Stabilisation of dehydrated nanoemulsions using sugar - protein matrices

There are numerous review papers discussing liquid nanoemulsions and how they compare to other emulsion systems. Little research is available on dried nanoemulsions. The objectives of this research were to (i) study the effect of varying the continuous phase of nanoemulsions with different carbohydrate/protein ratios on subsequent emulsion stability, and (ii) compare the physicochemical properties, lactose crystallisation properties, microstructure, and lipid oxidation of spray dried nanoemulsions compared to spray dried conventional emulsions having different water and sugar contents. Nanoemulsions containing sunflower oil (10% w/w), β-casein (2.5–10% w/w) and lactose or trehalose (10–17.5%) were produced following optimisation of the continuous phase by maximising and minimising viscosity and glass transition temperature (Tg’) using mixture design software. Increasing levels of β-casein from caused a significant increase in viscosity, particle size, and nanoemulsion stability, while resulting in a decrease in Tg’. Powders were made from spray drying emulsions/nanoemulsions consisting of lactose or a 70:30 mixture of lactose:sucrose (23.9%), sodium caseinate (5.1%) and sunflower oil (11.5%) in water. Nanoemulsions, produced by microfluidisation (100 MPa), had higher stability and lower viscosity than control emulsions (homogenization at 17 MPa) with lower solvent extractable free fat in the resulting powder. Partial replacement of lactose with sucrose decreased Tg and delayed Tcr. DVS and PLM showed that in powdered nanoemulsions, lactose crystallises faster than in powdered conventional emulsions. Microstructure of both powders (CLSM and cryo-SEM) showed different FGS in powders and different structure post lactose crystallisation. Powdered nanoemulsions had lower pentanal and hexanal (indicators of lipid oxidation) after 24 months storage due to their lower free fat and porosity, measured using a validated GC HS-SPME method, This research has shown the effect of altering the continuous phase of nanoemulsions on microstructure of spray dried nanoemulsions, which affects physical properties, sugar crystallisation, and lipid oxidation.

Gene expression profiling in hearts of transgenic mice overexpressing guanylyl cyclase domain of the GC-A receptor

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Ferulates and lignin structural composition in cork

The structure of lignin and suberin, and ferulic acid (FA) content in cork from Quercus suber L. were studied. Extractive-free cork (Cork), suberin, desuberized cork (Cork(sap)), and milled-cork lignins (MCL) from Cork and Cork(sap) were isolated. Suberin composition was determined by GC-MS/FID, whereas the polymers structure in Cork, Corksap, and MCL was studied by Py-TMAH and 2D-HSQC-NMR. Suberin contained 94.4% of aliphatics and 3.2% of phenolics, with 90% of omega-hydroxyacids and alpha,omega-diacids. FA represented 2.7% of the suberin monomers, overwhelmingly esterified to the cork matrix. Py-TMAH revealed significant FA amounts in all samples, with about 3% and 6% in cork and cork lignins, respectively. Py-TMAH and 2D-HSQC-NMR demonstrated that cork lignin is a G-lignin (>96% G units), with a structure dominated by beta-O-4' alkyl-aryl ether linkages (80% and 77% of all linkages in MCL and MCLsap, respectively), followed by phenylcoumarans (18% and 20% in MCL and MCLsap, respectively), and smaller amounts of resinols (ca. 2%) and dibenzodioxocins (1%). HSQC also revealed that cork lignin is heavily acylated (ca. 50%) exclusively at the side-chain gamma-position. Ferulates possibly have an important function in the chemical assembly of cork cell walls with a cross-linking role between suberin, lignin and carbohydrates.

