Capillary photoionization: interface for low flow rate liquid chromatography-mass spectrometry

This is the first report on capillary photoionization (CPI) interfacing a liquid chromatograph (LC) and mass spectrometer (MS). A new heated CPI ion source was developed, including a heated transfer capillary, a wide oval-shaped and low-depth ionization chamber with a vacuum ultraviolet (VUV) transparent magnesium fluoride (MgF2) window to increase the photoionization efficiency and thus the sensitivity. As both analytes and eluent are first vaporized and then photoionized inside the CPI ion source between the atmosphere and the vacuum of MS, the ion transfer efficiency into the MS and thus the sensitivity is improved. The effect of the most important operation parameters, the eluent flow rate and temperature of the CPI source, on the signal intensity was studied with selected steroids. The feasibility of LC-CPI-MS/MS for the quantitative analysis of steroids was also studied in terms of linearity, repeatability, and limits of detection. The method showed good quantitative performance and sensitivity down to the low femto-mole level.Peer reviewe

Cell adhesion and proliferation on common 3D printing materials used in stereolithography of microfluidic devices

Three-dimensional (3D) printing has recently emerged as a cost-effective alternative for rapid prototyping of microfluidic devices. The feature resolution of stereolithography-based 3D printing is particularly well suited for manufacturing of continuous flow cell culture platforms. Poor cell adhesion or material-induced cell death may, however, limit the introduction of new materials to microfluidic cell culture. In this work, we characterized four commercially available materials commonly used in stereolithography-based 3D printing with respect to long-term (2 month) cell survival on native 3D printed surfaces. Cell proliferation rates, along with material-induced effects on apoptosis and cell survival, were examined in mouse embryonic fibroblasts. Additionally, the feasibility of Dental SG (material with the most favored properties) for culturing of human hepatocytes and human-induced pluripotent stem cells was evaluated. The strength of cell adhesion to Dental SG was further examined over a shear force gradient of 1–89 dyne per cm² by using a custom-designed microfluidic shear force assay incorporating a 3D printed, tilted and tapered microchannel sealed with a polydimethylsiloxane lid. According to our results, autoclavation of the devices prior to cell seeding played the most important role in facilitating long-term cell survival on the native 3D printed surfaces with the shear force threshold in the range of 3–8 dyne per cm².Three-dimensional (3D) printing has recently emerged as a cost-effective alternative for rapid prototyping of microfluidic devices. The feature resolution of stereolithography-based 3D printing is particularly well suited for manufacturing of continuous flow cell culture platforms. Poor cell adhesion or material-induced cell death may, however, limit the introduction of new materials to microfluidic cell culture. In this work, we characterized four commercially available materials commonly used in stereolithography-based 3D printing with respect to long-term (2 month) cell survival on native 3D printed surfaces. Cell proliferation rates, along with material-induced effects on apoptosis and cell survival, were examined in mouse embryonic fibroblasts. Additionally, the feasibility of Dental SG (material with the most favored properties) for culturing of human hepatocytes and human-induced pluripotent stem cells was evaluated. The strength of cell adhesion to Dental SG was further examined over a shear force gradient of 1-89 dyne per cm(2)by using a custom-designed microfluidic shear force assay incorporating a 3D printed, tilted and tapered microchannel sealed with a polydimethylsiloxane lid. According to our results, autoclavation of the devices prior to cell seeding played the most important role in facilitating long-term cell survival on the native 3D printed surfaces with the shear force threshold in the range of 3-8 dyne per cm(2).Peer reviewe

Fish-Liver-on-Chip: A Microfluidic Model to Assess Bioaccumulation of Environmental Drug Residues In Vitro

Peer reviewe

Analysis of anabolic steroids in urine by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry with chlorobenzene as dopant

Corrigendum to J. Chromatogr. A 1312 (2013), p. 111-117: Support by one project was inadvertently not mentioned in the Acknowledgements. The Acknowledgement should read:Funding from the Academy of Finland (projects 251575 and 257316) and the Finnish Funding Agency for Technology and Innovation(project 1291/31/084) is acknowledged. L. Hintikka is grateful to the CHEMSEM graduate school for financial support. Dr. Ville Saarela isthanked for the design and fabrication of the microchips. J. Chromatogr. A 1448 (2016) p. 128.Peer reviewe

Analysis of steroids in urine by gas chromatography-capillary photoionization-tandem mass spectrometry

