In-line Monitoring of Monomer and Polymer Content During Microgel Synthesis Using Precipitation Polymerization via Raman Spectroscopy and Indirect Hard Modeling.

This contribution presents in-line monitoring of microgel synthesis by precipitation polymerization based on Raman spectroscopy. The spectra are evaluated via multivariate Indirect Hard Modeling (IHM) regression. Therefore, mechanistic models of the pure component spectra for solvent, monomer, and microgel are created by a sum of adaptable parameterized peak functions (Gaussian-Lorentzian). Instead of individual calibrations for each analyte, one comprehensive model is calibrated to predict both the monomer and microgel fraction while ensuring a consistent mass balance. As a novelty, this leads to an in-line microgel quantification based on an interactive spectral model. The results show cross-validation errors (RMSECV) of monomer and microgel fractions as low as 0.028 wt % and 0.084 wt %, respectively. The ability of IHM to account for non-linear spectral changes was found to reduce the microgel RMSECV by a factor of two compared to linear CLS regression. The calibration model allows simultaneous observation of the decrease in monomer content and the formation of microgels. Long as well as short focus immersion optics reveal characteristic vibrations of the turbid microgel suspension, although long focus optics are influenced by scattering particles to a greater extent. Precise examination of the model proves that the prediction is robust against changes in microgel particle size or temperature, which opens up the application of Raman spectroscopy as a comprehensive process analytical technology in microgel synthesis.

Is biomass fractionation by Organosolv-like processes economically viable? A conceptual design study.

In this work, the conceptual designs of the established Organosolv process and a novel biphasic, so-called Organocat process are developed and analyzed. Solvent recycling and energy integration are emphasized to properly assess economic viability. Both processes show a similar energy consumption (approximately 5 MJ/kg(dry biomass)). However, they still show a lack of economic attractiveness even at larger scale. The Organocat process is more favorable due to more efficient lignin separation. The analysis uncovers the remaining challenges toward an economically viable design. They largely originate from by-products formation, product isolation, and solvent recycling. Necessary improvements in process chemistry, equipment design, energy efficiency and process design are discussed to establish economically attractive Organosolv-like processes of moderate capacity as a building block of a future biorefinery.

An efficient process for the saccharification of wood chips by combined ionic liquid pretreatment and enzymatic hydrolysis.

A process concept combining pretreatment of wood in ionic liquids and subsequent enzymatic hydrolysis to sugars is herein investigated to identify operating conditions which allow for (i) the processing of larger wood chips of 10 mm length, (ii) low temperature, (iii) high sugar yield, and (iv) short processing time. A careful quantitative study of the interaction of pretreatment and hydrolysis reveals that hydrolysis is most effective if beech chips are first disintegrated in [EMIM][Ac] at 115 °C for 1.5 h. The cellulose conversion varies between 70.5 wt% and 90.2wt% for hydrolysis times between 5 h and 72 h. A complete recovery of cellulose and xylan resulting in a total saccharification of 65 wt% of the wood chips could be demonstrated. It is shown that short pretreatment times are required to enable high sugar yield as well as to limit product degradation.

State estimation for large-scale wastewater treatment plants.

Many relevant process states in wastewater treatment are not measurable, or their measurements are subject to considerable uncertainty. This poses a serious problem for process monitoring and control. Model-based state estimation can provide estimates of the unknown states and increase the reliability of measurements. In this paper, an integrated approach is presented for the optimization-based sensor network design and the estimation problem. Using the ASM1 model in the reference scenario BSM1, a cost-optimal sensor network is designed and the prominent estimators EKF and MHE are evaluated. Very good estimation results for the system comprising 78 states are found requiring sensor networks of only moderate complexity.

Conceptual design of distillation-based hybrid separation processes.

Hybrid separation processes combine different separation principles and constitute a promising design option for the separation of complex mixtures. Particularly, the integration of distillation with other unit operations can significantly improve the separation of close-boiling or azeotropic mixtures. Although the design of single-unit operations is well understood and supported by computational methods, the optimal design of flowsheets of hybrid separation processes is still a challenging task. The large number of operational and design degrees of freedom requires a systematic and optimization-based design approach. To this end, a structured approach, the so-called process synthesis framework, is proposed. This article reviews available computational methods for the conceptual design of distillation-based hybrid processes for the separation of liquid mixtures. Open problems are identified that must be addressed to finally establish a structured process synthesis framework for such processes.

Concentration measurements in ionic liquid-water mixtures by mid-infrared spectroscopy and indirect hard modeling.