Desenvolvimento de método para determinação de espécies de mercúrio empregando MSPD e GC-MS

Neste trabalho é proposto pela primeira vez, o desenvolvimento e validação de um método analítico baseado no emprego da dispersão da matriz em fase sólida (MSPD) modificada, para extração das espécies CH3Hg+ e Hg2+ em amostras de peixe e determinação por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS). O método de extração utilizando a MSPD combina o rompimento da estrutura física da amostra, através da maceração e do uso de SiO2 como suporte sólido, com o método da extração ácida, utilizando uma solução de HCl 4,2 mol L-1 e NaCl 0,5 mol L-1. Para otimização da MSPD, foram avaliados parâmetros como massa de amostra, massa de suporte sólido, concentração de HCl, concentração de NaCl, tipo de suporte sólido e o tempo de agitação, com auxílio da metodologia de superfície de resposta. Além disso, a etapa de derivatização e a separação cromatográfica também foram otimizadas na determinação de CH3Hg+ e Hg2+ por GC-MS. O método mostrouse adequado para extração e determinação de espécies de mercúrio através da aplicação em materiais de referência certificados de fígado de peixe (DOLT-3) e músculo de peixe (DORM-2), apresentando boas concordâncias com os valores certificados e desvio padrão relativo inferior a 9,5%. Os limites de detecção foram de 0,06 e 0,12 µg g-1 para CH3Hg+ e Hg2+, respectivamente. Além disso, foi observado um significativo efeito de matriz e, por isso, a calibração foi feita com curvas preparadas com o extrato da MSPD. O método mostrou boa concordância na comparação entre a soma da concentração das espécies e a concentração de mercúrio total determinada por espectrometria de massas com plasma indutivamente acoplado com geração de vapor frio (CVG-ICP-MS), após digestão assistida por micro-ondas (MAD) em peixes do tipo atum (Thunnus thynnus), cação anjo (Squatina squatina) e cação viola (Rhinobatos blochii.).

Evaluation and comparison of durability of polycyclic aromatic hydrocarbon compounds (PAHs) and its relation to the lipid content in smoked fishes, Silver carp (Hypophthalmichthys molitrix), Rutilus frisii kutum and Herring (Alosa caspia)

Cold smoking method is one of the commonest ways for fish smoking. It is done by the smoke that is the result of burning hard and soft woods is smoking rooms. Smoke includes a number of chemical constructs and its main part is poly aromatic hydrocarbons. More than one hundred kinds of these constructs are recognized in smoke that is produced from saturated hydrocarbons resulted from the solution of the woods Ligno cellulose in high temperature and lack of oxygen conditions. The high poisoning potentials and carcinogenic features sixteen constructs among them are proved and observed on humans. In this research, the PAH compounds were identified and observed in a three month period after smoking and during storing among three types of smoked fishes Silver carp and Caspian sea Sefid and herring. They are the most produced and consumed smoked fish in Iran. To find the relationship between the concentrations of PAH constructs and the amount of lipid in fish, first, the amount of lipid were determined separately in the skin and flesh of 30 samples of each type. The method used was Bligh and Dyer (1959). PAH compounds derivation were made for all skin and flesh samples smoked fish using organic solvents with Soxeleh and the derived samples were injected to gas chromatography (GC) by Hamilton injectors for determining their components quality and their quantity. The height of the used column was 25 meters and its diameter was 0.32 mm with the silica filler, nitrogen gas as carrier and flame ionization detector (FID) that are special for these constructs. For data analysis, Statistical tests were used by computer soft ware identified that the difference in the amount of lipid within the flesh and skin of each species and also among each other is significant. The largest amount was in Herrings flesh and skin, 18.74% in skin and 14.47% in flesh. The least amount in the skin 4.19% and the flesh 3.10% of Sefid. The amount in Silver carp was 13.28%in skin and 8.16% in flesh. The examination of the PAH compounds in smoked fish showed that is carcinogenic compounds; exist in these in these fish with different quantities in each. It seems that its amount is directly related to the amount of their lipid. The amount is different in flesh and skin. One of the most important reasons is the direct content of smoke and the concentration of lipid in tissues of all three types. The maintenance of the smoked fish for three months showed that most of PAH compounds were solved and their density decreased. The changes in density within time in different in each type and in flesh and skin. The amount of their receiving in human through the consumption of the smoked fish depends on the resulted density, the way and the amount of consumption and now we can determine and execute standards for the maximum dosage per day and per month regarding effective factors.

