A fundamental study of lignin reactions with formaldehyde and glyoxal
Lignin-glyoxal: a fully biobased wood adhesive.
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Lignin-glyoxal: a fully biobased wood adhesive.
Self-healing coatings have potential to reduce waste and minimize repair costs in industries where materials need to be protected from harsh environmental conditions and mechanical abrasion. These coatings can be created by embedding healing-agent filled microcapsules which release their contents and fill voids in the event of damage. To synthesize microcapsules that are ideal for self-healing coatings, they must have a diameter less than 100 microns, smooth surface morphology, and have improved dispersibility. Our current one-step method does not produce microcapsules within the desired size distribution, so a two-step route where oligomers of the shell wall material are formed prior to microcapsule formation was investigated. This was done by evaluating the effects of solution viscosity, size of reaction vessel, addition of poly (vinyl alcohol) (PVA), and core/shell ratio on microcapsule properties. Characterization of microcapsule size, morphology, and composition was done using optical microscopy, Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). Microcapsules with an average diameter of 78 ± 16 microns were successfully synthesized. Further work must be done to minimize PUF crystallites on the surface of the microcapsules.
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A product includes an aerogel having a single bulk structure, the single bulk structure having at least one dimension greater than 10 millimeters. The single bulk structure includes a plurality of pores, where each pore has a largest diameter defined as a greatest distance between pore walls of the respective pore. In addition, an average of the largest diameters of a majority of the pores is within a specified range, and the plurality of pores are distributed substantially homogenously throughout the single bulk structure.
This report describes our efforts to develop a partial electrochemical oxidation process to produce formaldehyde selectively from methanol. The effort examined numerous potential anode materials in pursuit of 70% Faradaic efficiency for conversion of methanol to formaldehyde. Among the various electrode materials tested herein both Pt and PtRu were identified as the most promising catalysts in this process as the Faradaic efficiency obtained in these cases are 40% and >70% respectively. Several other 3d transition metals, Pt group metals and their alloys were also studied in which the Faradaic efficiency was obtained within 5-30%. In case of Pt and PtRu bulk metal electrode shows higher selectivity to formaldehyde compared to their nanostructured materials. Based on the literature, nanostructured Pt and PtRu are considered as active catalysts for methanol fuel cells, thus, lower selectivity to formaldehyde with nano Pt and PtRu in our case was attributed to their preferential oxidation of methanol to CO 2 . Severe catalyst deactivation was noted when 0.5 (M) sulfuric acid was used as the electrolyte irrespective of catalyst formulation. On the other hand, much higher activity and selectivity for formaldehyde was noted when alkaline electrolyte was employed during oxidation. Considering selective electrochemical oxidation of methanol to formaldehyde is an area which is underexplored as of today, our findings about catalyst formulation and process condition is noteworthy in this direction. Both bulk metal electrodes of Pt and PtRu may be cost prohibitive and thus present challenges to the scale up this technology. Therefore, we recognize that additional efforts are needed to develop catalysts with high activities and Faradaic efficiencies similar to bulk electrodes for the electrooxidation of methanol to formaldehyde.
The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.
Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. Furthermore, while a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm -2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21-28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means.
