A nickel-based metal-organic framework (Ni-MOF) with mixed N- and O-donor linkers was synthesized via both mechanochemical and solvothermal routes and evaluated as an electrocatalyst for alcohol oxidation reactions (AORs). Despite having identical crystal and electronic structures, the mechanochemically synthesized Ni-MOF (termed as MC-MOF) exhibited markedly superior catalytic activity compared to its solvothermally synthesized analog (ST-MOF). Structural characterization confirmed that enhanced performance arises from the distinct morphology and higher density of accessible Ni active sites in MC-MOF. Specifically, the MC-MOF exhibited a roughly 4.4-fold higher electrochemically active surface area, enabling the highly stable, selective oxidation of various alcohols to valuable products over 24 h of continuous operation. Operando quick X-ray absorption spectroscopy revealed that under alkaline conditions, MC-MOF undergoes potential-dependent structural evolution, displaying distinct catalytic pathways for oxygen evolution and AORs. While Ni centers oxidize to higher valence states during the oxygen evolution reaction, they remain largely in the Ni2+ state during AORs, indicating selective suppression of high-valent Ni-oxygenated species in the presence of alcohol molecules in the electrolyte medium. This study demonstrates that mechanochemical synthesis can effectively tailor the morphology and catalytic behavior of MOF-based electrocatalysts, offering an environmentally benign and scalable route for developing advanced materials for sustainable energy conversion.

Single-use plastics strongly contribute to plastic pollution, and less than 10% of plastic waste is recycled globally. Here, we present a selective mechanochemical protocol for converting post-consumer polyethylene terephthalate (PET) transparent bottles and coloured textile waste into the porous metal-organic framework (MOF) UiO-66 materials. We used time-resolved in situ (TRIS) synchrotron powder X-ray diffraction and Raman spectroscopy to monitor the depolymerization of PET during ball milling. To convert disodium terephthalate to UiO-66, we developed base and base-free synthetic routes that lead to fcu and hcp UiO-66 phases, respectively, including the first ever synthesis of hcp UiO-66 by mechanochemistry. Our results demonstrate the potential of mechanochemistry to selectively access fcu and hcp UiO-66 phases using post-consumer PET waste.

NMR is a powerful analytical technique that combines an exquisite qualitative power, related to the unicity of the spectra of each molecule in a mixture, with an intrinsic quantitativeness, related to the fact that the integral of each peak only depends on the number of nuclei (i.e., the amount of substance times the number of equivalent nuclei in the signal), regardless of the molecule. Signal integration is the most common approach in quantitative NMR but has several drawbacks (vide infra). An alternative is to use hard modeling of the peaks. In this paper, we present pyIHM, a Python package for the quantification of the components of NMR spectra through indirect hard modeling, and we discuss some numerical details of the implementation that make this approach robust and reliable.

The use of low-field nuclear magnetic resonance (NMR) spectroscopy enables real-time reaction monitoring in contrast to time-consuming gas chromatography or off-line high-field NMR measurements. In this study, NMR spectroscopy is demonstrated as a novel process analytical technology (PAT) tool in the downstream processing of polyhydroxyalkanoate (PHA) biopolymers. On-line NMR spectroscopy measurements were performed using a Spinsolve 43 Carbon Ultra instrument in a fully automated mode with a flow-assembly based on PTFE tubing. Single-scan NMR spectra were acquired for real-time monitoring of the extraction process of the PHA copolymer poly(hydroxybutyrate-co-hydroxyhexanoate) with 13.5 mol.% hydroxyhexanoate [P(HB-co-13.5 mol.%HHx)] from Ralstonia eutropha biomass using chloroform or acetone as PHA solvents at lyophilized cell loadings of 20-120 g L- 1. The reproducibility and reliability of low-field NMR spectroscopy was comparable to high-field NMR spectroscopy, with superior performance in terms of time. The correlation between the results of on-line monitoring using low-field NMR spectroscopy and off-line analysis using gas chromatography (GC) showed a correlation coefficient of >94 %. The versatility of low-field NMR spectroscopy for elucidating reaction kinetics, facilitating endpoint determination and accelerating extraction processes by maximizing solubility is highlighted as plateau values were reached within 6-10 min for chloroform and acetone, respectively. This novel low-field NMR spectroscopy application promotes a new monitoring approach for downstream PHA processing and supports process development and optimization.

