Membrane contactors have proved to be effective for recovering ammonia from wastewater by absorbing it into a trapping solution. This study compares the performance of sulfuric acid and citric acid as trapping solutions in a pilot-scale plant for recovering ammonia from sludge digestion liquors using membrane contactors in a liquid–liquid configuration operating at pH 10 and a temperature of 37 °C and using ultrafiltration (UF) technology as pretreatment. The performance of the process using sulfuric acid at a lower pH (9.5) and temperature (30 °C) was also studied, as well as the advantage of including a CO2-stripping module in the process. The ammonia elimination efficiency was 88% and 86% when using sulfuric acid and citric acid, respectively. The nitrogen concentration of the produced ammonium sulfate and ammonium citrate reached 23.2 and 14.7 g NH3-N·L−1, respectively. The ammonia elimination efficiency when using sulfuric acid decreased to 49% when decreasing the pH to 9.5 and to 85% when decreasing the temperature to 31 °C. UF technology was able to reduce the concentration of suspended solids by 90% and the chemical oxygen demand by 37%. However, the UF membranes for the pretreatment and the membrane contactors for ammonia recovery had to be constantly cleaned with acid due to scaling, which significantly increased maintenance efforts. The CO2-stripping module reduced the consumption of the caustic soda solution by 23% for increasing the pH level of the treated water. Finally, the specific energy consumption of the plant was 8 kWh·m−3.
Hydrogels containing functional groups are highly interesting for sensor applications as they can change their physical properties by interaction with their environment. In this study, it is demonstrated that by monitoring the conductance of two different functional hydrogels, the concentrations of two different drugs in aqueous solution can be selectively and quantitatively measured simultaneously based on non-specific interactions. Detailed characterization of the competitive drug adsorption on the hydrogels allows the description of both hydrogel conductances as a function of the drug concentrations based on physical models. The result is a system of non-linear equations that can be solved for the drug concentrations. The different affinities and conductance responses of the hydrogels for the two drugs is a prerequisite, which is usually achieved with different materials. This approach is demonstrated with hydrogels based on poly(ethylene glycol), functionalized with the ionic monomers [2-(acryloyloxy)ethyl] trimethylammonium chloride (AETA) and 3-sulfopropyl acrylate potassium salt (SPA), and the drugs diclofenac and metoprolol. The hydrogel conductance is found to be linear with drug concentration in the hydrogels, which in turn is described by a non-linear Langmuir-type competitive adsorption isotherm. The proposed approach thus shows potential for future studies on more complex mixtures by including a larger variety of functional hydrogels.
Polyelectrolyte hydrogels containing negatively charged sulfonate groups or positively charged ammonium groups are characterized by their adsorption behavior toward the pharmaceuticals metoprolol (cationic) and diclofenac (anionic) in an aqueous solution. Additionally, the change in the hydrogel refractive index with metoprolol and diclofenac concentrations inside the hydrogel is investigated. Both metoprolol adsorption on sulfonate group containing hydrogels as well as diclofenac adsorption on the ammonium group containing hydrogels can be described using a modified Langmuir-type adsorption isotherm with K-s values around 0.1 and 10 mL mu mol(-1), respectively. In both cases, the adsorption capacities are close to the concentration of charged groups in the hydrogels. Thus, diclofenac concentrations inside the hydrogels are enhanced by a factor of approximately 1000 and metoprolol concentrations by a factor of approximately 10 compared to their concentrations in solution. In contrast, metoprolol was completely excluded from the ammonium group containing hydrogels, and diclofenac showed weak adsorption on the poly(ethylene glycol) fraction of the sulfonate group containing hydrogels, resulting in lower concentration enhancements. Hydrogel refractive indices increased linearly with the concentration of metoprolol and diclofenac inside the hydrogels. Thus, monitoring the refractive index of sulfonate group containing hydrogels is shown to be efficient in measuring the solution concentrations of metoprolol up to 10 mu mol mL(-1) and of ammonium group containing hydrogels for diclofenac concentrations up to 0.1 mu mol mL(-1), both values corresponding to the reciprocal of the K-s values. In the case of Langmuir-type adsorption, maximizing K-s values therefore leads to the best refractive index sensor sensitivities at low analyte concentrations, whereas lower K-s values lead to lower sensitivities at low concentrations but to superior sensitivities at rather high analyte concentrations. Inkjet printing of the hydrogel formulations is demonstrated to facilitate their future use as spatially resolved coatings on sensor surfaces.