An analytical method for the quantitative characterization of binary mixtures of water and ionic liquids (ILs) is presented. Mid-infrared (mid-IR) spectroscopy in combination with indirect hard modeling (IHM) is employed to quantify the water content in 1-butyl-3-methylimidazolium chloride (BMIMCl), 1,3-dimethylimidazolium dimethylphosphate (DMIMDMP), and 1-ethyl-3-methylimidazolium acetate (EMIMAc). Despite significant nonlinear shifts of the spectral bands, a good spectral fit with calibration errors of less than 2.3 wt % can be achieved almost over the whole concentration range. A profound analysis of the spectral models including peak assignment substantiates the physico-chemical foundation of the spectral models. Furthermore, the shift of peak functions in the spectral models is shown to provide a measure of molecular interaction in IL-water mixtures, which can also be utilized quantitatively. The vibrational bands of the water dipole reveal differences in the strength of hydrogen bonding with water in the IL studied. These properties of the spectral hard models demonstrate their quantitative analytical potential and set the stage for multiway calibration in comprehensive reaction monitoring in these highly interacting mixtures of IL and water.

Volatile methacrylates in dental practices.

PURPOSE: In recent years, an increase of occupational respiratory diseases, such as asthma caused by methacrylates, has been observed in dental personnel. In this study, the exposure of dental personnel to various volatile methacrylates was investigated. MATERIALS AND METHODS: The air levels of methacrylates were measured during filling treatment while bonding agents were used in 4 dental practices in Munich, Germany. Short-term air sampling (15 min) was performed using solid phase microextraction (SPME). The SPME fibers were coated with carbowax/divinyl benzene to enrich the analytes. For analysis, the analytes were thermically desorbed from the fiber and subsequently analyzed directly by gas chromatography/mass spectrometry. RESULTS: The methacrylates methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA), and triethylene glycol dimethacrylate (TEG-DMA) were identified in the air of dental practices. The exposure levels of the four methacrylates varied during the filling treatments. The maximum concentrations found were 0.4 mg/m3 for MMA, 45 microg/m3 for HEMA, 13 microg/m3 for EGDMA, and 45 microg/m3 for TEG-DMA. The detection of TEG-DMA correlated with the application of bonding agents during performance of dental fillings. CONCLUSION: Exposure levels of different methacrylates were observed at all investigated dental practices. The maximum levels of MMA measured in this study were at least 200 times lower than the toxicologically relevant maximum allowable concentrations defined in various countries. Nevertheless, the exposure levels of methacrylates should be kept as low as possible due to the allergenic potential of some methacrylates.

Excretion of dental resin monomers and metabolic intermediates via urine in guinea pigs.

OBJECTIVE: Monomers like BisGMA (Bisphenol-A-glycidyldimethacrylate) and comonomers like TEGDMA (triethyleneglycoldimethacrylate) are used in dental restorative materials in order to build up the three-dimensional network of filling materials. Since earlier investigations revealed uptake and subsequent metabolism of unpolymerized remainders of (co)monomers, the present experiment investigates the metabolic urine pattern of guinea pigs (n=4) after application of TEGDMA or BisGMA (each dose=0.02 mmol/kg body weight=100%), respectively. METHODS: For the investigations BisGMA was pre-dissolved in DMSO and subsequently diluted with 0.9% NaCl solution (final DMSO concentration 1%) and TEGDMA was dissolved in 0.9% NaCl solution. The solutions were administered with a gastric tube into the animals. Control animals received either 0.9% NaCl or 0.9% NaCl solution with 1% DMSO solution. RESULTS: After 24h in collected urine the following metabolites were identified. After administration of TEGDMA (mean relative concentration of administered substances)+/-s.d. [%]; n=4): unchanged TEGDMA: 12+/-1.5%, MA: 2.4+/-0.8%, and triethyleneglycol: 35+/-2.2%. After administration of BisGMA (mean+/-s.d. [%]; n=4): unchanged BisGMA: 11.4+/-2.7%, MA: 2.2+/-0.6%, and bisphenol-A-bis(2,3-dihydroxypropyl)ether: 60.1+/-5.2%). CONCLUSION: No further metabolites like the previously identified intermediate 2,3-epoxymethacrylic acid and derived reaction products were identified in the urine, indicating that these metabolites must have reacted further.

Mechanistic kinetic model for symmetric carboligations using benzaldehyde lyase.