An accurate measurement of the amount fraction of hydrogen in gas mixtures is mandatory for practical applications, requiring methods that are fast, continuous, robust, and cost-effective. This study compares the performance of Raman and benchtop NMR process spectroscopy for determining the hydrogen amount fraction in gas mixtures. A setup was designed to integrate both techniques, enabling measurements of the same sample. Tests were conducted with gravimetrically prepared gas mixtures of reference quality ranging from 1.20 cmol/mol to 85.83 cmol/mol of hydrogen. The results demonstrate that Raman spectroscopy provides superior performance, with a minimal root mean square error (RMSE) of 0.22 cmol/mol and excellent linearity. In contrast, benchtop NMR spectroscopy faced challenges, such as overlapping peaks and longer measurement times, resulting in a higher RMSE of 0.71 cmol/mol. Raman spectroscopy proves to be particularly well-suited for practical applications due to its high accuracy and linearity. Meanwhile, benchtop NMR spectroscopy holds potential for future enhancements through ongoing technological advances, such as higher magnetic field strengths. In summary, the results from our study indicate that Raman spectroscopy is already a serviceable method for precise hydrogen quantification, whereas benchtop NMR spectroscopy can be attributed potential for future applications.

A new azo-bridged compound with triazole moieties featuring trifluoromethyl groups was synthesized, exhibiting encouraging properties in the field of energetic materials. The new compound was synthesized in two steps from common starting materials using cyclocondensation, followed by oxidation reaction. The compound was characterized using nuclear magnetic resonance spectroscopy, mass spectrometry, infrared spectroscopy, and single-crystal X-ray diffraction. Impact and friction sensitivities were measured using BAM standard methods, and electrostatic discharge (ESD) sensitivity was measured using an ESD device from OZM Research. Heat of formation was calculated computationally using the CBS-4m method, density was determined by the pycnometric method, and energetic properties were calculated using Explo5 software.

The application of compact NMR instruments to hot flowing samples or exothermically reacting mixtures is limited by the temperature sensitivity of permanent magnets. Typically, such temperature effects directly influence the achievable magnetic field homogeneity and hence measurement quality. The internal-temperature control loop of the magnet and instruments is not designed for such temperature compensation. Passive insulation is restricted by the small dimensions within the magnet borehole. Here, we present a design approach for active heat shielding with the aim of variable temperature control of NMR samples for benchtop NMR instruments using a compressed airstream which is variable in flow and temperature. Based on the system identification and surface temperature measurements through thermography, a model predictive control was set up to minimise any disturbance effect on the permanent magnet from the probe or sample temperature. This methodology will facilitate the application of variable-temperature shielding and, therefore, extend the application of compact NMR instruments to flowing sample temperatures that differ from the magnet temperature.

Mechanochemistry is an environmentally friendly synthetic approach enabling the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous large-scale process. Meeting this challenge requires the use of in situ monitoring techniques for gaining insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real-time at the crystalline level.

Plastic pollution is the biggest environmental concern of our time. Breakdown products like micro- and nanoplastics inevitably enter the food chain and pose unprecedented health risks. In this scenario, bio -based and biodegradable plastic alternatives have been given a momentum aiming to bridge a transition towards a more sustainable future. Polyhydroxyalkanoates (PHAs) are one of the few thermoplastic polymers synthesized 100 % via biotechnological routes which fully biodegrade in common natural environments. Poly(hydroxybutyrate-co- hydroxyhexanoate) [P(HB-co-HHx)] is a PHA copolymer with great potential for the commodity polymers industry, as its mechanical properties can be tailored through fine-tuning of its molar HHx content. We have recently developed a strategy that enables for reliable tailoring of the monomer content of P(HB-co-HHx). Nevertheless, there is often a lack of comprehensive investigation of the material properties of PHAs to evaluate whether they actually mimic the functionalities of conventional plastics. We present a detailed study of P(HB-co-HHx) copolymers with low to moderate hydroxyhexanoate content to understand how the HHx monomer content influences the thermal and mechanical properties and to link those to their abiotic degradation. By increasing the HHx fractions in the range of 2 - 14 mol%, we impart an extension of the processing window and application range as the melting temperature (Tm) and glass temperature (Tg) of the copolymers decrease from Tm 165 degrees C to 126 degrees C, Tg 4 degrees C to -5.9 degrees C, accompanied by reduced crystallinity from 54 % to 20 %. Elongation at break was increased from 5.7 % up to 703 % at 14 mol% HHx content, confirming that the range examined was sufficiently large to obtain ductile and brittle copolymers, while tensile strength was maintained throughout the studied range. Finally, accelerated abiotic degradation was shown to be slowed down with an increasing HHx fraction decreasing from 70 % to 55 % in 12 h.

