Search

The current study presented a porous liquid (PL) prepared from propylene glycol-based deep eutectic solvent (DES) and hyper-crosslinked polymers (HCP) that are liquids over wide temperature ranges, including ambient temperature. It was shown that the solvent molecules are too large to penetrate the pores of HCP, so the PL is maintained as a suspension with permanent free volume for several months and can absorb large amounts of gases. This study marks the pioneering use of DESs as the liquid medium, replacing ionic liquids due to their closely matched properties. The structural features of both DES and HCP are retained; the increase in CO2 absorption capacity compared to pure DES is due to the presence of a porous solid and is proportional to the amount of solid. The absorbed CO2 amount rises from 1.0105 mmol·g−1 in pure DES to 1.3232, 1.6027, and 1.2168 mmol·g−1 in PL-1, PL-2, and PL-3, respectively. Thermodynamic analysis revealed that the enthalpy of gas absorption allows straightforward regeneration of the PLs in the studied cases. The investigated PLs show great potential as gas absorbents, with the incorporation of just 0.5 wt% of porous polymer material leading to an impressive increase in solvent absorption capacity, up to 59 %.

The capture and separation of carbon dioxide (CO2) has been the focus of a plethora of research in order to mitigate its emissions and contribute to global development. Given that CO2 is commonly found in natural gas streams, there have been efforts to seek more efficient materials to separate gaseous mixtures such as CO2/CH4. However, there are only a few reports regarding adsorption processes within pressurized systems. In the offshore scenario, natural gas streams still exhibit high moisture content, necessitating a greater understanding of processes in moist systems. In this article, a metal-organic framework synthesis based on zirconium (MOF-808) was carried out through a conventional solvothermal method and autoclave for the adsorption of CO2 and CH4 under different temperatures (45–65 °C) and pressures up to 100 bar. Furthermore, the adsorption of humid CO2 was evaluated using thermal analyses. The MOF-808 synthesized in autoclave showed a high surface area (1502 m2/g), a high capacity for CO2 adsorption at 50 bar and 45 °C and had a low selectivity to capture CH4 molecules. It also exhibited a fine stability after five cycles of CO2 adsorption and desorption at 50 bar and 45 °C − as confirmed by structural post-adsorption analyses while maintaining its adsorption capacity and crystallinity. Furthermore, it can be observed that the adsorption capacity increased in a humid environment, and that the adsorbent remained stable after adsorption cycles in the presence of moisture. Finally, it was possible to confirm the occurrence of physisorption processes through nuclear magnetic resonance (NMR) analyses, thus validating the choice of mild temperatures for regeneration and contributing to the reduction of energy consumption in processing plants.

El capítulo 9 está sujeto a confidencialidad por la autora. 289 p., Esta tesis investiga diferentes aspectos de la manipulación de biofluidos complejos, como son el sudor, la sangre y el semen a microescala, para mejorar los enfoques de detección, separación y selección en dispositivos microfluídicos. Esto implica la fabricación de materiales sensores basados en alginato, así como su integración en diferentes plataformas microfluídicas para mejorar la detección de analitos. Además, también se investiga la generación de nuevas herramientas para la separación de plasma a partir de muestras de sangre humana completa mediante tecnología de impresión 3D. Por último, también se contempla el diseño y fabricación de novedosas configuraciones de dispositivos microfluídicos para la selección de espermatozoides viables con fines reproductivos.

224 p., Los dispositivos microfluídicos ideales deben ser pequeños, fáciles de operar, portátiles, autónomos y capaces de integrar todas las funciones analíticas requeridas dentro de un mismo chip. El control de flujo es un aspecto crítico a tener en cuenta al diseñar estos sistemas microfluídicos, sin embargo, a menudo se utilizan componentes convencionales y voluminosos que requieren fuentes de alimentación externas y reducen su portabilidad. En esta tesis se investigó la integración de microbombas poliméricas modulares en cartuchos microfluídicos plásticos para el desarrollo de dispositivos microfluídicos autónomos, dando como resultado el desarrollo de una arquitectura universal altamente versátil y adaptable para una amplia gama de volúmenes y tiempos de actuación. Además, los cartuchos microfluídicos se pueden fabricar fácilmente mediante técnicas de prototipado rápido y un proceso de fabricación capa-a-capa, lo que, en combinación con las bajas presiones generadas por las microbombas poliméricas, permite el desarrollo rápido de operaciones fluídicas complejas para el análisis de muestras. A modo de ejemplo, se demostró la aplicabilidad de estos sistemas autónomos para realizar la calibración de la reacción de Griess en el interior de ionogeles o la separación de plasma a partir de muestras de sangre completa. En conclusión, estas arquitecturas combinadas están destinadas a ser un referente en el diseño de operaciones microfluídicas autónomas y personalizables debido a su versatilidad y facilidad de fabricación.

248 p., Los fullerenos, como el C60 y el C70, son alótropos de carbono esféricos que exhiben una alta movilidad electrónica, una destacada riqueza electroquímica y una excepcional estabilidad térmica y fotolumínica. Además, sus propiedades electrónicas y físicas pueden ser ajustadas mediante modificaciones químicas en su estructura, y se aplican en diversas áreas, especialmente en la fotovoltaica, donde destacan las celdas solares de perovskita (PSCs). A pesar de los numerosos informes sobre derivados de fullereno funcionalizados en PSCs, todavía se requieren esfuerzos significativos para mejorar el rendimiento y la estabilidad de estos dispositivos. Esta tesis comprende la síntesis, caracterización estructural y aplicación en PSCs de dos conjuntos distintos de materiales fullerénicos utilizados como transportadores de electrones (ETMs) y transportadores de huecos (HTMs) en PSCs de arquitectura invertida y regular, respectivamente. Los ETMs empleados son derivados de C60 y C70, mientras que los HTMs son derivados de hexakis-C60, incluyendo un material polimérico obtenido mediante fotoreticulación. La estructura química utilizada en cada conjunto de materiales muestra correlaciones tanto con las eficiencias alcanzadas en los dispositivos como con su estabilidad a largo plazo. Esta tesis demuestra que el diseño estructural químico es uno de los métodos que permiten la obtención de nuevos materiales para abordar los desafíos inherentes de estas celdas con miras a su futura comercialización.