Systematic variation of the composition of calcium alginate/polyacrylamide double network hydrogels paves the way for the optimization of mechanical properties.
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To reduce the usage of classical lubricants in deep drawing, a new tribological system based on volatile lubricants was developed. Therefore, a volatile medium is injected under high pressure into the interstice between drawing tool and sheet metal. Depending on temperature and pressure, the temporary lubricant may exist in its gaseous or liquid phase. In this study, a novel high fluid pressure tribometer was designed to investigate the friction and wear of dry steel contacts under comparable conditions like in dry deep drawing. Therefore, a new ball-on-disc tribometer was designed and integrated into a high-pressure vessel. To specifically investigate the effects of different environments (technical air, liquid and gaseous carbon dioxide, nitrogen, argon) at atmospheric and high pressure (0.1 MPa, 6 MPa) on tribology, the specimens and all components were operating unlubricated. During the experiments, the friction was measured continuously. Results show that the highest friction occurs in air and the lowest in carbon dioxide environment. Subsequent to the experiments, the wear of the specimens was assessed along with changes in surface chemistry related to tribochemical reactions. Therefore, the tribology of the dry sliding contacts is correlated to changes of the surface chemistry. Also differences as well as similarities regarding the different fluid environments are shown. As the results show, the differences between the media used are most pronounced at elevated pressure. Concluding, this work gives clear indications on the suitability of volatile lubricants in dry friction or rather gas lubrication, especially for dry deep drawing.
The outcome of three-dimensional (3D) bioprinting heavily depends, amongst others, on the interaction between the developed bioink, the printing process, and the printing equipment. However, if this interplay is ensured, bioprinting promises unmatched possibilities in the health care area. To pave the way for comparing newly developed biomaterials, clinical studies, and medical applications (i.e. printed organs, patient-specific tissues), there is a great need for standardization of manufacturing methods in order to enable technology transfers. Despite the importance of such standardization, there is currently a tremendous lack of empirical data that examines the reproducibility and robustness of production in more than one location at a time. In this work, we present data derived from a round robin test for extrusion-based 3D printing performance comprising 12 different academic laboratories throughout Germany and analyze the respective prints using automated image analysis (IA) in three independent academic groups. The fabrication of objects from polymer solutions was standardized as much as currently possible to allow studying the comparability of results from different laboratories. This study has led to the conclusion that current standardization conditions still leave room for the intervention of operators due to missing automation of the equipment. This affects significantly the reproducibility and comparability of bioprinting experiments in multiple laboratories. Nevertheless, automated IA proved to be a suitable methodology for quality assurance as three independently developed workflows achieved similar results. Moreover, the extracted data describing geometric features showed how the function of printers affects the quality of the printed object. A significant step toward standardization of the process was made as an infrastructure for distribution of material and methods, as well as for data transfer and storage was successfully established.
