimización de la geometría. Los parámetros de la geometría molecular (longitudes de enlace y ángulos) para los complejos de Cu²+ y Zn²+ fueron comparados con datos cristalográficos previamente reportados, mostrando una buena correlación. Las energías de asociación para todos los complejos fueron determinadas a un nivel de teoría B3LYP/6-31G++(d, p) mostrando que el complejo menos favorable es Cu-L, correspondiente al catión más pequeño del estudio. Por otro lado Ca-L, uno de los menos estables, corresponde al catión más grande analizado. Se llevó a cabo un análisis de orbitales moleculares en el cual los complejos exhibieron diferentes valores de ΔE HOMO-LUMO en función del metal empleado.

A geometria molecular da (E)-4-dimetilamino-N'-[(piridin-2-il) metilideno-kN] benzohidrazida (C15H16N4O) acomplexada com íons M²+ (M=Zn, Cu, Ni, Fe, Mn, Ca y Co) foi calculada usando a teoria funcional da densidade (B3LYP) utilizando um conjunto de bases 6-31G(d, p). As frequências vibracionais foram calculadas com o objetivo de comprovar a ausência de frequências vibracionais imaginárias, fato que confirma o mínimo global na otimização da geometria. Os parâmetros da geometria molecular (longitudes de enlace e ângulos) para os complexos de Cu²+ y Zn²+ foram comparados com dados cristalográficos previamente reportados e mostraram boa correlação. As energias de associação para todos os complexos foram determinadas ao nível de teoria B3LYP/6-31G++(d, p) mostrando que o complexo menos favorável é Cu-L, correspondente ao cátion mais pequeno do estudo. Por outro lado Ca-L, um dos menos estáveis, corresponde ao cátion mais grande analisado. Foi feita uma análise de orbitais moleculares no qual os complexos exibiram diferentes valores de ΔE HOMO-LUMO em função do metal utilizado.

Optimization of a multi-residue method for 101 pesticides in green tea leaves using gas chromatography–tandem mass spectrometry

ABSTRACT A method for analysis of 101 pesticide residues in tea leaves was developed and validated for the first time. Pure acetonitrile was used as extraction solvent rather than acetonitrile after matrix hydration based on the amount of co-extracts and recoveries performance. During clean-up procedure, primary-secondary amine/graphitized carbon black (500 mg) was selected, which exhibited outstanding properties in clean-up capabilities and recoveries of pesticides comparing to primary-secondary amine/graphitized carbon black (250 mg), NH2-Carbon and TPT absorbents. The method was validated employing gas chromatography coupled to tandem mass spectrometry at the spiked concentration levels of 0.050 and 0.100 mg kg−1. For most of the targeted pesticides, the percent recoveries range from 70 to 120%, with relative standard deviations <20%. The linear correlation coefficients (r 2) were higher than 0.99 at concentration levels of 0.025–0.250 mg kg−1. Limits of quantification ranged from 1.1 to 25.3 µg kg−1 for all pesticides. The developed method was successfully applied to the determination of pesticides in tea leaf samples.

Detección del alucinógeno 25C-NBOMe en orina por dos técnicas cromatográficas / Detection of hallucinogen 25C-NBOMe in urine by two chromatographic techniques / Detecção de alucinógeno 25C-NBOME na urina através de duas técnicas cromatográficas

El consumo de drogas de síntesis ha ido en aumento. Estos nuevos derivados sintéticos son análogos estructurales de la feniletilamina N-sustituida. Este grupo ha provocado severos casos de intoxicación e incluso probablemente la muerte de varios consumidores. El principal derivado es conocido como 25C-NBOMe y se consume en estampillas idénticas al LSD. En este trabajo se desarrolla una metodología analítica para la determinación de 25C-NBOMe mediante cromatografía planar instrumental (cromatografía en capa delgada de alta resolución) y cromatografía de gases con detector de masas (CG/EM) como técnicas alternativas de fácil manejo y costo. Estas metodologías demostraron ser robustas y confiables para el propósito previsto.

Consumption of synthetic drugs has increased. These new synthetic derivatives are structural analogs of N-substituted phenylethylamine, and this group has caused severe cases of poisoning and even probably the death of several users. The main derivative is known as 25C-NBOMe and it is consumed in blotters in the same manner as LSD. In this work, an analytical methodology for 25C-NBOMe determination by instrumental planar chromatography high-performance thin-layer chromatography (HPTLC) and gas chromatography with mass detector (GC/MS) were developed as alternative techniques; they are easy to use and low cost. These methods proved to be robust and reliable for the intended purpose.

O consumo de drogas sintéticas vem aumentando. Esses novos derivados sintéticos são análogos estruturais de feniletilamina N-substituída, este grupo tem causado casos graves de intoxicação e, até mesmo, provavelmente, a morte de vários consumidores. O principal derivado é conhecido como 25C-NBOMe e consumido em selos idênticos ao LSD. Neste trabalho é desenvolvida uma metodologia analítica para a determinação de 25C-NBOMe através de cromatografia planar instrumental (cromatografia em camada delgada de alta resolução) e cromatografia gasosa com detector de massas (CG/EM) como técnicas alternativas de fácil utilização e custo. Estas metodologias demonstraram serem robustas e fiáveis para a finalidade a que se destinam.