In this study, overloaded elution profiles under ultra-high-pressure liquid chromatographic (UHPLC) conditions and accounting for the severe pressure and temperature gradients generated, are compared with experimental data. The model system consisted of an C18 column packed with 1.7-µm particles (i.e., a UHPLC column) and the solute was 1,3,5-tri‑tert-butylbenzene eluted with a mobile phase composed of 85/15 (v/v) acetonitrile/water. Two thermal modes were considered, and the solute was eluted at the very high inlet pressures necessary to achieve a highly efficient and rapid chromatographic process, as provided by using columns packed with small particles. However, the high inlet pressure and high linear velocity of the mobile phase caused the production of a significant amount of heat, and consequently, the formation of axial and radial temperature gradients. Due to these gradients, the retention and the mobile phase velocity were no longer constant. Thus, simple mathematical models consisting only of the mass balance equations are unsuitable to properly model the elution profiles. Here, the elution concentration profiles were predicted using a combined two-dimensional heat and mass transfer model, also including the calculation of the mobile phase velocity distribution. The isotherm adsorption model was the bi-Langmuir isotherm model with Henry constants that depended on the local temperature and pressure in the column. These adjustments allowed us to precisely account for changes in the shape and retention of the overloaded concentration profiles in the mobile phase. The proposed model provided accurate predictions of the overloaded concentration profiles, demonstrating good agreement with experimental profiles eluted under severe pressure and temperature gradients in the column even in the most extreme cases where the pressure drops reached 846 bar and the temperature gradients equaled 0.15 K mm−1 and 0.95 K mm−1 in the axial and the radial directions, respectiv

Many strains among spore-forming bacteria species are associated with food spoilage, foodborne disease, and hospital-acquired infections. Understanding the impact of environmental conditions and decontamination techniques on the metabolic activity, viability, and biomarkers of these spores is crucial for combatting them. To distinguish and track spores and to understand metabolic mechanisms, spores must be labeled. Staining or genetic modification are current methods for this, however, these methods can be time-consuming, and affect the viability and function of spore samples. In this work, we investigate the use of heavy water for permanent isotope labeling of spores and Raman spectroscopy for tracking sporulation/germination mechanisms. We also discuss the potential of this method in observing decontamination. We find that steady-state deuterium levels in the spore are achieved after only ∼48 h of incubation with 30% D2O-infused broth and sporulation, generating Raman peaks at cell silent region of 2200 and 2300 cm−1. These deuterium levels then decrease rapidly upon spore germination in non-deuterated media. We further find that unlike live spores, spores inactivated using various methods do not lose these Raman peaks upon incubation in growth media, suggesting these peaks may be used to indicate the viability of a spore sample. We further observe several Raman peaks exclusive to deuterated DPA, a spore-specific chemical biomarker, at e.g. 988 and 2300 cm−1, which can be used to track underlying changes in spores involving DPA. In conclusion, permanent spore labeling using deuterium offers a robust and non-invasive way of labeling bacterial spores for marking, viability determination, and characterising spore activity.

Beech sawdust was treated with a ternary solvent system based on binary aqueous ethanol with partial substitution of ethanol by acetone at four different water contents (60, 50, 40, and 30%v/v). In addition to standard, i.e., noncatalyzed treatments, the application of inorganic acid in the form of 20 mm H2SO4 was evaluated. The various solvent systems were applied at 180 °C for 60 min. The obtained biomass fractions were characterized by standard biomass compositional methods, i.e., sugar monomer and oligomer contents, dehydration product contents of the aqueous product, and lignin, cellulose, and hemicellulose contents in isolated solid fractions. More advanced analyses were performed on the lignin fractions, including quantitative 13C NMR analyses, 1H–13C HSQC analysis, size exclusion chromatography, and pyrolysis-GC/MS, and the aqueous product, in the form of size exclusion chromatography and determination of total phenol contents. The picture emerging from the thorough analytical investigation performed on the lignin fractions is consistent with that resulting from the characterization of the other fractions: results point toward greater deconstruction of the lignocellulosic recalcitrance upon higher organic solvent content, replacing ethanol with acetone during the extraction, and upon addition of mineral acid. A pulp with cellulose content of 94.23 wt % and 95% delignification was obtained for the treatment employing a 55/30/15 EtOH/water/acetone mixture alongside 20 mm H2SO4. Furthermore, the results indicate the formation of two types of organosolv furan families during treatment, which differ in the substitution of their C1 and C5. While the traditional lignin aryl–ether linkages present themselves as indicators for process severity for the nonacid catalyzed systems, the distribution of these furan types can be applied as a severity indicator upon employment of H2SO4, including their presence in the isolated lignin fractions., Validerad;2024;Nivå 2;2024-01-29 (joosat);Full text license: CC BY

Given the rapid development of data-driven experimental procedures within the life sciences, it is important to equip students with proper skills and knowledge on how to obtain and interpret complex data. While laboratory exercises have for a long time been well established as a teaching method for life sciences, we consider there is room for improvement in how laboratory exercises are conducted. Hence, we designed a laboratory exercise course in which students at the graduate level in the European education system (M.Sc.) are challenged to pose their own biological question and write their own laboratory protocol for a proteomic study to investigate their hypothesis. Here, students are supported in their task with lectures and seminars that take them through the required details on experimental sample preparation, analysis with LC-MS, and proteomic data evaluation of biological function and relevance. According to student interviews, the inquiry-based learning concept we used here provided a deeper understanding of the laboratory protocols they wrote, according to which they eventually performed their own experiments.