Ratiometric green–red fluorescent nanosensors for fluorometrically monitoring pH in the acidic range were designed from 80 nm-sized polystyrene (PS) and silica (SiO 2 ) nanoparticles (NPs), red emissive reference dyes, and a green emissive naphthalimide pH probe, analytically and spectroscopically characterized, and compared regarding their sensing performance in aqueous dispersion and in cellular uptake studies. Preparation of these optical probes, which are excitable by 405 nm laser or LED light sources, involved the encapsulation of the pH-inert red-fluorescent dye Nile Red (NR) in the core of self-made carboxylated PSNPs by a simple swelling procedure and the fabrication of rhodamine B (RhB)-stained SiO 2 -NPs from a silane derivative of pH-insensitive RhB. Subsequently, the custom-made naphthalimide pH probe, that utilizes a protonation-controlled photoinduced electron transfer process, was covalently attached to the carboxylic acid groups at the surface of both types of NPs. Fluorescence microscopy studies with the molecular and nanoscale optical probes and A549 lung cancer cells confirmed the cellular uptake of all probes and their penetration into acidic cell compartments, i.e., the lysosomes, indicated by the switching ON of the green naphthalimide fluorescence. This underlines their suitability for intracellular pH sensing, with the SiO 2 -based nanosensor revealing the best performance regarding uptake speed and stability.

Hydrolysis of protein samples into amino acids facilitates the use of NMR spectroscopy for protein and peptide quantification. Different conditions have been tested for quantifying aromatic amino acids and proteins. The pH-dependent signal shifts in the aromatic region of amino acid samples were examined. A pH of 12 was found to minimize signal overlap of the four aromatic amino acids. Several aromatic compounds, such as terephthalic acid, sulfoisophthalic acid, and benzene tricarboxylic acid, were applied as internal standards. The quantification of amino acids from an amino acid standard was performed. Using the first two suggested internal standards, recovery was ~97% for histidine, phenylalanine, and tyrosine at a concentration of approximately 1 mM in solution. Acidic hydrolysis of a certified reference material (CRM) of bovine serum albumin (BSA) and subsequent quantification of Phe and Tyr yielded recoveries of 98% ± 2% and 88% ± 4%, respectively, at a protein concentration of 16 g/L or 250 µM.

Chemie Ingenieur TechnikVolume 94, Issue 9 p. 1318-1318 Vortrag Modular production involving benchtop NMR: Current application examples driven by digitalization M. Bornemann-Pfeiffer, Corresponding Author M. Bornemann-Pfeiffer martin.bornemann@bam.de Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, Germany Technical University Berlin, Chemical Engineering, Marchstr. 23, 10587 Berlin, GermanyCorrespondence: M. Bornemann-Pfeiffer (martin.bornemann@bam.de), Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorS. Kern, S. Kern Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, Germany S-Pact GmbH, Burtscheider Str. 1, 52064 Aachen, GermanySearch for more papers by this authorL. Wander, L. Wander Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorK. Meyer, K. Meyer Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Maiwald, M. Maiwald Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this author M. Bornemann-Pfeiffer, Corresponding Author M. Bornemann-Pfeiffer martin.bornemann@bam.de Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, Germany Technical University Berlin, Chemical Engineering, Marchstr. 23, 10587 Berlin, GermanyCorrespondence: M. Bornemann-Pfeiffer (martin.bornemann@bam.de), Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorS. Kern, S. Kern Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, Germany S-Pact GmbH, Burtscheider Str. 1, 52064 Aachen, GermanySearch for more papers by this authorL. Wander, L. Wander Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorK. Meyer, K. Meyer Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Maiwald, M. Maiwald Bundesanstalt für Materialforschung und -prüfung (BAM), 1.4 Prozessanalytik, Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this author First published: 25 August 2022 https://doi.org/10.1002/cite.202255268AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume94, Issue9Special Issue: (Bio)Process Engineering – a Key to Sustainable Development: ProcessNet and DECHEMA-BioTechNet Jahrestagungen 2022 together with 13th ESBES SymposiumSeptember 2022Pages 1318-1318 RelatedInformation

Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, EDS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids were used to introduce functional groups for further conjugations. The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower non-specific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). A binding capacity of 1.8 mg IgG per gram of corundum powder was achieved. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application.