Cellobiose lipids (CL) are glycolipids secreted by many Ustilaginaceae species in aerobic fermentations characterised by excessive foaming. While increasing CL concentrations remains an aim for its industrial production, excessive foaming during fermentation presents a challenge even at laboratory scale. Foam fractionation (FF) provides a solution to the foaming problem and facilitates the proceeding purification of CL. Here, we present a first CL fermentation process applying FF. With our set-up, we manage to exploit the excessive foaming for continuous product separation. The set-up includes a foam collecting vessel (FCV) with inserts for CL accumulation and foamate recirculation to minimise biomass and nutrient loss. Integrating a foam column (FC) into the fermenter headspace enabled foam enrichment, resulting in the recovery of > 90% of the produced CL from the separated fractions consisting of foam depositions in the fermenter headspace and the FCV. We also increased the fermenter filling volume and thus achieved a higher fermentation capacity. The separated CL fraction was purified via ethanol extraction to obtain CL with purities > 90%. We further examined the effects of different culture media constituents, including biomass and CL, on foam generation and decay and assessed the effect of FC geometries on product enrichment and recovery. In this work, a FF set-up is presented that enables a stable CL fermentation without additional foam mitigation methods. At the same time, the application of FF separated a fraction that was highly enriched in CL during fermentation, resulting in highly pure CL after a simple ethanol extraction.
In order to reduce the use of classic lubricants such as synthetic or mineral oils, emulsions or waxes in the deep drawing process, a new tribological system based on volatile lubricants was investigated. In this system, a volatile medium is injected under high pressure through laser drilled micro holes directly into the contact zone between the tool and the sheet metal and serves as a temporary lubricant. In order to investigate this tribological system under realistic conditions, strip drawing experiments with different volatile lubricants (air, nitrogen, carbon dioxide and argon) were performed on galvanized sheets. Therefore, a new generation of strip drawing tools was designed and numerically calculated for low elastic deformations to ensure a uniform contact pressure distribution over the entire friction contact area. To obtain a homogeneous distribution of the volatile lubricants, a number of micro holes with a depth of several millimeters were drilled into the hardened strip drawing jaws using ultrashort pulsed laser radiation. Taking into account the capabilities of this laser drilling technique in terms of size and shape of the micro holes, computational fluid dynamics simulations were performed to predict the flow behavior of the lubricant within the micro hole as well as the contact zone and were compared with observable effects in outflow tests. The chemical composition of the acting tribological layers was characterized by means of X-ray photoelectron spectroscopy and their changes during the deep drawing process were correlated with the lubricants used as well as the measured wear and friction values.
Abstract The light conditions are of utmost importance in any microalgae production process especially involving artificial illumination. This also applies to a chrysolaminarin (soluble 1,3‐β‐glucan) production process using the diatom Phaeodactylum tricornutum. Here we examine the influence of the amount of light per gram biomass (specific light availability) and the influence of two different biomass densities (at the same amount of light per gram biomass) on the accumulation of the storage product chrysolaminarin during nitrogen depletion in artificially illuminated flat‐panel airlift photobioreactors. Besides chrysolaminarin, other compounds (fucoxanthin, fatty acids used for energy storage [C16 fatty acids], and eicosapentaenoic acid) are regarded as well. Our results show that the time course of C‐allocation between chrysolaminarin and fatty acids, serving as storage compounds, is influenced by specific light availability and cell concentration. Furthermore, our findings demonstrate that with increasing specific light availability, the maximal chrysolaminarin content increases. However, this effect is limited. Beyond a certain specific light availability (here: 5 µmolphotons gDW−1 s−1) the maximal chrysolaminarin content no longer increases, but the rate of increase becomes faster. Furthermore, the conversion of light to chrysolaminarin is best at the beginning of nitrogen depletion. Additionally, our results show that a high biomass concentration has a negative effect on the maximal chrysolaminarin content, most likely due to the occurring self‐shading effects.