Abstract. Gas-phase oxidation of isoprene by ozone (O3) and the hydroxyl (OH) and nitrate (NO3) radicals significantly impacts tropospheric oxidant levels and secondary organic aerosol formation. The most comprehensive and up-to-date chemical mechanism for isoprene oxidation consists of several hundred species and over 800 reactions. Therefore, the computational expense of including the entire mechanism in large-scale atmospheric chemical transport models is usually prohibitive, and most models employ reduced isoprene mechanisms ranging in size from ∼ 10 to ∼ 200 species. We have developed a new reduced isoprene oxidation mechanism using a directed-graph path-based automated model reduction approach, with minimal manual adjustment of the output mechanism. The approach takes as inputs a full isoprene oxidation mechanism, the environmental parameter space, and a list of priority species which are protected from elimination during the reduction process. Our reduced mechanism, AMORE-Isoprene (where AMORE stands for Automated Model Reduction), consists of 12 species which are unique to the isoprene mechanism as well as 22 reactions. We demonstrate its performance in a box model in comparison with experimental data from the literature and other current isoprene oxidation mechanisms. AMORE-Isoprene's performance with respect to predicting the time evolution of isoprene oxidation products, including isoprene epoxydiols (IEPOX) and formaldehyde, is favorable compared with other similarly sized mechanisms. When AMORE-Isoprene is included in the Community Regional Atmospheric Chemistry Multiphase Mechanism 1.0 (CRACMM1AMORE) in the Community Multiscale Air Quality Model (CMAQ, v5.3.3), O3 and formaldehyde agreement with Environmental Protection Agency (EPA) Air Quality System observations is improved. O3 bias is reduced by 3.4 ppb under daytime conditions for O3 concentrations over 50 ppb. Formaldehyde bias is reduced by 0.26 ppb on average for all formaldehyde measurements compared with the base CRACMM1. There was no significant change in computation time between CRACMM1AMORE and the base CRACMM. AMORE-Isoprene shows a 35 % improvement in agreement between simulated IEPOX concentrations and chamber data over the base CRACMM1 mechanism when compared in the Framework for 0-D Atmospheric Modeling (F0AM) box model framework. This work demonstrates a new highly reduced isoprene mechanism and shows the potential value of automated model reduction for complex reaction systems.
Data were collected in 70 detached houses built in 2011-2017 in compliance with the mechanical ventilation requirements of California's building energy efficiency standards. Each home was monitored for a 1-week period with windows closed and the central mechanical ventilation system operating. Pollutant measurements included time-resolved fine particulate matter (PM 2.5 ) indoors and outdoors and formaldehyde and carbon dioxide (CO 2 ) indoors. Time-integrated measurements were made for formaldehyde, NO 2 , and nitrogen oxides (NO X ) indoors and outdoors. Operation of the cooktop, range hood, and other exhaust fans was continuously recorded during the monitoring period. Onetime diagnostic measurements included mechanical airflows and envelope and duct system air leakage. All homes met or were very close to meeting the ventilation requirements. On average, the dwelling unit ventilation fan moved 50% more airflow than the minimum requirement. Pollutant concentrations were similar to or lower than those reported in a 2006-2007 study of California new homes built in 2002-2005. Mean and median indoor concentrations were lower by 44% and 38% for formaldehyde and 44% and 54% for PM 2.5 . Ventilation fans were operating in only 26% of homes when first visited, and the control switches in many homes did not have informative labels as required by building standards.
The recalcitrance of complex organic polymers such as lignocellulose is one of the major obstacles to sustainable energy production from plant biomass, and the generation of toxic intermediates can negatively impact the efficiency of microbial lignocellulose degradation. Here, we describe the development of a model microbial consortium for studying lignocellulose degradation, with the specific goal of mitigating the production of the toxin formaldehyde during the breakdown of methoxylated aromatic compounds. Included are Pseudomonas putida, a lignin degrader; Cellulomonas fimi, a cellulose degrader; and sometimes Yarrowia lipolytica, an oleaginous yeast. Unique to our system is the inclusion of Methylorubrum extorquens, a methylotroph capable of using formaldehyde for growth. We developed a defined minimal “Model Lignocellulose” growth medium for reproducible coculture experiments. We demonstrated that the formaldehyde produced by P. putida growing on vanillic acid can exceed the minimum inhibitory concentration for C. fimi, and, furthermore, that the presence of M. extorquens lowers those concentrations. We also uncovered unexpected ecological dynamics, including resource competition, and interspecies differences in growth requirements and toxin sensitivities. Finally, we introduced the possibility for a mutualistic interaction between C. fimi and M. extorquens through metabolite exchange. This study lays the foundation to enable future work incorporating metabolomic analysis and modeling, genetic engineering, and laboratory evolution, on a model system that is appropriate both for fundamental eco-evolutionary studies and for the optimization of efficiency and yield in microbially-mediated biomass transformation.