The ability to detect and inactivate spore-forming bacteria is of significance within, for example, industrial, healthcare, and defense sectors. Not only are stringent protocols necessary for the inactivation of spores but robust procedures are also required to detect viable spores after an inactivation assay to evaluate the procedure’s success. UV radiation is a standard procedure to inactivate spores. However, there is limited understanding regarding its impact on spores’ spectral and morphological characteristics. A further insight into these UV-induced changes can significantly improve the design of spore decontamination procedures and verification assays. This work investigates the spectral and morphological changes to Bacillus thuringiensis spores after UV exposure. Using absorbance and fluorescence spectroscopy, we observe an exponential decay in the spectral intensity of amino acids and protein structures, as well as a logistic increase in dimerized DPA with increased UV exposure on bulk spore suspensions. Additionally, using micro-Raman spectroscopy, we observe DPA release and protein degradation with increased UV exposure. More specifically, the protein backbone’s 1600–1700 cm–1 amide I band decays slower than other amino acid-based structures. Last, using electron microscopy and light scattering measurements, we observe shriveling of the spore bodies with increased UV radiation, alongside the leaking of core content and disruption of proteinaceous coat and exosporium layers. Overall, this work utilized spectroscopy and electron microscopy techniques to gain new understanding of UV-induced spore inactivation relating to spore degradation and CaDPA release. The study also identified spectroscopic indicators that can be used to determine spore viability after inactivation. These findings have practical applications in the development of new spore decontamination and inactivation validation methods., Published as part of The Journal of Physical Chemistry B virtual special issue “Advances in Cellular Biophysics”.

Calibration-free sensors are generally understood as analytical tools with no need for calibration apart from the initial one (i.e., after its fabrication). However, an "ideal" and therefore "more restricted" definition of the concept considers that no calibration is necessary at all, with the sensor being capable of directly providing the analyte concentration in the sample. In the electroanalysis field, investigations have been directed to charge-based readouts (i.e., coulometry) that allow for concentration calculation via the Faraday Law: The sample volume must be precisely defined and the absoluteness of the electrochemical process in which the analyte is involved must be ensured (i.e., the analyte in the sample is similar to 100% converted/transported). Herein, we report on the realization of calibration-free coulometric ISEs based on ultrathin ion-selective membranes, which is demonstrated for the detection of potassium ions (K+). In essence, the K+ transfer at the membrane-sample interface is modulated by the oxidation state of the conducting polymer underlying the membrane. The accumulation/release of K+ to/from the membrane is an absolute process owing to the confinement of the sample to a thin-layer domain (thickness of <100 mu m). The capacity of the membrane expressed in charge is fixed to ca. 18 mu C, and this dictates the detection of micromolar levels of K+ present in ca. 5 mu L sample volume. The system is interrogated with cyclic voltammetry to obtain peaks related to the K+ transfer that can be treated charge-wise. The conceptual and technical innovative steps developed here made the calibration-free detection of K+ possible in artificial and real samples with acceptable accuracy (<10% difference compared with the results obtained from a current-based calibration and ion chromatography). The charge-based analysis does not depend on temperature and appeared to be repetitive, reproducible, and reversible in the concentration range from 1 to 37, QC 20240209

Selective copper recovery from copper tailings reduces environmental pollution caused by mining activities and provides a valuable source of copper. Furthermore, polymer waste accumulation and handling small functional materials like resins remains challenging. In this study, a 3D-printed adsorbent for selective copper recovery from copper tailings was designed by functionalizing recycled polymer with a chelating resin and 3D-printing using selective laser sintering technique. The 3D-printed adsorbent was characterized, and its adsorption performance examined under varying conditions. The adsorption kinetics and adsorption isotherm fitted well to the pseudo-second-order kinetics and Langmuir isotherm models, suggesting chemical and monolayer adsorption processes. FTIR indicated coordination as the possible adsorption mechanism. Thermodynamics revealed an endothermic process. The 3D-printed adsorbent demonstrated an excellent Cu(II) adsorption, high selectivity towards Cu(II), and reusability. This work offers a promising 3D-printed adsorbent for selective Cu(II) recovery, while also addressing polymer waste and particle handling issues.

Isotope dilution ultrahigh-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS) is commonly used for trace analysis of polyfluoroalkyl and perfluoroalkyl substances (PFAS) in difficult matrices. Commercial nontargeted analysis of major PFAS where relative concentrations are obtained cost effectively is rapidly emerging and is claimed to provide comparable results to that of absolute quantification using matrix matched calibration and isotope dilution UHPLC–MS/MS. However, this remains to be demonstrated on a large scale. We aimed to assess the performance of a targeted absolute quantification isotope dilution LC–MS/MS assay versus a commercial nontargeted relative quantification assay for detection of three major PFAS in human blood. We evaluated a population-based cohort of 503 individuals. Correlations were assessed using Spearman's rank correlation coefficients (rho). Precision and bias were assessed using Bland–Altman plots. For perfluorooctane sulfonic acid, the median concentrations were 5.10 ng/mL (interquartile range [IQR] 3.50–7.24 ng/mL), the two assays correlated with rho 0.83. For perfluorooctanoic acid, the median concentrations were 2.14 ng/mL (IQR 1.60–3.0 ng/mL), the two assays correlated with rho 0.92. For perfluorohexanesulfonate, the median concentrations were 5.5 ng/mL (IQR 2.50–11.61 ng/mL), the two assays correlated with rho 0.96. The Bland–Altman statistical test showed agreement of the mean difference for the majority of samples (97–98%) between the two assays. Absolute plasma concentrations of PFAS obtained using matrix matched calibration and isotope dilution UHPLC–MS/MS show agreement with relative plasma concentrations from a nontargeted commercial platform by Metabolon. We observed striking consistency between the two assays when examining the associations of the three PFAS with cholesterol, offering additional confidence in the validity of utilizing the nontargeted approach for correlations with various he

Fentanyls are synthetic opioids up to 10,000 times more potent than morphine. Although initially developed for medical applications, fentanyl and its analogues have recently grown synonymous with the ongoing opioid epidemic. To combat the continued spread of these substances, there is a need for rapid and sensitive techniques for chemical detection. Surface-enhanced Raman spectroscopy (SERS) has the potential for trace detection of harmful chemical substances. However, vibrational spectra obtained by SERS often differ between SERS substrates, as well as compared with spectra from normal Raman (NR) spectroscopy. Herein, SERS and NR responses from two fentanyl analogues, carfentanil (CF) and thiofentanil (TF), were measured and analysed with support from density functional theory (DFT) modelling. Using commercially available silver nanopillar SERS substrates, the SERS signatures of samples diluted in acetonitrile between 0.01 and 1000 µg/mL were studied. Relative SERS peak intensities measured in the range of 220–1800 cm−1 vary with concentration, while SERS and NR spectra largely agree for CF at higher concentrations ((Formula presented.) 100 µg/mL). For TF, three distinct NR peaks at 262, 366 and 667 cm−1 are absent or strongly suppressed in the SERS spectrum, attributed to the lone-pair electrons of the thiophene's sulphur atom binding to the Ag surface. The concentration dependence of the Raman peak at (Formula presented.) 1000 cm−1, assigned to trigonal bending of the phenyl ring, approximately follows a Langmuir adsorption isotherm. This work elucidates similarities and differences between SERS and NR in fentanyl detection and discusses the chemical rationale behind these differences.