Desenvolvimento e validação de método para determinação do perfil graxo do biodiesel de Tungue e Blendas com soja empregando GC-MS

No Brasil o biodiesel é utilizado em misturas com óleo diesel em proporções de 5%, sem que haja modificações nos motores. Com o intuito de diversificar a utilização de oleaginosas não comestíveis no ramo dos biocombustíveis, e ainda vincular a produção com agricultura sustentável, uma alternativa para o RS é a utilização do óleo de tungue para a produção de biodiesel. A caracterização e quantificação de ácidos graxos do biodiesel de tungue, torna-se importante devido à seu exclusivo perfil graxo. Neste trabalho, foi estudado o desenvolvimento e validação de método para a determinação do perfil graxo do biodiesel metílico de tungue e blendas com soja utilizando GC-MS. Os parâmetros de validação considerados foram: curva analítica, linearidade, seletividade, limite de detecção e quantificação, robustez, precisão e exatidão. Para determinar as melhores condições cromatográficas, foram testadas diferentes programações de temperatura no forno cromatográfico; fluxo de gás; temperatura do injetor, detector e interface; e modo de injeção. As condições do GCMS após a otimização foram: injeção de 1 µL com injeção em alta pressão (300 kPa), T do injetor: 250 ºC, injeção split 1:30, fluxo de 1 mL min-1, coluna Rtx-5MS com dimensões 30 m x 0,25 mm x 0,25 µm, T forno: isoterma de 2 min a 130 ºC, aumento de 20 ºC/min até 220 ºC, aumento de 0,5ºC/min até 223ºC, aumento de 7 ºC/min até 250 ºC e isoterma em 250 ºC por 3 min, resultando em 20 min de análise. A temperatura da fonte e interface foram de 200 ºC e 250 ºC, respectivamente, com o MS no modo full scan, ionização por impacto eletrônico a 70 eV, e intervalo de massas de 30 a 500 u.m.a. A identificação do α-eleosteárico foi baseada na fragmentação característica do composto, pela comparação com o espectro do ácido linolênico, e ainda pelo tempo de retenção do composto. Na validação, as curvas analíticas apresentaram valores de r maiores que 0,99. O LD e LQ foram adequados, permitindo a quantificação de ésteres na concentração mínima de 0,6%. Os valores de exatidão ficaram entre 86 e 117%, com RSD% menores que 8%. O efeito matriz também foi avaliado, sendo que esse efeito foi considerado médio para a maioria dos compostos, ficando entre ± 20 e 50%. Durante a aplicação do método, o mesmo se mostrou adequado para amostras de biodiesel metílico de tungue e blendas com soja, nas proporções de 15:85, 20:80 e 25:75 (T:S, v/v). A aplicabilidade do método também foi testada para o biodiesel de soja, obtendo resultados satisfatórios, mostrando-se assim, além de tudo, ser um método robusto.

Development of procedures for the triazole fungicides determination in fruits and liquid samples using microextraction techniques and chromatographic separation