Here, we assessed the catalytic properties of the Cu/ZrO 2 interface in methanol and formaldehyde steam reforming (MSR and FSR) on powder catalysts by using a comparative approach with respect to the influence of the ZrO 2 polymorph support structure (monoclinic (m-)ZrO 2 vs. tetragonal (t-)ZrO 2 ), its synthesis routine and the choice of the precursor material on the CO 2 selectivity. Our studies reveal that ZrO 2 exhibits a pronounced versatility as a support material and its catalytic properties depend most strongly on its surface properties governed by its synthesis, especially by the choice of the Zr precursor. The way of combining the support with copper introduces an additional layer of complexity, but its influence on the MSR performance is limited to a modification of the conditions provided by the ZrO 2 support. Exploiting the comparative approach regarding the Cu-ZrO 2 catalysts in FSR and MSR – including the pure support materials – in combination with in situ Fourier transform infrared (FT-IR) spectroscopy shows that the CO observed in MSR on Cu/m-ZrO 2 can be attributed to a spillover of formaldehyde to the support. Side reactions of m-ZrO 2 are suppressed at lower temperatures due to its lack of highly reactive sites, resulting in a CO 2 -selective MSR performance. In Cu/t-ZrO 2 , however, the amount of CO is higher and a combination of a formaldehyde spillover to the support and a Cu-ZrO 2 phase boundary yielding CO leads to the lower CO 2 selectivity of these samples. An elevated number of defects and reactive Lewis acidic and Brønsted basic centers of t-ZrO 2 explains this increased activity towards side reactions in contrast to Cu/m-ZrO 2 catalysts.
The alanine transaminase enzyme catalyzes the transfer of an amino group from alanine to α-ketoglutarate to produce pyruvate and glutamate. Isotope fractionation factors (IFFs) for the reaction +H 3 NCH(CH 3 )COO – + – OOCCH 2 CH 2 C(O)COO – ↔ CH 3 C(O)COO – + + H 3 NCH(CH 2 CH 2 COO – )COO – (zwitterionic neutral alanine + doubly deprotonated α-ketoglutarate ↔ pyruvate + zwitterionic glutamate anion) were calculated from the partition functions of explicitly and implicitly solvated molecules at 298 K. Calculations were done for alanine (noncharge separated, zwitterion, deprotonated), pyruvic acid (neutral, deprotonated), glutamic acid (noncharge separated, zwitterion, deprotonated, doubly deprotonated), and α-ketoglutaric acid (neutral, deprotonated, doubly deprotonated). The computational results, calculated from gas phase- and aqueous-optimized clusters with explicit H 2 O molecules at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVDZ/COSMO levels, respectively, predict that substitution of 13 C at the C2 position of alanine and pyruvic acid and their various forms leads to the C2 position of pyruvic acid/pyruvate being enriched in 13 C/ 12 C ratio by 9‰. Simpler approaches that estimate the IFFs based solely on changes in the zero-point energies (ZPEs) are consistent with the higher-level model. ZPE-based IFFs calculated for simple analogues formaldehyde and methylamine (analogous to the C2 positions of pyruvate and alanine, respectively) predict a 13 C enrichment in formaldehyde of 7–8‰ at the MP2/aug-cc-pVDZ and aug-cc-pVTZ levels. A simple predictive model using canonical functional group frequencies and reduced masses for 13 C exchange between R 2 C=O and R 2 CH–NH 2 predicted enrichment in R 2 C=O that is too large by a factor of two but is qualitatively accurate compared with the more sophisticated models. Our models are all in agreement with the expectation that pyruvate and formaldehyde will be preferentially enriched in 13 C because of the strength of their >C=O bond relative to that of ≡C–NH 2 in alanine and methylamine. 13 C/ 12 C substitution is also modeled at the methyl and carboxylic acid sites of alanine and pyruvic acid, respectively.