A new heated capillary photoionization (CPI) ion source design was developed to photoionize analytes inside a transfer capillary between a gas chromatograph (GC) and a mass spectrometer (MS). The CPI setup included a wide, oval-shaped vacuum-ultraviolet (VUV) transparent magnesium fluoride (MgF2) window to maximize photoionization efficiency and thus sensitivity. The source contained a nitrogen housing around the ionization chamber inlet to avoid undesirable hydrolysis and oxidation reactions with ambient air and to maximize the proportion of formed molecular radical cations of analytes. The feasibility of the ion source was studied by analyzing 18 endogenous steroids in urine as their trimethylsilyl (TMS) derivatives with gas chromatography-tandem mass spectrometry (GC-MS/MS). The method was validated and applied to human urine samples. To our best knowledge, this is the first time that a capillary photoionization ion source has been applied for quantitative analysis of biological samples. The GC-CPI-MS/MS method showed good chromatographic resolution (peak half-widths between 3.1 to 5.3 s), acceptable linearity (coefficient of determination between 0.981 to 0.996), and repeatability (relative standard deviation (RSD%) between 5 to 18%). Limits of detection (LOD) were between 2 to 100 pg mL(-1) and limits of quantitation (LOQ) were between 0.05 to 2 ng mL(-1). In total, 15 steroids were quantified either as a free steroid or glucuronide conjugate from the urine of volunteers. The new CPI source design showed excellent sensitivity for analysis of steroids in complex biological samples. (C) 2019 Elsevier B.V. All rights reserved.Peer reviewe

A miniaturised 3D printed polypropylene reactor for online reaction analysis by mass spectrometry

Correction: Reaction Chemistry & Engineering, vol. 2:5, p. 811 DOI: 81110.1039/C7RE90018JA miniaturised polypropylene reactor was fabricated by 3D printing using fused deposition modeling. A stainless steel nanoelectrospray ionisation capillary and a magnetic stir bar were integrated into the reactor during the printing process. The integrated nanoelectrospray ionisation capillary allows direct sampling of a reaction solution without external pumping. It also allows ionisation of the analytes. Therefore, very rapid online mass spectrometric chemical reaction monitoring is possible. Operation of the miniaturised reactor is shown by the online nanoelectrospray mass spectrometry characterisation of a Diels–Alder reaction and the subsequent retro Diels–Alder reaction.Peer reviewe

Simple 3D printed stainless steel microreactors for online mass spectrometric analysis

A simple flow chemistry microreactor with an electrospray ionization tip for real time mass spectrometric reaction monitoring is introduced. The microreactor was fabricated by a laser-based additive manufacturing technique from acid-resistant stainless steel 316L. The functionality of the microreactor was investigated by using an inverse electron demand Diels-Alder and subsequent retro Diels-Alder reaction for testing. Challenges and problems encountered are discussed and improvements proposed. Adsorption of reagents to the rough stainless steel channel walls, short length of the reaction channel, and making a proper ESI tip present challenges, but the microreactor is potentially useful as a disposable device.Peer reviewe

Method for the Intraoperative Detection of IDH Mutation in Gliomas with Differential Mobility Spectrometry

Isocitrate dehydrogenase (IDH) mutation status is an important factor for surgical decision-making: patients with IDH-mutated tumors are more likely to have a good long-term prognosis, and thus favor aggressive resection with more survival benefit to gain. Patients with IDH wild-type tumors have generally poorer prognosis and, therefore, conservative resection to avoid neurological deficit is favored. Current histopathological analysis with frozen sections is unable to identify IDH mutation status intraoperatively, and more advanced methods are therefore needed. We examined a novel method suitable for intraoperative IDH mutation identification that is based on the differential mobility spectrometry (DMS) analysis of the tumor. We prospectively obtained tumor samples from 22 patients, including 11 IDH-mutated and 11 IDH wild-type tumors. The tumors were cut in 88 smaller specimens that were analyzed with DMS. With a linear discriminant analysis (LDA) algorithm, the DMS was able to classify tumor samples with 86% classification accuracy, 86% sensitivity, and 85% specificity. Our results show that DMS is able to differentiate IDH-mutated and IDH wild-type tumors with good accuracy in a setting suitable for intraoperative use, which makes it a promising novel solution for neurosurgical practice.Peer reviewe