Agricultural crops can be damaged by funguses, insects, worms and other organisms that cause diseases and decrease the yield of production. The effect of these damaging agents can be reduced using pesticides. Among them, triazole compounds are effective substances against fungus; for example, Oidium. Nevertheless, it has been detected that the residues of these fungicides in foods as well as in derivate products can affect the health of the consumers. Therefore, the European Union has established several regulations fixing the maximum residue of pesticide levels in a wide range of foods trying to assure the consumer safety. Hence, it is very important to develop adequate methods to determine these pesticide compounds. In most cases, gas or liquid chromatographic (GC, LC) separations are used in the analysis of the samples. But firstly, it is necessary to use proper sample treatments in order to preconcentrate and isolate the target analytes. To reach this aim, microextraction techniques are very effective tools; because allow to do both preconcentration and extraction of the analytes in one simple step that considerably reduces the source of errors. With these objectives, two remarkable techniques have been widely used during the last years: solid phase microextraction (SPME) and liquid phase microextraction (LPME) with its different options. Both techniques that avoid the use or reduce the amount of toxic solvents are convenient coupled to chromatographic equipments providing good quantitative results in a wide number of matrices and compounds. In this work simple and reliable methods have been developed using SPME and ultrasound assisted emulsification microextraction (USAEME) coupled to GC or LC for triazole fungicides determination. The proposed methods allow confidently determine triazole concentrations of μg L‐1 order in different fruit samples. Chemometric tools have been used to accomplish successful determinations. Firstly, in the selection and optimization of the variables involved in the microextraction processes; and secondly, to overcome the problems related to the overlapping peaks. Different fractional factorial designs have been used for the screening of the experimental variables; and central composite designs have been carried out to get the best experimental conditions. Trying to solve the overlapping peak problems multivariate calibration methods have been used. Parallel Factor Analysis 2 (PARAFAC2), Multivariate Curve Resolution (MCR) and Parallel Factor Analysis with Linear Dependencies (PARALIND) have been proposed, the adequate algorithms have been used according to data characteristics, and the results have been compared. Because its occurrence in Basque Country and its relevance in the production of cider and txakoli regional wines the grape and apple samples were selected. These crops are often treated with triazole compounds trying to solve the problems caused by the funguses. The peel and pulp from grape and apple, their juices and some commercial products such as musts, juice and cider have been analysed showing the adequacy of the developed methods for the triazole determination in this kind of fruit samples.

GC-MS Analysis, Antimicrobial and Antioxidant Activities of Extracts of the Aerial Parts of Conyza sumatrensis

Phytochemical analyses as well as antimicrobial and antioxidant activities of the extracts of C. sumatrensis aerial parts were investigated in this study. METHODS: The aerial parts of C. sumatrensis were air dried, weighed and exhaustively extracted with hexane, ethyl acetate and methanol successively. The crude extracts were screened for metabolites. These extracts of the plant were evaluated for antimicrobial and antioxidant activities using agar diffusion and DPPH method respectively. The extracts were also analysed using Gas chromatography – Mass spectrometry, and the chromatogram coupled with mass spectra of the compounds were matched with a standard library. RESULTS: Preliminary phytochemical investigation of crude n-hexane, ethyl acetate and methanol extracts of the aerial parts of Conyza sumatrensis revealed the presence of anthraquinones, flavonoids, terpenoids, phenolics, tannin, glycosides and carbohydrate. All the crude extracts gave a clear zone of inhibition against the growth of the test bacteria ( Staphylococcus aureus , Escherichia coli , Bacillus subtilis , Pseudomona aeruginosa, Salmonella typhi , Klebsiellae pneumonae ) at moderate to high concentrations, as well as test fungi ( Candida albicans , Aspergillus niger , penicillium notatum and Rhizopus stolonifer ) at high concentration. Methanolic extract exhibited significant radical scavenging property with IC50 of 17.08 μg/mL while n-hexane and ethyl acetate extracts showed no significant antioxidant activity. GC-MS of N-hexane extract showed a total number of eleven chemical constituents with α-Farnesene and spathulenol being the most abundance compounds constituting 20.27 and 22.28% of the extract respectively. Ethyl acetate extract revealed thirteen compounds with two most abundant compounds, cis-β-farnesene (16.64 %) and cis-pinane (21.09 %). While methanolic extract affords seventeen compounds with Ephytol being the most abundant compound (19.36 %).

UTILIZING ELECTRONIC NOSE AND GC-MS TO EXAMINE CRITICAL FACTORS INFLUENCING THE FORMATION OF ODOROUS VOC’S IN BIOSOLIDS.