Raman spectroscopy is widely used in monitoring and controlling cell cultivations for biopharmaceutical drug manufacturing. However, its implementation for culture monitoring in the cell line development stage has received little attention. Therefore, the impact of clonal differences, such as productivity and growth, on the prediction accuracy and transferability of Raman calibration models is not yet well described. Raman OPLS models were developed for predicting titer, glucose and lactate using eleven CHO clones from a single cell line. These clones exhibited diverse productivity and growth rates. The calibration models were evaluated for clone-related biases using clone-wise linear regression analysis on cross validated predictions. The results revealed that clonal differences did not affect the prediction of glucose and lactate, but titer models showed a significant clone-related bias, which remained even after applying variable selection methods. The bias was associated with clonal productivity and lead to increased prediction errors when titer models were transferred to cultivations with productivity levels outside the range of their training data. The findings demonstrate the feasibility of Raman-based monitoring of glucose and lactate in cell line development with high accuracy. However, accurate titer prediction requires careful consideration of clonal characteristics during model development.

Doping is defined as the use of prohibited substances or methods by the World Anti-Doping Agency and the aim with doping control analysis is to detect the use of these illicit substances or methods. Substances that are prohibited in human or equine sports have either a positive or negative impact on the performance. Since administered drugs generally are metabolized to a varying degree and thereby not only excreted in their original form, their metabolite profiles are of high interest because drug metabolites may be present in the body for a longer time than the administered drug itself. Thereby detection of metabolites can improve the window of detection. Unfortunately, the metabolite profiles of non-approved drugs that are mainly available on the Internet, such as Selective Androgen Receptor Modulators (SARMs) are often unknown. This thesis consists of four papers that all encompass drug metabolite profiling either in vivo, in vitro or in a combination, utilizing separation with liquid chromatography and detection with high resolution mass spectrometry. In paper I and II, the equine in vivo metabolite profiles of the two SARMs ACP-105 and LGD-3303 were investigated and the results showed that using drug metabolites as analytical targets can prolong the detection time. For ACP-105, the in vivo metabolite profile was compared with different incubation models such as liver microsomes, S9 fractions and the fungus Cunninghamella elegans. The in vivo and in vitro metabolite profiles showed an interesting overlap for several metabolites, demonstrating the importance and usefulness for in vitro methods in doping control, especially since microsome incubates are allowed as reference material. An optimization of microsome incubation conditions utilizing experimental design was presented in paper III and IV, showing that the optimized conditions greatly impacted the yield of drug metabolites, but also that the optimal conditions are substance dependent. In paper III, a mult

High-resolution mass spectrometry (HRMS)-based suspect and nontarget screening has identified a growing number of novel per- and polyfluoroalkyl substances (PFASs) in the environment. However, without analytical standards, the fraction of overall PFAS exposure accounted for by these suspects remains ambiguous. Fortunately, recent developments in ionization efficiency (IE) prediction using machine learning offer the possibility to quantify suspects lacking analytical standards. In the present work, a gradient boosted tree-based model for predicting log IE in negative mode was trained and then validated using 33 PFAS standards. The root-mean-square errors were 0.79 (for the entire test set) and 0.29 (for the 7 PFASs in the test set) log IE units. Thereafter, the model was applied to samples of liver from pilot whales (n = 5; East Greenland) and white beaked dolphins (n = 5, West Greenland; n = 3, Sweden) which contained a significant fraction (up to 70%) of unidentified organofluorine and 35 unquantified suspect PFASs (confidence level 2–4). IE-based quantification reduced the fraction of unidentified extractable organofluorine to 0–27%, demonstrating the utility of the method for closing the fluorine mass balance in the absence of analytical standards.

Simultaneous identification and quantification of per- and polyfluoroalkyl substances (PFAS) were evaluated for three quadrupole time-of-flight mass spectrometry (QTOF) acquisition methods. The acquisition methods investigated were MS-Only, all ion fragmentation (All-Ions), and automated tandem mass spectrometry (Auto-MS/MS). Target analytes were the 25 PFAS of US EPA Method 533 and the acquisition methods were evaluated by analyte response, limit of quantification (LOQ), accuracy, precision, and target-suspect screening identification limit (IL). PFAS LOQs were consistent across acquisition methods, with individual PFAS LOQs within an order of magnitude. The mean and range for MS-Only, All-Ions, and Auto-MS/MS are 1.3 (0.34–5.1), 2.1 (0.49–5.1), and 1.5 (0.20–5.1) pg on column. For fast data processing and tentative identification with lower confidence, MS-Only is recommended; however, this can lead to false-positives. Where high-confidence identification, structural characterisation, and quantification are desired, Auto-MS/MS is recommended; however, cycle time should be considered where many compounds are anticipated to be present. For comprehensive screening workflows and sample archiving, All-Ions is recommended, facilitating both quantification and retrospective analysis. This study validated HRMS acquisition approaches for quantification (based upon precursor data) and exploration of identification workflows for a range of PFAS compounds.

