The use of bioprocess to convert low valued biomass or agroindustrial byproducts into high-value chemicals is an emerging area. However, laboratories usually use outdated analytical techniques to identify bioproducts, losing valuable information, such as the identification of unexpected compounds. In this work, we presented a successful systematic and modern analytical approach based on direct infusion mass spectrometry (DIMS) for an automated high-throughput screening of untargeted compounds from glycerin bioconversion process. We describe advantages of DIMS and its combined application with chemometrics towards an untargeted metabolomics approach to analyze several samples in a short time (11 samples per h). Three batches with 34 samples from the bioconversion of glycerin using several filamentous fungi strains were analyzed. Batch 347 was selected as promising, since high value chemicals, such as amide, phenolic and acid compounds, were identified. The platform presented was fast, robust, and versatile, then it could be applied to different bioprocesses.

Jatropha curcas L. is an oil crop that has been studied as a potential source of biodiesel. A high protein pie is produced as a byproduct of the biodiesel production, which could be used as animal feed. However, the pie has toxic compounds, as phorbol esters and other toxins, which prevents the use as animal feed. For this reason, Embrapa (Brazilian Agricultural Research Corporation) has been working in genetic breeding to develop non-toxic J. curcas genotypes. To evaluate this process, a simple and fast analytical technique was employed to obtain responses in a short time. Leaf spray (LS) is a recent ambient ionization mass spectrometry technique in which the sample itself serves as support and ion source. Here, toxic and non-toxic J. curcas leaves were differentiated by LS using a linear ion trap mass spectrometer and partial least squares discriminant analysis (PLS-DA) model chemometrics. It was possible to differentiate toxic and non-toxic leaves and to identify the m/z values that contribute to discrimination between the groups.

Quantificação e identificação de misturas de biodiesel de soja com petrodiesel foram realizadas via espectrometria de massas utilizando duas técnicas de ionização: electrospray (ESI) e Venturi easy ambient sonic-spray em seu modo líquido (V L-EASI). Diferentes misturas de biodiesel/petrodiesel (de B0 até B100) foram diluídas e diretamente injetadas e analisadas por ambas as técnicas. Para investigar a adulteração em blendas Bn, misturas óleo de soja/biodiesel e óleo de soja/petrodiesel foram analisadas. Curvas analíticas foram obtidas em triplicata. As duas técnicas apresentaram quantificação suficientemente precisa na faixa de B1-B20. Estas técnicas foram úteis também na detecção de contaminação ou adulteração das misturas Bn com óleos vegetais. A técnica de ESI é hoje largamente difundida e comercialmente acessível enquanto que uma fonte de V L-EASI pode ser facilmente montada usando peças comuns de laboratório dispensando a aplicação de altas voltagens. As duas técnicas não necessitam de etapas de pré-separação ou derivatização e, portanto, oferecem métodos simples e rápidos para quantificação de misturas Bn. A detecção instantânea e abrangente da composição molecular permite o controle de qualidade e tipificação de biodiesel e, eventualmente, de óleos vegetais em misturas ilegais.

Quantitation and identification of blends of soybean biodiesel with petrodiesel were performed via mass spectrometry using two ionization techniques: electrospray ionization (ESI) and Venturi easy ambient sonic-spray ionization in its liquid mode (V L-EASI). Different soybean biodiesel/petrodiesel blends (from B0 to B100) were diluted and then directly infused and analyzed by both techniques. To investigate adulteration of Bn blends, different soybean oil/biodiesel and soybean oil/petrodiesel blends were analyzed. Analytical curves were obtained in three replicates. The two techniques were shown to provide reasonably accurate quantitation in the B1-B20 range. These techniques were also successfully used to detect contamination or adulteration of Bn blends with vegetable oils. ESI is a widely used and commercially available technique whereas a V L-EASI source can be easily mounted using common laboratory parts requiring no use of high voltages. Both techniques require no pre-separation or derivatization steps and offer, therefore, simple and fast methods for the quantitation of Bn blends. The comprehensive snapshots of the molecular composition also allow quality control and typification of the biodiesel and eventually of the vegetable oils in illegal admixtures.

Reações de 4-O-alil-2,3-di-O-benzil-6-desoxi-6-(3-iodobenzoilamino)-α-D-galactopiranosídeo de metila, seu epímero glico, 2,3-di-O-benzil-6-desoxi-6-(3-iodobenzoilamino)-4-O-(1-pentenil)-α-D-glicopiranosídeo de metila e seu regioisômero orto-iodobenzamida com hidreto de tri-n-butilestanho foram realizadas em diferentes condições. Dependendo das condições, os três precursores que contêm o átomo de iodo em posição meta conduziram a uma surpreendente quantidade de compostos bifenílicos, nos quais o átomo de iodo foi substituído por um grupo fenila. O substrato 2-iodobenzamida levou apenas ao produto de hidrogenólise. Nenhum produto ciclizado foi isolado de nenhuma das reações. As estruturas dos compostos bifenílicos inéditos foram elucidadas utilizando-se as espectrometrias de massa, de RMN ¹H e 13C e experimentos DEPT, COSY, HMQC e HMBC. Foram propostos mecanismos de formação dos compostos bifenílicos e hipóteses para explicar os diferentes comportamentos dos isômeros orto- e meta-iodobenzamidas na reação radicalar.

Reactions of methyl 4-O-allyl-2,3-di-O-benzyl-6-deoxy-6-(3-iodobenzoylamino)-α-D-galactopyranoside, its gluco epimer, methyl 2,3-di-O-benzyl-6-deoxy-6-(3-iodobenzoylamino)-4-O-(1-pentenyl)-α-D-glucopyranoside and its ortho-regioisomer with tri-n-butyltin hydride were performed in different conditions. Depending on reaction conditions the three meta-iodo isomers gave a surprising amount of biphenyl compounds. The 2-iodo isomer led only to the undesired but expected hydrogenolysis product. No cyclized products were isolated in all the reactions. The structures of the new biphenyl products were elucidated by ¹H and 13C NMR spectroscopy, DEPT, COSY, HMQC and HMBC experiments and ESI-MS/MS. Mechanisms for the formation of these new biphenyl derivatives and hypotheses to explain the different outcomes for radical reactions of 3- or 2-iodobenzamides were presented.