Imatran kaupunkipuron suunnittelu, toteutus ja seuranta

Rakennettu luonnonmukainen elinympäristö voi edistää vaelluskalojen poikastuotantoa vesivoimalaitoksen tai muun patorakenteen yhteydessä. Elinympäristö toimii samalla kokonaisen ekosysteemin perustana. Tyypillisesti vesivoiman rakentamisessa on menetetty huomattavasti virtavesien eliöstölle soveltuvaa elinympäristöä, jota luonnonmukaiset ratkaisut voivat korvata osana ekologista kompensaatiota. Toimenpiteellä voidaan siis parantaa rakennetun vesistön ekologista arvoa ja tilaa. Tässä raportissa kuvataan Imatran kaupunkipuron suunnittelu- ja rakennusvaiheet sekä raportoidaan seurannan tulokset rakennusvaiheen jälkeen. Imatran kaupunkipuron suunnittelussa korostettiin puron soveltuvuutta taimenelle sopivana elinympäristönä. Vaikka kaupunkipuroa ei ole suunniteltu vaellusreitiksi, käytettyjä suunnitteluperiaatteita voi soveltaa suoraan myös luonnonmukaisiin ohitusuomiin. Imatran kaupunkipuro valmistui vuonna 2014 puistomaiselle alueelle ja joutomaalle Imatrankosken voimalaitoksen läheisyyteen. Puro on noin yhden kilometrin mittainen ja sen leveys vaihtelee 2–10 metrin välillä. Uoman suunnittelussa huomioitiin erilaisten elinympäristöjen ja taimenen kutu- ja poikasalueiden lisäksi myös maisemalliset tekijät ja soveltuvuus virkistyskäyttöön. Imatrankosken padon putouskorkeus, 24 m, ja käytettävissä oleva alue pyrittiin hyödyntämään mahdollisimman hyvin. Lisäksi mutkittelemalla uomaa sen pituus voitiin maksimoida. Uoman materiaalina käytettiin (vaihtelevan kokoista) soraa, isompia kiviä sekä puumateriaalia. Kaupunkipuron virtaama on kesäaikaan noin 250 l/s ja talvella noin 100 l/s. Tavoite purosta taimenen lisääntymisympäristönä näyttää toteutuneen, sillä taimen ja muutkin kala- ja eliölajit ovat ottaneet puron käyttöönsä. Imatran kaupunkipurossa taimenen lisääntyminen on onnistunut jopa odotuksia paremmin ja poikastiheys on korkeampi kuin vastaavissa luonnonpuroissa. Kaupunkipuron pinta-ala on huomattavan vähäinen verrattuna valtavaan määrään patoamisen seurauksena menetettyä koskipinta-alaa. Rakennettu luonnonmukainen elinympäristö kuitenkin tarjoaa uhanalaiselle taimenelle soveltuvaa elinympäristöä. Jokaista luonnossa syntynyttä yksilöä voidaan pitää lajin kannalta tärkeänä. Pohjaeläimistö on runsastunut lajirikkaudeltaan joka vuosi. Samalla pohjaeläinten lukumäärä on moninkertaistunut neljän tarkkailuvuoden aikana. Luonnolle, lajistolle ja ekosysteemeille aiheutettujen haittojen vähentäminen on tulossa myös olemassa olevan vesivoiman vastuulle. Pelkät kalataloudelliset kompensaatiot tai pelkkä kalatie eivät riitä ratkaisemaan ongelmia, jotka vesirakentaminen ja vesivoima ovat aiheuttaneet erityisesti soveltuvien elinympäristöjen määrälle ja laadulle. Imatran kaupunkipurolta saadut tulokset rohkaisevat jatkossa nostamaan erilaiset rakennetut luonnonmukaiset elinympäristöt ja kompensaatiohabitaatit toimivaksi vaihtoehdoksi virtavesien tilan parantamisessa.Abstract Nature-like habitat as ecological compensation in streams Built nature-like habitat can promote the juvenile production of migratory fish in vicinity of a hydropower plant or a distinct dam structure. At the same time, the habitat serves as the basis for the entire ecosystem. Typically, the construction of hydropower has resulted in a significant loss of habitat suitable for aquatic life, which can be replaced by nature-like solutions as part of ecological compensation. The measure can therefore improve the ecological value and status of the human-modified water body. This report describes the design and construction phases of the Imatra City Brook and reports the results of monitoring after the construction phase. The design of the Imatra City Brook emphasized that the brook will become suitable habitat for trout. However, brook is not designed as a bypass, albeit the design principles used can be applied directly to natural bypasses. The Imatra City Brook was completed in 2014 in a park-like area in the vicinity of the Imatrankoski power plant. The brook is about one kilometer long and varies in width from 2 to 10 meters. In addition to different habitats and spawning and juvenile areas for trout, landscape design and suitability for recreational use were also taken into account in the design of the area. The height of the Imatrankoski dam, 24 m, and the available area were utilized to make the best possible use, and by meandering the brook, its length could be maximized. Gravel of varying sizes, larger stones and wood were used as the base material for the structures. The flow of the brook is about 250 l/s in summer and about 100 l/s during winter. The goal of the stream being a spawning and rearing ground for trout seems to have been achieved, as trout and other species of fish and organisms have taken over the stream. In the Imatra City Brook, trout reproduction has been even better than expected and the density of juvenile fish is higher than in the compared natural streams. The total area of the brook is remarkably small compared to the huge amount of rapids and riverine habitats lost for hydropower production and construction of dams. However, the built natural-like habitat provides a suitable habitat for trout as an endangered species and any individual born in the wild can be considered important for the population of the species. The species richness of benthic macroinvertebrates increases every year. At the same time, the number of macroinvertebrate individuals has multiplied during the four years of observation. Reducing damage to nature, species and ecosystems is becoming the responsibility of existing hydropower. Fisheries compensation alone (stockings) or the technical fishways alone are not enough to solve the problems that hydropower and damming have caused, especially for the quantity and quality of suitable habitats. In the future, the results from the Imatra City Brook will encourage the upgrading of various built natural-like habitats or compensatory habitats as one viable option for improving the status of the water bodies