The detection of volatile organic compounds (VOCs) is an important topic for environmental safety and public health. However, the current commercial VOC detectors suffer from cross-sensitivity and low reproducibility. In this work, we present species-selective detection for VOCs using an electrochemical cell based on ionic liquid (IL) electrolytes with features of high selectivity and reliability. The voltammograms measured with the IL-based electrolyte absorbing different VOCs exhibited species-selective features that were extracted and classified by linear discriminant analysis (LDA). The detection system could identify as many as four types of VOCs, including methanol, ethanol, acetone, formaldehyde, and additional water. A mixture of methanol and formaldehyde was detected as well. The sample required for the VOCs classification system was 50 μL, or 1.164 mmol, on average. The response time for each VOC measurement is as fast as 24 s. The volume of VOCs such as formaldehyde in solution could also be quantified by LDA and electrochemical impedance spectroscopy techniques, respectively. The system showed a tunable detection range for 1.6 and 16% (w/v) CH 2 O solution by adjusting the composition of the electrolyte. The limit of detection was as low as 1 μL. For the 1.6% CH 2 O solution, the linearity calibration range was determined to be from 5.30 to 53.00 μmol with a limit of detection at 0.53 μmol. The mechanisms for VOCs determination and quantification are also thoroughly discussed. Finally, it is expected that this work could provide a new insight into the concept of electrochemical detection of VOCs with machine learning analysis and be applied to both VOCs gas monitoring and fluid detection.
A bipolar membrane electrolyzer coupling bicarbonate electrolysis with formaldehyde oxidation directly produces syngas (H 2 : CO = 1) at 1.7 V and 200 mA cm −2 with 200% combined Faradaic efficiency. We demonstrate an electrochemical syngas production platform that couples bicarbonate electrolysis with formaldehyde oxidation in a bipolar membrane electrode assembly. This strategy doubles syngas (CO + H 2 ) throughput compared to conventional CO 2 electrolysis by generating CO at the cathode and H 2 at the anode. The system achieves a full-cell voltage of 1.7 V while operating at an industrially relevant current density of 200 mA cm −2 . The system maintained a combined Faradaic efficiency of 200% over 8 hours. The process produces syngas with a 1 : 1 H 2 : CO ratio, aligning with downstream requirements for Fischer–Tropsch synthesis. We further investigated how Cu anode active sites and electrolyte composition affect formaldehyde oxidation activity. Our integrated electrolytic system reduces levelized energy by 45–61% relative to conventional electrochemical syngas production platforms.
This work presents pollutant concentrations and performance data for code-required mechanical ventilation equipment in 23 low-income apartments at 4 properties constructed or renovated 2013-2017. All apartments had natural gas cooking burners. Occupants pledged to not use windows for ventilation during the study but several did. Measured airflows of range hoods and bathroom exhaust fans were lower than product specifications. Only eight apartments operationally met all ventilation code requirements. Pollutants measured over one week in each apartment included time-resolved fine particulate matter (PM 2.5 ), nitrogen dioxide (NO 2 ), formaldehyde and carbon dioxide (CO 2 ) and time-integrated formaldehyde, NO 2 and nitrogen oxides (NO X ). Compared to a recent study of California houses with code-compliant ventilation, apartments were smaller, had fewer occupants, higher densities, and higher mechanical ventilation rates. Mean PM 2.5 , formaldehyde, NO 2 , and CO 2 were 7.7 µg/m 3 , 14.1 ppb, 18.8 ppb, and 741 ppm in apartments; these are 4% lower, 25% lower, 165% higher, and 18% higher compared to houses with similar cooking frequency. Four apartments had weekly PM 2.5 above the California annual outdoor standard of 12 µg/m 3 and also discrete days above the World Health Organization 24-h guideline of 25 µg/m 3 . Two apartments had weekly NO 2 above the California annual outdoor standard of 30 ppb.