Hydrogels can be equipped with functional groups for specific purposes. Isothiouronium groups can enhance adsorptivity, or allow coupling of other functional groups through mild reactions after transformation to thiol groups. Here we present a method to prepare multifunctional hydrogels by introducing isothiouronium groups into poly(ethylene glycol) diacrylate (PEGDA) hydrogels, and convert them into thiol-functionalized hydrogels by the reduction of the isothiouronium groups. For this purpose, the amphiphilic monomer 2-(11-(acryloyloxy)-undecyl)isothiouronium bromide (AUITB), containing an isothiouronium group, was synthesized and copolymerized with PEGDA. In this convenient way, it was possible to incorporate up to 3 wt% AUITB into the hydrogels without changing their equilibrium swelling degree. The successful functionalization was demonstrated by surface analysis of the hydrogels with water contact angle measurements and increased isoelectric points of the hydrogel surfaces from 4.5 to 9.0 due to the presence of the isothiouronium groups. The hydrogels showed a suitability as an adsorbent, as exemplified by the pronounced adsorption of the anionic drug diclofenac. The potential of the functionalization for (bio)conjugation reactions was demonstrated by the reduction of isothiouronium groups to thiols and subsequent immobilization of the functional enzyme horseradish peroxidase on the hydrogels. The results show that fully accessible isothiouronium groups can be introduced into radically cross-linked hydrogels.
An all-soft multi-material combination consisting of a hydrogel based on poly(ethylene glycol) (PEG) coated with spatially defined spots of gelatin methacryloyl (GM) containing selectively addressable viral nanorods is presented, and its basic application as a qualitative biosensor with reporter enzymes displayed on the tobacco mosaic virus (TMV) bioscaffolds within the GM is demonstrated. Biologically inert PEG supports are equipped with GM spots serving as biological matrix for enzymes clustered on TMV particles preventing diffusion out of the gel. For this multi-material combination, i) the PEG-based hydrogel surface is modified to achieve a clear boundary between coated and non-coated regions by introducing either isothiouronium or thiol groups. ii) Cross-linking of the GM spots is studied to achieve anchoring to the hydrogel surface. iii) The enzymes horseradish peroxidase or penicillinase (Pen) are conjugated to TMV and integrated into the GM matrix. In contrast to free enzymes, enzyme-decorated TMVs persist in GM spots and show sustained enzyme activity as evidenced by specific color reaction after 7 days of washing, and for Pen after 22 months after dry storage. Therefore, the integration of enzyme-coupled TMV into hydrogel matrices is a promising and versatile approach to obtaining reusable and analyte-specific sensor components.
Introduction: The Bouguer-Lambert-Beer law is widely used as the fundamental equation for quantification in absorption spectroscopy. However, deviations from the Bouguer-Lambert-Beer law have also been observed, such as chemical deviation and light scattering effect. While it has been proven and shown that the Bouguer-Lambert-Beer law is valid only under very restricted limitations, there are only a few alternatives of analytical models to this law. Based on the observation in the experiments, we propose a novel model to solve the problem of chemical deviation and light scattering effect.Methods: To test the proposed model, a systematic verification was conducted using potassium dichromate solutions and two types of microalgae suspensions with varying concentrations and path lengths.Results: Our proposed model demonstrated excellent performance, with a correlation coefficient (R2) exceeding 0.995 for all tested materials, significantly surpassing the Bouguer-Lambert-Beer law, which had an R2 as low as 0.94. Our results confirm that the absorbance of pure pigment solutions follows the Bouguer-Lambert-Beer law, while the microalgae suspensions do not due to the light scattering effect. We also show that this scattering effect leads to huge deviations for the commonly used linear scaling of the spectra, and we provide a better solution based on the proposed model.Discussion: This work provides a powerful tool for chemical analysis and especially for the quantification of microorganisms, such as the concentration of biomass or intracellular biomolecules. Not only the high accuracy but also the simplicity of the model makes it a practical alternative to the existing Bouguer-Lambert-Beer law.