Kaffe Bueno, ett bioteknologiskt start-up-företag dedikerat till framsteg inom naturliga och gröna produkter, fokuserar på att utnyttja den outnyttjade potentialen hos kaffebiprodukter genom grön kemi och bioteknik. Då endast 1% av kaffet används för bryggning, extraherar företaget lösliga och olösliga produkter genom en uppdelning mellan ett oljeutvinning och ett efterföljande vattenuttag, vilket bidrar till att sänka CO2-utsläppen per värde och en cirkulär ekonomi. Inom hudvård har Kaffe Bueno tidigare utvecklat en BB-kräm med återvunnen kaffesump för pigmentering och hudvårdsfördelar, men stötte på utmaningar när det gäller täckning jämfört med syntetiska BB-krämer, vilket ledde till målet med detta examensarbete. Målet med denna studie är att formulera en helt växtbaserad BB-kräm med optimal täckning, överträffa standarden satt av syntetiska kemiska BB-krämer. Den centrala fråga som styr forskningen är: "Vilka är de optimala formuleringsrstrategierna och växtbaserade ingredienserna för att uppnå högsta täckning i en helt växtbaserad BB-kräm samtidigt som stabilitet säkerställs?". Denna forskning stämmer överens med den globala kosmetikindustrins växande efterfråga av hållbara, växtbaserade formuleringar, som svar på konsumenternas preferenser för miljövänliga produkter. Forskningen inkluderar utveckling av en växtbaserad vit baskräm utan titanoxid eller zinkoxid, och sedan användning av naturliga pigment som KAFFAGE® för att justera färgen, säkerställa hållbarhet, täckning och stabilitet över tid, vid ljusexponering och användning. Sammanfattningsvis formulerades under denna studie framgångsrikt en växtbaserad BB-kräm med täckning jämförbar med marknadsstandarder, undvikande av traditionella järnoxider och med användning av hållbara ingredienser som KAFFAGE-BD®-pigment, även om användning av titandioxid (TiO2) fortfarande krävs. Forskningen betonade vikten av texturoptimering, färgmatchning och sensorisk perception, vilket positionerar BB-krämen som en pålitlig, Kaffe Bueno, a bioscience startup company dedicated to advancing natural and green products, focuses on harnessing the untapped potential of coffee by-products through green chemistry and biotechnology. With only 1% of coffee utilized for brewing, the company extracts soluble and insoluble products through a partion between an oil extraction and a subsequent water extraction, contributing to lowering the CO2 emissions per value from coffee consumption and a circular economy. In skincare, Kaffe Bueno previously developed a Beauty Balm cream using ingredients from upcycled spent coffee grounds for pigmentation and skincare benefits, but faced challenges in achieving coverage comparable to synthetic BB creams, prompting the goal of this master thesis. The objective of this study is to formulate an all plant-based BB cream with optimal coverage, surpassing the standard set by synthetic BB creams. The central question guiding the research is: "What are the optimal formulation strategies and plant-based ingredients for achieving the highest coverage in an all plant-based BB cream while ensuring stability?". This research aligns with the global cosmetic industry's growing demand for sustainable, plant-based formulations, responding to consumer preferences for eco-friendly products. The research includes developing a white plant-based base cream without titanium dioxide or zinc oxide, and then utilizing natural pigments like KAFFAGE® to adjust the tint, ensuring sustainability, up-to-standard coverage, stability over time, light exposition and use. Tests conducted to validate the product’s performance and quality include a stability test, a sensory panel evaluation, a sweat test, and other relevant assessments to ensure the cream's effectiveness, user satisfaction, and compliance with industry standards. In conclusion, this study successfully formulated a plant-based BB cream with coverage comparable to market benchmarks, circumventing traditional iron oxides and relying on

Patulin (PAT) commonly contaminates fruits, posing a significant risk to human health. Therefore, a highly effective and sensitive approach in identifying PAT is warranted. Herein, a SERS aptasensor was constructed based on a two-dimensional film -like structure. GO@Au nanosheets modified with SH-cDNA were employed as capture probes, while core -shell Au@Ag nanoparticles modified with 4 -MBA and SH-Apt were utilized as signal probes. Through the interaction between capture probes and signal probes, adjustable hotspots were formed, yielding a significant Raman signal. During sensing, the GO@Au-cDNA competitively attached to Au@AgNPs@MBA-Apt, resulting in an inverse relationship between PAT levels and SERS intensity. The acquired results exhibited linear responses to PAT within the range of 1-70 ng/mL, with a calculated limit of detection of 0.46 ng/mL. In addition, the SERS aptasensor exhibited satisfactory recoveries in apple samples, which aligned closely with HPLC. With high sensitivity and specificity, this method holds significant potential for PAT detection.

A biographical approach of Francisco Buscarons Úbeda, professor of Analytical Chemistry (1945-1975) and rector (1951-1956) at the University of Barcelona is presented. His trajectory allows us to know sig-nificant aspects of the Spanish university during the Franco dictatorship. Despite the limitations of the pe-riod, he was able as a researcher to establish a fruitful school of analytical chemistry. As rector he faced, with a dignified attitude, the first student protest movements against the repressive policy of the regime., Se presenta una aproximación biográfica de Francisco Buscarons Úbeda, catedrático de Química Ana-lítica de la Universidad de Barcelona (1945-1975) y rector de la misma (1951-1956). Su trayectoria permite conocer aspectos significativos de la universidad española en la época franquista. A pesar de las limitaciones del momento supo, como investigador, establecer una escuela de química analítica y, como rector, hacer frente a los primeros movimientos de protesta estudiantiles con una actitud digna frente la política represora del régimen.

Alzheimer’s Disease (AD), a prevalent neurodegenerative disorder, is the primary cause of dementia. Despite significant advancements in neuroscience, a definitive cure or treatment for this debilitating disease remains elusive. A notable characteristic of AD is oxidative stress, which has been identified as a potential therapeutic target. Polyphenols, secondary metabolites of plant origin, have attracted attention due to their potent antioxidant properties. Epidemiological studies suggest a correlation between the consumption of polyphenol-rich foods and the prevention of chronic diseases, including neurodegenerative disorders, which underscores the potential of polyphenols as a therapeutic strategy in AD management. Hence, this comprehensive review focuses on the diverse roles of polyphenols in AD, with a particular emphasis on neuroprotective potential. Scopus, ScienceDirect, and Google Scholar were used as leading databases for study selection, from 2018 to late March 2024. Analytical chemistry serves as a crucial tool for characterizing polyphenols, with a nuanced exploration of their extraction methods from various sources, often employing chemometric techniques for a holistic interpretation of the advances in this field. Moreover, this review examines current in vitro and in vivo research, aiming to enhance the understanding of polyphenols’ role in AD, and providing valuable insights for forthcoming approaches in this context., Depto. de Química Analítica, Fac. de Ciencias Químicas, TRUE, pub