ABSTRACT Context-specific genome-scale model (CS-GSM) reconstruction is becoming an efficient strategy for integrating and cross-comparing experimental multi-scale data to explore the relationship between cellular genotypes, facilitating fundamental or applied research discoveries. However, the application of CS modeling for non-conventional microbes is still challenging. Here, we present a graphical user interface that integrates COBRApy, EscherPy, and RIPTiDe, Python-based tools within the BioUML platform, and streamlines the reconstruction and interrogation of the CS genome-scale metabolic frameworks via Jupyter Notebook. The approach was tested using -omics data collected for Methylotuvimicrobium alcaliphilum 20Z R , a prominent microbial chassis for methane capturing and valorization. We optimized the previously reconstructed whole genome-scale metabolic network by adjusting the flux distribution using gene expression data. The outputs of the automatically reconstructed CS metabolic network were comparable to manually optimized i IA409 models for Ca-growth conditions. However, the CS model questions the reversibility of the phosphoketolase pathway and suggests higher flux via primary oxidation pathways. The model also highlighted unresolved carbon partitioning between assimilatory and catabolic pathways at the formaldehyde-formate node. Only a very few genes and only one enzyme with a predicted function in C1 metabolism, a homolog of the formaldehyde oxidation enzyme ( fae1-2 ), showed a significant change in expression in La-growth conditions. The CS-GSM predictions agreed with the experimental measurements under the assumption that the Fae1-2 is a part of the tetrahydrofolate-linked pathway. The cellular roles of the tungsten (W)-dependent formate dehydrogenase ( fdhAB ) and fae homologs ( fae1-2 and fae3 ) were investigated via mutagenesis. The phenotype of the f dhAB mutant followed the model prediction. Furthermore, a more significant reduction of the biomass yield was observed during growth in La-supplemented media, confirming a higher flux through formate. M. alcaliphilum 20Z R mutants lacking fae1-2 did not display any significant defects in methane or methanol-dependent growth. However, contrary to fae1, the fae1-2 homolog failed to restore the formaldehyde-activating enzyme function in complementation tests. Overall, the presented data suggest that the developed computational workflow supports the reconstruction and validation of CS-GSM networks of non-model microbes. IMPORTANCE The interrogation of various types of data is a routine strategy to explore the relationship between genotype and phenotype. An efficient approach for integrating and cross-comparing experimental multi-scale data in the context of whole-genome-based metabolic network reconstruction becomes a powerful tool that facilitates fundamental and applied research discoveries. The present study describes the reconstruction of a context-specific (CS) model for the methane-utilizing bacterium, Methylotuvimicrobium alcaliphilum 20Z R . M. alcaliphilum 20Z R is becoming an attractive microbial platform for the production of biofuels, chemicals, pharmaceuticals, and bio-sorbents for capturing atmospheric methane. We demonstrate that this pipeline can help reconstruct metabolic models that are similar to manually curated networks. Furthermore, the model is able to highlight previously overlooked pathways, thus advancing fundamental knowledge of non-model microbial systems or promoting their development toward biotechnological or environmental implementations.
Data were collected to characterize whole-house mechanical ventilation (WHMV) and indoor air quality (IAQ) in 55 homes in the Marine climate of Oregon and the Cold-Dry climate of Colorado in the U.S. Sixteen homes were monitored for two weeks, with and without WHMV operating. Ventilation airflows; airtightness; time-resolved CO 2 , PM2.5 and radon; and time-integrated NO 2 , NO X and formaldehyde were measured. Participants provided information about IAQ-impacting activities, perceptions and ventilation use. All homes had operational cooktop ventilation and bathroom exhaust. Thirty homes had equipment that could meet the ASHRAE 62.2–2010 standard with continuous or controlled runtime and 34 had some WHMV operating as found. Thirty-five of 46 participants with WHMV reported they did not know how to operate it, and only half of the systems were properly labeled. Two-week homes had lower formaldehyde, radon, CO 2 and NO (NO X -NO 2 ) when operated with WHMV, and had faster PM 2.5 decays following indoor emission events. Overall IAQ satisfaction was similar in Oregon and Colorado, but more Colorado participants (19% vs 3%) felt their IAQ could be improved and more reported dryness as a problem (58% vs. 14%). The collected data indicate that there are benefits of operating WHMV, even when continuous use may not be needed because outdoor pollutant concentrations are low and indoor sources do not present substantial challenges.