The Bouguer-Lambert-Beer (BLB) law serves as the fundamental basis for the spectrophotometric determination of pigment content in microalgae. Although it has been observed that the applicability of the BLB law is compromised by the light scattering effect in microalgae suspensions, in-depth research concerning the relationship between the light scattering effect and the accuracy of spectrophotometric pigment determination remains scarce. We hypothesized that (1) the precision of spectrophotometric pigment content determination using the BLB law would diminish with increasing nonlinearity of absorbance, and (2) employing the modified version of the BLB (mBLB) law would yield superior performance. To assess our hypotheses, we cultivated Phaeodactylum tricornutum under varying illumination conditions and nitrogen supplies in controlled indoor experiments, resulting in suspensions with diverse pigment contents. Subsequently, P. tricornutum samples were diluted into subsamples, and spectral measurements were conducted using different combinations of biomass concentrations and path lengths. This was carried out to assess the applicability of the BLB law and the nonlinearity of absorbance. The chlorophyll a and fucoxanthin contents in the samples were analyzed via high-performance liquid chromatography (HPLC) and subsequently used in our modeling. Our findings confirm our hypotheses, showing that the modified BLB law outperforms the original BLB law in terms of the normalized root mean square error (NRMSE): 6.3% for chlorophyll a and 5.8% for fucoxanthin, compared to 8.5% and 7.9%, respectively.
Beta-glucans are polysaccharides that can be used for different applications, for example as an immunomodulator in food or feed or for managing high cholesterol levels. Certain microalgae species use beta-glucans as energy storage, accumulating them during nutrient depletion. In this study, we examined and compared beta-glucan production during nitrogen depletion in three different algae species, Phaeodactylum tricornutum , Monodopsis subterranea and Cylindrotheca fusiformis, grown in artificially illuminated flat panel airlift reactors, in order to determine the most promising microalgae species for beta-glucan production. Co-products such as fatty acids (especially eicosapentaenoic acid) and the carotenoid fucoxanthin (not produced by M. subterranea ) were also considered. Biomass analysis showed that P. tricornutum cultures reached a maximal beta-glucan content of 317 ± 9 mg g DW −1 , M. subterranea cultures reached 188 ± 6 mg g DW −1 and C. fusiformis cultures reached 129 ± 13 mg g DW −1 . Furthermore, beta-glucan production was faster in P. tricornutum cultures. However, the maximum volumetric beta-glucan concentration reached was higher in M. subterranea cultures compared to P. tricornutum cultures as M. subterranea cultures produced more biomass during nitrogen depletion. In terms of possible co-products, P. tricornutum produced fucoxanthin and EPA, whereas M. subterranea did not produce fucoxanthin. However, M. subterranea exhibited a higher EPA content, which remained above 45 mg g −1 even after several days of nitrogen depletion. Overall, our results suggest that P. tricornutum and M. subterranea are both suitable species for beta-glucan production in flat panel airlift reactors.
Accurate prediction of microalgae growth is crucial for understanding the impacts of light dynamics and optimizing production. Although various mathematical models have been proposed, only a few of them have been validated in outdoor cultivation. This study aims to investigate the use of machine learning algorithms in microalgae growth modeling. Outdoor cultivation data of Phaeodactylum tricornutum in flat-panel airlift photobioreactors for 50 days were used to compare the performance of Long Short-Term Memory (LSTM) and Support Vector Regression (SVR) with traditional models, namely Monod and Haldane. The results indicate that the machine learning models outperform the traditional models due to their ability to utilize light history as input. Moreover, the LSTM model shows an excellent ability to describe the light acclimation effect. Last, two potential applications of these models are demonstrated: 1) use as a biomass soft sensor and 2) development of an optimal harvest strategy for outdoor cultivation.