Despite the efforts to better manage biosolids field application programs, biosolids managers still lack of efficient and reliable tools to apply large quantities of material while avoiding odor complaints. Objectives of this research were to determine the capabilities of an electronic nose in supporting process monitoring of biosolids production and, to compare odor characteristics of biosolids produced through thermal-hydrolysis anaerobic digestion (TH-AD) to those of alkaline stabilization in the plant, under storage and in the field. A method to quantify key odorants was developed and full scale sampling and laboratory simulations were performed. The portable electronic nose (PEN3) was tested for its capabilities of distinguishing alkali dosages in the biosolids production process. Frequency of recognition of unknown samples was tested achieving highest accuracy of 81.1%. This work exposed the need for a different and more sensitive electronic nose to assure its applicability at full scale for this process. GC-MS results were consistent with those reported in literature and helped to elucidate the behavior of the pattern recognition of the PEN3. Odor characterization of TH-AD and alkaline stabilized biosolids was achieved using olfactometry measurements and GC-MS. Dilution-to-threshold of TH-AD biosolids increased under storage conditions but no correlation was found with the target compounds. The presence of furan and three methylated homologues in TH-AD biosolids was reported for the first time proposing that these compounds are produced during thermal hydrolysis process however, additional research is needed to fully describe the formation of these compounds and the increase in odors. Alkaline stabilized biosolids reported similar odor concentration but did not increase and the ‘fishy’ odor from trimethylamine emissions resulted in more offensive and unpleasant odors when compared to TH-AD. Alkaline stabilized biosolids showed a spike in sulfur and trimethylamine after 3 days of field application when the alkali addition was not sufficient to meet regulatory standards. Concentrations of target compounds from field application of TH-AD biosolids gradually decreased to below the odor threshold after 3 days. This work increased the scientific understanding on odor characteristics and behavior of two types of biosolids and on the application of electronic noses to the environmental engineering field.

Significati particolari di ἀπάτη e ἀπατάω nel greco koiné e l’interpretazione di ἀπατῶν καρδίαν αὐτοῦ in Gc 1,26

L.T. Johnson ha interpretado ἀπατῶν καρδίαν αὐτοῦ in Sant 1,26 como “indulging his heart”. La propuesta requiere una revisión de los casos en los que ἀπάτη y ἀπατάω tienen un significado diferente del original “engaño” / “engañar” en varias fuentes antiguas. La investigación ha conducido a la identificación de tres significados del verbo y del nombre, todos ellos relacionados con la semántica del placer y la diversión. En Sant 1:26 podemos admitir el significado de “dar placer” para ἀπατάω. Llegamos a la conclusión, sin embargo, que esta interpretación es muy poco probable y es preferible dar a ἀπατάω el sentido de “engañar”.

Rapid portable GC-MS analysis for on-site screening of phytochemical leaf oils in an Australian Native Botanic Garden.

2016

Avaliação preliminar da contaminação por BTEX, em água subterrânea de poços tubulares, no município de Natal-RN

Among the different types of pollutants typically attributed to human activities, the petroleum products are one of the most important because of its toxic potential. This toxicity is attributed to the presence of substances such as benzene and its derivatives are very toxic to the central nervous system of man, with chronic toxicity, even in small concentrations. The area chosen for study was the city of Natal, capital of Rio Grande do Norte, where samples were collected in six different areas in the city, comprising 10 wells located in the urban area, being carried out in three distinct periods March/2009, December / June/2010 and 2009, and were evaluated for contamination by volatile hydrocarbons (BTEX - benzene, toluene, ethylbenzene and xylenes), so this work aimed to assess the quality of groundwater wells that supply funding for public supply and trade in the urban area of the city of Natal, in Rio Grande do Norte, contributing to the environmental assessment of the municipality. The analysis of BTEX in water was performed according to EPA Method 8021b. Was used the technique of headspace (TriPlus TP100) coupled to high resolution gas chromatography with selective photoionization detector (PID) and flame ionization (FID) - model Trace GC Ultra, Thermo Electron Corporation brand. The procedure adopted allowed the detection of concentrations of the order of μg.L-1. Data analysis with respect to BTEX in groundwater in the area monitored so far, shows that water quality is still preserved, because it exceeds the limits imposed by the potability Resolution CONAMA Nº. 396, April 2008

Análise de hidrocarbonetos policíclicos aromáticos (HPA's) em amostras de lodo de esgoto por GC-MS/MS.

2009

Fast Detection and Chemical Characterization of Gunshot Residues by CMV-GC-MS and LIBS

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.