For reactions using thiamine diphosphate (ThDP)-dependent enzymes many empirically-derived kinetic models exist. However, there is a lack of mechanistic kinetic models. This is especially true for the synthesis of symmetric 2-hydroxy ketones from two identical aldehydes, with one substrate acting as the donor and the other as the acceptor. In this contribution, a systematic approach for deriving such a kinetic model for thiamine diphosphate (ThDP)-dependent enzymes is presented. The derived mechanistic kinetic model takes this donor-acceptor principle into account by containing two K(m)-values even for identical substrate molecules. As example the stereoselective carbon-carbon coupling of two 3,5-dimethoxy-benzaldehyde molecules to (R)-3,3',5,5'-tetramethoxy-benzoin using benzaldehyde lyase (EC 4.1.2.38) from Pseudomonas fluorescens is studied. The model is derived using a model-based experimental analysis method which includes parameter estimation, model analysis, optimal experimental design, in silico experiments, sensitivity analysis and model revision. It is shown that this approach leads to a robust kinetic model with accurate parameter estimates and an excellent prediction capability.

Toxicity potentiation by H2O2 with components of dental restorative materials on human oral cells.

Toxicity potentiation of two monomers [bisphenol-A-glycidyldimethacrylate (BisGMA) and urethanedimethacrylate (UDMA)] as well as two comonomers [triethyleneglycoldimethacrylate (TEGDMA) and 2-hydroxyethylmethacrylate (HEMA)], each in combination with H(2)O(2), was investigated on the viability on human gingival fibroblasts (HGF) and human pulpal fibroblasts (HPF). The applied concentration of H(2)O(2) was 0.06 or 0.1 mmol/l, respectively, corresponding to the EC(0) of H(2)O(2) in HGF or HPF. The cell viability was assessed by the XTT test. From this test the half maximum effect concentrations (EC(50)) were calculated from fitted sigmoidale curves. EC(50) values were (HGF; mmol/l; mean +/- s.e.m.; n = 5): HEMA 11.9 +/- 0.9, TEGDMA 3.7 +/- 0.3, H(2)O(2) 0.36 +/- 0.04, UDMA 0.27 +/- 0.08, and BisGMA 0.11 +/- 0.03. No significant (P < 0.05) differences in the EC(50) values were observed when HGF was exposed to substances, as compared to HPF. No significant decrease of the EC(50) values was found when HGF or HPF, respectively, was exposed to HEMA or BisGMA in addition with H(2)O(2) up to the concentration of 0.1 mmol/l, as compared to those EC(50) values of each compound without H(2)O(2) addition. A significant decrease of the TEGDMA EC(50) value from 3.7 to 2.1 or 0.4 mmol/l, respectively, was found when cells were exposed to TEGDMA in combination with H(2)O(2) (0.06 or 0.1 mmol/l), as compared to that TEGDMA EC(50) value without H(2)O(2) addition. A significant decrease of the UDMA EC(50) value from 0.27 to 0.11 or 0.08 mmol/l, respectively, was found when HGF or HPF was exposed to UDMA in combination with H(2)O(2) (0.06 or 0.1 mmol/l), as compared to that UDMA EC(50) value without H(2)O(2) addition. The addition of H(2)O(2) (0.06 or 0.1 mmol/l) resulted in a toxicity potentiation of TEGDMA and UDMA, but not of HEMA and BisGMA, on HGF or HPF.

Indirect spectral hard modeling for the analysis of reactive and interacting mixtures.

We present an indirect hard modeling (IHM) approach for the quantitative analysis of reactive multicomponent mixtures with intermolecular interaction. It can be used when it is not possible to obtain calibration data in the composition region of interest. The goal of this work, specifically, is to analyze reactive systems, although the validation of the method is done with nonreactive systems. Compared to conventional hard modeling, the new approach reduces the manual work required for modeling and renders unnecessary the assignment of bands in mixture spectra to individual components. It is based on parametric models of the pure component spectra that are made just flexible enough to fit the spectra of the unknown mixtures, and it only requires small calibration data sets that may lie in different regions of the composition space. The application to infrared (IR) and Raman spectra of multicomponent systems is discussed.

Automatic generation of peak-shaped models.

We describe how parametric spectral models for analytical applications can be generated by an automatic curve-fitting algorithm. The algorithm does not require initial choices of parameters or other human intervention, in contrast to established approaches that rely on deconvolution or derivative spectroscopy. This algorithm has been applied for quantitative analysis but can potentially be used in other applications that are based on parametric representations of peak-shaped models or could benefit from using such models, such as calibration transfer.