Sphingolipids are an essential subset of bioactive lipids found in most eukaryotic cells that contribute to membrane biophysical properties and are involved in cellular differentiation, recognition, and mediating interactions. The described nanoHPLC-ESI-Q/ToF methodology utilizes known biosynthetic pathways, accurate mass detection, optimized collision-induced disassociation, and a robust nanoflow chromatographic separation for the analysis of intact sphingolipids found in human tissue, cells, and serum. The methodology was developed and validated with an emphasis on addressing the common issues experienced in profiling these amphipathic lipids, which are part of the glycocalyx and lipidome. The high sensitivity obtained using nanorange flow rates with robust chromatographic reproducibility over a wide range of concentrations and injection volumes results in confident identifications for profiling these low-abundant biomolecules.

Nuclear magnetic resonance (NMR) spectroscopy is an important analytical technique in synthetic organic chemistry, but its integration into high-throughput experimentation workflows has been limited by the necessity of manually analyzing the NMR spectra of new chemical entities. Current efforts to automate the analysis of NMR spectra rely on comparisons to databases of reported spectra for known compounds and, therefore, are incompatible with the exploration of new chemical space. By reframing the NMR spectrum of a reaction mixture as a joint probability distribution, we have used Hamiltonian Monte Carlo Markov Chain and density functional theory to fit the predicted NMR spectra to those of crude reaction mixtures. This approach enables the deconvolution and analysis of the spectra of mixtures of compounds without relying on reported spectra. The utility of our approach to analyze crude reaction mixtures is demonstrated with the experimental spectra of reactions that generate a mixture of isomers, such as Wittig olefination and C-H functionalization reactions. The correct identification of compounds in a reaction mixture and their relative concentrations is achieved with a mean absolute error as low as 1%.

Glycosylation is a keystone of mammalian cells found primarily on membrane proteinsand lipids, extending into the extracellular space to form the outer-most membrane layer known as the glycocalyx. The physiological functions of glycans are still constantly being discovered in relation to specific glycan structures. These functions include alteration of protein tertiary structure, protection of the peptide backbone, and mediation of interactions. Each of these functionalities, namely the mediation of interactions, has been a recent focus in the field of glycomics. Glycans have been shown to play a significant role in signaling pathways, cancer pathology, neurodegeneration, immune response, and viral, bacterial, and fungal susceptibility pathology. Glycan-mediated interactions are of unique interest in neural physiology and pathology. Previous research has shown aberrant glycosylation of both proteins and lipids to play a significant role in neurological diseases such as multiple sclerosis, Huntington's disease, and Alzheimer's disease. The complexity of elucidating pathology mechanisms stems from the diversity of glycan structures specific to each cell type and how they shape interactions in vivo. Developing analytical methodologies that provide sensitive and reproducible profiles with structural information is critical to elucidate the mechanisms behind glycan interactions. The sheer structural diversity in glycans and their untemplated biosynthesis makes this challenging. The development of robust high-performance liquid chromatography-mass spectrometry workflows capable of generating structural profiles and their application was the primary focus presented in this work.

Rice production in California is a thriving, multi-billion dollar industry, with the Sacramento Valley alone producing over 95% of the nation’s short- and medium-grained rice. The sustainability of this industry is threatened, however, by the rapid evolution of herbicide resistant weeds spurred by long-term monoculture and a lack of herbicides with alternative modes of action. One agent proposed to ameliorate the lack of chemical control options is oxyfluorfen (OXY). OXY is a broad-spectrum, diphenyl ether herbicide that disrupts chlorophyll synthesis through inhibition of the protoporphyrinogen oxidase (protox) enzyme. It has demonstrated effectiveness against rice weeds, including weedy rice (Oryza sativa f. spontanea), a pest for which no herbicide is currently registered, and resistance to its mode of action has not been reported by rice growers. However, OXY is not currently registered for use with rice and its use in- or near-aquatic resources is currently prohibited due to its high toxicity to aquatic organisms. As rice field floodwater is ultimately released into nearby waterways, use of OXY with rice introduces the potential for its transport to the Sacramento River Basin where sensitive aquatic organisms may be harmed. Thus, it is imperative that registered uses be informed by a clear understanding of its transport and dissipation processes and potential for environmental impacts when it’s used as a rice herbicide. To that end, it is the objective of this work to elucidate the environmental fate and aquatic risk of OXY when used as an herbicide in California rice fields.Partitioning processes greatly influence overall fate by determining where a pesticide is found and which processes contribute most to dissipation. Thus, the soil-water partitioning behavior of OXY under simulated California rice conditions was characterized using a batch equilibrium method. Soil-water partitioning was investigated in two soils collected from Sacramento Valley rice fields

This paper introduces an innovative approach to 3D environmental mapping through the integration of a compact, handheld sensor package with a two-stage sensor fusion pipeline. The sensor package, incorporating LiDAR, IMU, RGB, and thermal cameras, enables comprehensive and robust 3D mapping of various environments. By leveraging Simultaneous Localization and Mapping (SLAM) and thermal imaging, our solution offers good performance in conditions where global positioning is unavailable and in visually degraded environments. The sensor package runs a real-time LiDAR-Inertial SLAM algorithm, generating a dense point cloud map that accurately reconstructs the geometric features of the environment. Following the acquisition of that point cloud, we post-process these data by fusing them with images from the RGB and thermal cameras and produce a detailed, color-enriched 3D map that is useful and adaptable to different mission requirements. We demonstrated our system in a variety of scenarios, from indoor to outdoor conditions, and the results showcased the effectiveness and applicability of our sensor package and fusion pipeline. This system can be applied in a wide range of applications, ranging from autonomous navigation to smart agriculture, and has the potential to make a substantial benefit across diverse fields.