Chemie Ingenieur TechnikVolume 94, Issue 9 p. 1362-1362 Poster Compact NMR Spectroscopy in the Field: A Versatile PAT Tool for Production of Specialty Chemicals K. Meyer, Corresponding Author K. Meyer klas.meyer@bam.de Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanyCorrespondence: K. Meyer (klas.meyer@bam.de), Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorS. Kern, S. Kern S-PACT GmbH, Burtscheider Str. 1, 52064 Aachen, GermanySearch for more papers by this authorS. Guhl, S. Guhl Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Bornemann-Pfeiffer, M. Bornemann-Pfeiffer Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorL. Wander, L. Wander Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Maiwald, M. Maiwald Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this author K. Meyer, Corresponding Author K. Meyer klas.meyer@bam.de Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanyCorrespondence: K. Meyer (klas.meyer@bam.de), Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorS. Kern, S. Kern S-PACT GmbH, Burtscheider Str. 1, 52064 Aachen, GermanySearch for more papers by this authorS. Guhl, S. Guhl Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Bornemann-Pfeiffer, M. Bornemann-Pfeiffer Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorL. Wander, L. Wander Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this authorM. Maiwald, M. Maiwald Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, GermanySearch for more papers by this author First published: 25 August 2022 https://doi.org/10.1002/cite.202255362AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume94, Issue9Special Issue: (Bio)Process Engineering – a Key to Sustainable Development: ProcessNet and DECHEMA-BioTechNet Jahrestagungen 2022 together with 13th ESBES SymposiumSeptember 2022Pages 1362-1362 RelatedInformation

Mass Spectrometry (MS) and Nuclear Magnetic Resonance Spectroscopy (NMR) are critical components of every industrial chemical process as they provide information on the concentrations of individual compounds and by-products. These processes are carried out manually and by a specialist, which takes a substantial amount of time and prevents their utilization for real-time closed-loop process control. This paper presents recent advances from two projects that use Artificial Neural Networks (ANNs) to address the challenges of automation and performance-efficient realizations of MS and NMR. In the first part, a complete toolchain has been developed to develop simulated spectra and train ANNs to identify compounds in MS. In the second part, a limited number of experimental NMR spectra have been augmented by simulated spectra to train an ANN with better prediction performance and speed than state-of-the-art analysis. These results suggest that, in the context of the digital transformation of the process industry, we are now on the threshold of a possible strongly simplified use of MS and MRS and the accompanying data evaluation by machine-supported procedures, and can utilize both methods much wider for reaction and process monitoring or quality control.

Ergot alkaloids are mycotoxins formed by fungi of the Claviceps genus, which are some of the most common contaminants of food and feed worldwide. These toxins are a structurally heterogeneous group of compounds, sharing an ergoline backbone. Six structures and their corresponding stereoisomers are typically quantified by either HPLC-FLD or HPLC-MS/MS and the values subsequently summed up to determine the total ergot alkaloid content. For the development of a screening method targeting all ergot alkaloids simultaneously, the alkaloids need to be transferred to one homogeneous structure: a lysergic acid derivative. In this study, two promising cleaving methods—acidic esterification and hydrazinolysis—are compared, using dihydroergocristine as a model compound. While the acidic esterification proved to be unsuitable, due to long reaction times and oxidation sensitivity, hydrazinolysis reached a quantitative yield in 40‒60 min. Parallel workup of several samples is possible. An increasing effect on the reaction rate by the addition of ammonium iodide was demonstrated. Application of hydrazinolysis to a major ergot alkaloid mix solution showed that all ergopeptines were cleaved, but ergometrine/-inine was barely affected. Still, hydrazinolysis is a suitable tool for the development of a sum parameter screening method for ergot alkaloids in food and feed.

A big problem with the chemistry literature is that it is not standardized with respect to precise operational parameters, and real time corrections are hard to make without expert knowledge. This lack of context means difficult reproducibility because many steps are ambiguous, and hence depend on tacit knowledge. Here we present the integration of online NMR into an automated chemical synthesis machine (CSM aka. "Chemputer" which is capable of small-molecule synthesis using a universal programming language) to allow automated analysis and adjustment of reactions on the fly. The system was validated and benchmarked by using Grignard reactions which were chosen due to their importance in synthesis. The system was monitored in real time using online-NMR, and spectra were measured continuously during the reactions. This shows that the synthesis being done in the Chemputer can be dynamically controlled in response to feedback optimizing the reaction conditions according to the user requirements.

The digitization of chemistry requires that synthesis procedures can be written and optimized in a chemical programming language to perform reliable "chemputation" for the synthesis on the "chemputer" robot, a universal synthesis machine. The cover image shows how a universal chemical synthesis engine equipped with an NMR sensor can be used to optimize reactions producing the automated synthesis procedure as an optimized process code ensuring that the chemputation can be improved and is reliable. Details are reported by Leroy Cronin, Franziska Emmerling et al. in their Communication on page 23202.