Residues determination of oxytetracycline, tetrarcycline and chlortetracycline in zaosheng cattle meat by SPE-HPLC / 国际药学研究杂志

Objective To establish a method for simultaneous determination of 3 tetracyline antibiotics (TCs) oxytetra-cycline (OTC), tetracycline (TC), chlorotetecycline (CTC)) residues in Zaosheng cattle meat using solid phase extraction-high performance liquid chromatography (SPE-HPLC). Methods The samples were extracted by Na2EDTA-Mcllvaine buffer solution (pH=4.0), and 15% trichloroacetic acid (TCA) as the protein precipitation solution, then the targets were cleaned up and enriched by C18 solid phase extraction column. HPLC Mobile phase consisted of oxalic acid (0.01mol/L), acetonitrile as well as methanol. The detection wavelength was 350 nm and external standard method was adopted for quantification. Results The calibration curves of 3 TCs had good linearity with correlation coefficients of 0.998. The limits of detection of OTC, TC and CTC were 18, 15, 30 μg/kg, respectively, while their average recoveries were 76.10%-95.22%, with relative standard deviations (RSD) lower than 10% after optimized pretreatment and analytical conditions. Conclusion The method has high sensitivity, precision, and good repeatability, and can meet the needs of residue determination of TCs in meat.

Allogeneic hematopoietic stem cell transplantation followed by donor derived lymphocyte and EBV specif-ic cytotoxic T-lymphocyte immunotherapy for hydroa vacciniforme-like lymphoma:A case report and literature review / 实用肿瘤学杂志

The hydroa vacciniforme -like lymphoma is clinically manifested by rash ,fever,hepatospleno-megaly and lymphadenectasis .Pathological character showed that lymphocytes infiltrated into dermis and there were some heterocysts.Immunohistochemistory showed that Bcl -6,Bcl -2,CD3,CD8,TIA,CD4,granzyme, EBER were positive,CD56,CD20 all tested negative.The rearrangement of TCR of bone marrow cell was positive . The hydroa vacciniforme-like lymphoma is uncommon clinically ,and it is easy to misdiagnosed .The effect of tra-ditional therapy is poor ,while the allogeneic hematopoietic stem cell transplantation followed by lymphocyte and donor-derived EBV-specific cytotoxic T -lymphocyte immunotherapy is effective ,which may offer an curable therapy for HVLL.

Determination of Two Components in Shangyangyu Ointment by Solid Phase Extraction Coupled with HPLC Method / 中国药师

To develop a determination method forβ,β'-dimethylacrylalkannin and salvianolic acid B in Shangyangyu ointment by solid phase extraction coupled with HPLC. Methods:Solid phase extraction coupled with HPLC was used with a C18 (250 mm × 4. 6 mm, 5 μm) column, the mobile phase was acetonitrile-water-methanol-formic acid (700∶300∶30∶15) with the flow rate of 1. 0 ml·min-1. For β, β'-dimethylacrylalkannin, the detection wavelength was 275nm, and for salvianolic acid B, the detection wavelength was 286nm. Under the above conditions, the contents of main componentsβ,β'-dimethylacrylalkannin and salvianolic acid B in Shangyangyu ointment were determined. Results:The linear relationship was promising when the concentration ofβ,β'-dimethyl-acrylshikonin was within the range of 23. 780-118. 900μg·ml-1(r=0. 999 5) with the recovery of 99. 5% (RSD=1. 07%) and that of salvianolic acid B was within the range of 19.840-99.200 μg·ml-1(r=0.999 3) with the recovery of 98.2% (RSD=2.1%). Conclusion:The method is simple, accurate and fast with good separation, which can be used in the quality control of Shangyangyu ointment.

Discussion on the strategy of standardized resident training model of vascular ultrasonogra-phy / 中华医学教育探索杂志

Resident doctor is the beginning period of a doctor career. Resident standardization training is the basement period for the clinical ability training and is the important part for medical students after graduation education. Vascular ultrasonography belongs to ultrasound medicine and has its own discipline characteristics. The diagnosis accuracy of vascular ultrasonography largely depends on the accumulation of basic knowledge of multiple clinical sciences , standardization of operation techniques and especially the accurate application of hemodynamic theory. According to the discipline characteristics of vascular ultrasonography, we train the residents from the following five aspects: basic theory knowledge, operation techniques, clinic thinking ability, sciences research ability, communica-tion and team work ability. On the basis of practice, we explore the establishment of standardized training mode for medical professionals of vascular ultrasnography in China, training practical, innova-tive and independent talents, to provide reference for improving the professional level of vascular ultra-sound in our country.