My research develops tools to enable understanding of how information is encoded in chemical messengers (neurotransmitters; e.g., serotonin, dopamine) in the brain by measuring them in real-time, in awake, behaving mice models. A molecular scale understanding of complex behavior and brain (dys)function would enable better treatments for neuropsychiatric disorders such as anxiety and depression (which affect 50% of families worldwide). A major challenge is the lack of analytical techniques that can detect multiple neurotransmitters simultaneously, across physiologically and behaviorally relevant time scales (ms, min, h). To date, the most suitable technique is voltammetry, which applies a specific voltage waveform to a micron-sized brain-implantable sensor. However, voltammetry is limited by the number of analytes and timescales that can be achieved for in vivo monitoring, impeding an understanding of how our brains encode information across neurotransmitters in a coordinated manner. My graduate work involves developing a new voltammetry technique that combines novel voltammetry waveforms with machine learning. The technique is called rapid pulse voltammetry with partial least squares regression (RPV-PLSR), which utilizes a new type of pulse waveform and data analysis approach. Using RPV-PLSR, we published a proof-of-concept study to monitor serotonin and dopamine at both basal and stimulated levels, simultaneously, and compared these results to conventional approaches. We showed the utility of faradaic and non-faradaic current responses to build robust statistical models. The unique electrochemical signals present in pulse, rather than sweep, waveforms provide valuable chemical information in the background current that other methods do not generate. However, the design of RPV waveforms (and voltammetry waveforms in general) is an arduous and inefficient process. To address this challenge, I developed a machine learning-guided approach for systematic design of novel

The Delta Smelt is a largely zooplank­tivorous, endangered fish endemic to the San Francisco Estuary (the estuary). High flows increase the availability of fresh and brackish water habitat for Delta Smelt, but also may mobilize contaminants, potentially increasing toxicological stress. Here, we examine the association between contaminants and Delta Smelt health across contrasting water year types and flow-related management actions. Our study spanned the fall season of three years: 1 dry year (2018) bracketed by 2 wet years (2017 and 2019) and coincided with several management actions meant to benefit Delta Smelt. We collected field water from six sites in the estuary that encompass the freshwater and low-salinity habitat of Delta Smelt and analyzed the water for contaminant concentrations. After a 96-hour exposure to the field water, we assessed cultured Delta Smelt survival and the histopathological condition of the gill and liver. Insecticides, particularly fipronil metabolites, were the most prevalent contaminants detected in 2017 and 2018, and a variety of contaminants associated with the rice harvest were detected in 2019. No acute toxicity was observed during any exposure, but we observed negative effects in the livers of Delta Smelt exposed to agricultural water from the Toe Drain and Cache Slough during a 2019 pulse flow action, which coincided with elevated detections and concentrations of organic pesticides. Other noteworthy sub-lethal effects, likely occurring in response to contaminant mixtures, included severe gill lesions in Delta Smelt exposed to Decker Island water in 2019. In the drier year of 2018, lesions were generally mild or absent. Thus, the trade-offs between increased habitat availability and contaminant loading may provide one explanation for why Delta Smelt abundance does not consistently respond positively to outflow.

The valorization of lignin, a currently underutilized component of lignocellulosic biomass, has attracted attention to promote a stable and circular bioeconomy. Successful approaches including thermochemical, biological, and catalytic lignin depolymerization have been demonstrated, enabling opportunities for lignino-refineries and lignocellulosic biorefineries. Although significant progress in lignin valorization has been made, this review describes unexplored opportunities in chemical and biological routes for lignin depolymerization and thereby contributes to economically and environmentally sustainable lignin-utilizing biorefineries. This review also highlights the integration of chemical and biological lignin depolymerization and identifies research gaps while also recommending future directions for scaling processes to establish a lignino-chemical industry.

Proteins congregate into complexes to perform fundamental cellular functions. Phenotypic outcomes, in health and disease, are often mechanistically driven by the remodeling of protein complexes by protein-coding mutations or cellular signaling changes in response to molecular cues. Here, we present an affinity purification-mass spectrometry (APMS) proteomics protocol to quantify and visualize global changes in protein-protein interaction (PPI) networks between pairwise conditions. We describe steps for expressing affinity-tagged "bait" proteins in mammalian cells, identifying purified protein complexes, quantifying differential PPIs, and visualizing differential PPI networks. Specifically, this protocol details steps for designing affinity-tagged "bait" gene constructs, transfection, affinity purification, mass spectrometry sample preparation, data acquisition, database search, data quality control, PPI confidence scoring, cross-run normalization, statistical data analysis, and differential PPI visualization. Our protocol discusses caveats and limitations with applicability across cell types and biological areas. For complete details on the use and execution of this protocol, please refer to Bouhaddou et al. 20231.

Plastic pollution is overrunning the planet. To combat this, it is important to be able to generate biodegradable alternative plastics and measure their biodegradability. The research aimed to develop a method for quantifying the biodegradation of these plastics using peroxide digestion with Fenton’s Reagent. The results show that peroxide digestion can be used in tandem with other analytical methods to quantify biodegradation, namely with mass loss, compression analysis, and supplemental FTIR spectroscopy.

The direct and indirect interactions of aerosols with solar and terrestrial radiation represent the most significant uncertainty in our understanding of Earth’s climate. Marine aerosols, comprised of freshly emitted or nascent sea spray aerosols (SSA), aged SSA, and secondary marine aerosol (SMA), significantly impact the global radiative budget, cloud and fog formation, and visibility and air quality in coastal marine environments. Biological processes in seawater impact marine aerosol chemical and physical properties. An important but understudied property of marine aerosol is its phase state or viscosity. Viscosity significantly influences gas-to-particle partitioning, liquid and ice cloud nucleation rates, and heterogeneous reaction kinetics, which can affect aerosol chemical composition, wet deposition rates, size, and thus aerosol impacts on climate and air quality. This work investigates the influence of biological activity, particle size, and oxidative aging processes on marine aerosol's molecular composition and phase states. Empirical observations of particle phase state are made through online particle bounce/rebound measurements and offline with atomic force microscopy. Findings indicate nascent SSA particles exhibit increasingly viscous or solid-like characteristics with greater seawater phytoplankton activity and decreasing particle size. SSA aged by OH radical is more viscous than nascent SSA. Increasing organic carbon content and chemical species with higher molecular weights were enriched in SSA during elevated phytoplankton growth in seawater and smaller SSA. We attribute the higher molecular weight and more viscous organic components in SSA to the production of colloidal or gel-like SSA formed through the complexation of polyanionic organic components with divalent cations, specifically Ca2+. In polluted air with high concentrations of marine volatile organic compounds and oxidants equivalent to a week of chemical aging in the atmosphere, SSA beco