The water-soluble polymer poly(vinyl alcohol) (PVA) is a well-known coating material for the fabrication of composite membranes. In order to limit swelling and prevent dissolution in aqueous environments, PVA layers must be cross-linked before use. For this purpose, in this work, water-soluble, photoreactive PVA derivatives were synthesized and spin coated onto silanized silicon wafers, and their cross-linking was investigated. Moreover, composite membranes were formed via doctor blading, followed by cross-linking the resulting polymer layers and determination of the water vapor permeance. In a one-pot synthesis, PVA was reacted with 1,3-propane sultone and 4-fluorobenzophenone, yielding sulfopropyl and benzophenone-modified PVA (sPVA-BP). The modification degrees were successfully controlled via the reaction conditions and amounted to values between 6 and 26% for benzophenone modification and 6 and 12% for sulfopropyl modification. All synthesized polymers had a solubility of at least 10% (w/w) in water. Thin layers of sPVA-BP with thicknesses of around 30 nm on silanized silicon wafers formed insoluble networks upon irradiation. The gel contents (Y) of the cross-linked networks were approximately 80%. The equilibrium degree of swelling (EDS) strongly depended on the modification degrees of the polymers and decreased while cross-linking. After 30 min of irradiation with UV light, EDS plateaus between 4 and 12 were reached, indicating a completed network formation. In order to prove the applicability of sPVA-BP layers for membrane applications, polypropylene/sPVA-BP composite membranes with an sPVA-BP layer thickness of 3.3 mu m were tested for their water vapor permeance. The membranes reached a water vapor permeance (J(w)) of approximately 2000 GPU, which is comparable to those of other PVA-based composite membranes. We therefore conclude that sPVA-BP is a promising photoreactive coating material, e.g., for the fabrication of composite humidifier membranes.
High power stray radiation is a problem that affects heating systems of fusion reactors. Due to the harsh environment in such a device an absorption mechanism was investigated in both experiment and modeling, which allows the use of thermically and chemically very stable ceramic coatings, while providing very good absorption.
Microwave absorbing layer materials (MALMs) are extremely important for many components in fusion reactors to absorb microwave radiation in a controlled manner and with predictable power density. Therefore, a detailed knowledge of absorption properties of absorber coating materials used is necessary. Plasma-sprayed mixed oxide coatings are most commonly used in those applications where moderate power density is expected. In this paper, a plane wave absorption model is presented using refractive index and absorption coefficient as internal parameters and incidence angle, polarization, and layer thickness as external parameters. The model has been calculated assuming radiation of 170 GHz, as envisaged for the ITER research facility. Three atmospheric plasma-sprayed coating materials were considered in this work: titanium dioxide (TiO 2 ), chromium oxide (Cr 2 O 3 ), and a mixed aluminum-titanium oxide Al 2 O 3 -TiO 2 (40/60). Theoretical results are compared with free wave measurements with two antennas. Different coating thicknesses have been prepared and measured in different polarization and incidence angles. Results are discussed regarding polarization, incidence angle, layer thickness, absorption coefficient, and refractive index.
Polyvinyl alcohol (PVA) is a hydrophilic polymer well known for good film forming properties, high water vapor permeance J(W), and low nitrogen permeance. However, depending on molar mass and temperature, PVA swells strongly in water until complete dissolution. This behavior affects the usability of PVA in aqueous environments and makes cross-linking necessary if higher structural integrity is envisaged. In this work, PVA networks are formed by thermal cross-linking in the presence of p-toluenesulfonic acid (TSA) and investigated in a design of experiments approach. Experimental parameters are the cross-linking period t(c), temperature & thetasym; and the TSA mass fraction w(TSA). Cross-linking is found to proceed via ether bond formation at all reaction conditions. Degradation is promoted especially by a combination of high w(TSA), t(c) and & thetasym;. Thermal stability of the networks after preparation is strongly improved by neutralizing residual TSA. Humidification membranes with a J(W) of 6423 +/- 63.0 gas permeation units (GPU) are fabricated by coating PVA on polyvinyliden fluoride hollow fibers and cross-linking with TSA. Summarizing, the present study contributes to a clearer insight into the cross-linking of PVA in presence of TSA, the thermal stability of the resulting networks and the applicability as selective membrane layers for water vapor transfer.