Small extracellular vesicles (sEVs) are cell-released vesicles ranging from 30-150nm in size. They have garnered increasing attention because of their potential for both the diagnosis and treatment of disease. The diversity of sEVs derives from their biological composition and cargo content. Currently, the isolation of sEV subpopulations is primarily based on bio-physical and affinity-based approaches. Since a standardized definition for sEV subpopulations is yet to be fully established, it is important to further investigate the correlation between the biomolecular composition of sEVs and their physical properties. In this study, we employed a platform combining single-vesicle surface-enhanced Raman spectroscopy (SERS) and machine learning to examine individual sEVs isolated by size-exclusion chromatography (SEC). The biomolecular composition of each vesicle examined was reflected by its corresponding SERS spectral features (biomolecular "fingerprints"), with their roots in the composition of their collective Raman-active bonds. Origins of the SERS spectral features were validated through a comparative analysis between SERS and mass spectrometry (MS). SERS fingerprinting of individual vesicles was effective in overcoming the challenges posed by EV population averaging, allowing for the possibility of analyzing the variations in biomolecular composition between the vesicles of similar and/or different sizes. Using this approach, we uncovered that each of the size-based fractions of sEVs contained particles with predominantly similar SERS spectral features. Indeed, more than 84% of the vesicles residing within a particular group were clearly distinguishable from that of the other EV sub-populations, despite some spectral variations within each sub-population. Our results suggest the possibility that size-based EV fractionation methods produce samples where similarly eluted sEVs are correlated with their respective biochemical contents, as reflected by their SERS spec

Plastics have become ubiquitous in the world’s oceans, and recent work indicates that they can transfer from the ocean to the atmosphere in sea spray aerosol (SSA). SSA is the largest contributor to annual aerosol mass load and is a significant source of plastic to the atmosphere. Plastic additives, including bisphenol-A (BPA), represent a sizable fraction of consumer plastics and have been measured consistently in air over both terrestrial and marine environments. However, the chemical lifetimes of BPA and mechanisms by which it degrades with respect to photochemical and heterogeneous oxidation processes in aerosols are unknown. The work in this dissertation utilized an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) to monitor changes in aerosol composition with high time resolution. In Chapter 3, the photosensitized and OH- initiated heterogeneous oxidation kinetics of BPA in the aerosol phase consisting of pure-component BPA and internal mixtures of BPA, NaCl, and dissolved photosensitizing organic matter are presented. OH-initiated degradation is enhanced in the presence of chloride, likely due to the enhanced mobility of BPA in the more liquid-like particle due to the hygroscopicity of NaCl increasing the liquid water content within the aerosol. In contrast, photosensitized reactions were limited in the presence of chloride, which was attributed to quenching of triplet state formation by dissolved Cl− in the less viscous aqueous aerosol mixtures. In Chapter 4, the composition changes in SSA during a phytoplankton bloom are determined, including the temporal variability and trends dependent on specific biological processes occurring in seawater. Through this study, it was also established that EESI-TOF sensitivity is critically dependent on the sample's relative humidity after adjusting for pressure variations at the inlet and normalization to the reagent ion. In Chapter 5, the photosensitized degradation of BPA at high and low pH

A variety of scattering-based, microscopy-based, and mobility-based methods are frequently used to probe the size distributions of colloidal nanoparticles with transmission electron microscopy (TEM) often considered to be the "gold standard". Charge detection mass spectrometry (CDMS) is an alternative method for nanoparticle characterization that can rapidly measure the mass and charge of individual nanoparticle ions with high accuracy. Two low polydispersity, ∼100 nm diameter nanoparticle size standards with different compositions (polymethyl methacrylate/polystyrene copolymer and 100% polystyrene) were characterized using both TEM and CDMS to explore the merits and complementary aspects of both methods. Mass and diameter distributions are rapidly obtained from CDMS measurements of thousands of individual ions of known spherical shape, requiring less time than TEM sample preparation and image analysis. TEM image-to-image variations resulted in a ∼1-2 nm range in the determined mean diameters whereas the CDMS mass precision of ∼1% in these experiments leads to a diameter uncertainty of just 0.3 nm. For the 100% polystyrene nanoparticles with known density, the CDMS and TEM particle diameter distributions were in excellent agreement. For the copolymer nanoparticles with unknown density, the diameter from TEM measurements combined with the mass from CDMS measurements enabled an accurate measurement of nanoparticle density. Differing extents of charging for the two nanoparticle standards measured by CDMS show that charging is sensitive to nanoparticle surface properties. A mixture of the two samples was separated based on their different extents of charging despite having overlapping mass distributions centered at 341.5 and 331.0 MDa.

The complexity of information processing in the brain requires the development of technologies that can provide spatial and temporal resolution by means of dense electrode arrays paired with high-channel-count signal acquisition electronics. In this work, we present an ultra-low noise modular 512-channel neural recording circuit that is scalable to up to 4096 simultaneously recording channels. The neural readout application-specific integrated circuit (ASIC) uses a dense 8.2 mm × 6.8 mm 2D layout to enable high-channel count, creating an ultra-light 350 mg flexible module. The module can be deployed on headstages for small animals like rodents and songbirds, and it can be integrated with a variety of electrode arrays. The chip was fabricated in a TSMC 0.18 µm 1.8 V CMOS technology and dissipates a total of 125 mW. Each DC-coupled channel features a gain and bandwidth programmable analog front-end along with 14 b analog-to-digital conversion at speeds up to 30 kS/s. Additionally, each front-end includes programmable electrode plating and electrode impedance measurement capability. We present both standalone and in vivo measurements results, demonstrating the readout of spikes and field potentials that are modulated by a sensory input.