Chemical Degradation Research Articles

Digital Twin‐Assisted Degradation Diagnosis and Quantification of NMC Battery Aging Effects During Fast Charging

AbstractA comprehensive understanding of aging mechanisms and degradation diagnosis under fast charging in battery electric vehicles is needed. However, there is a lack of tools to capture both macroscopic and microscopic parameters, still focusing on experiment results analysis. To get a comprehensive degradation insight for improved service life, this study explores aging mechanisms in LiNi0.5Co0.2Mn0.3O2 graphite batteries under different fast charging conditions (0.6C to 2C) for up to 1000 equivalent full cycles (EFCs). An improved digital twin is used to quantify aging effects and identify aging modes, combining electrochemical techniques with post‐mortem analysis for assessing chemical and structural degradation. After 1000 EFCs, the dominant aging modes are loss of active material (LAM) in the negative electrode and loss of lithium inventory (LLI), surpassing LAM in the positive electrode. Compared to constant current charging, multistep fast charging effectively mitigates Li plating effects and graphite cracking, resulting in a 13% reduction in LAM. Additionally, optimizing the depth of discharge leads to at least 4% reductions in LLI and 16% in LAMpos. This study proves the electrochemical digital twin's potential for quantifying aging effects and serves as a basis for future physics‐informed machine learning to predict aging behavior and modes.

Stability of Protein Pharmaceuticals: Recent Advances.

There have been significant advances in the formulation and stabilization of proteins in the liquid state over the past years since our previous review. Our mechanistic understanding of protein-excipient interactions has increased, allowing one to develop formulations in a more rational fashion. The field has moved towards more complex and challenging formulations, such as high concentration formulations to allow for subcutaneous administration and co-formulation. While much of the published work has focused on mAbs, the principles appear to apply to any therapeutic protein, although mAbs clearly have some distinctive features. In this review, we first discuss chemical degradation reactions. This is followed by a section on physical instability issues. Then, more specific topics are addressed: instability induced by interactions with interfaces, predictive methods for physical stability and interplay between chemical and physical instability. The final parts are devoted to discussions how all the above impacts (co-)formulation strategies, in particular for high protein concentration solutions.'

Geministatins: new depside antibiotics from the fungus Austroacremonium gemini

Two new depside antibiotics, geministatins A (1) and B (2), were isolated from the fungus Austroacremonium gemini MST-FP2131 (Sordariomycetes, Ascomycota), which was recovered from rotting wood in the wet tropics of northern Australia. The structures of the geministatins were elucidated by detailed spectroscopic analysis, chemical degradation and comparison with literature values. Chemical degradation of 1 and 2 yielded three new analogues, geministatins C–E (3–5), as well as a previously reported compound dehydromerulinic acid A (6). Compounds 1, 2 and 6 exhibited antibacterial activity against the Gram-positive bacteria Bacillus subtilis (MIC 0.2–1.6 µg mL−1) and Staphylococcus aureus (MIC 0.78–6.3 µg mL−1), including methicillin-resistant S. aureus (MRSA), while 4 exhibited antifungal activity against the yeast Saccharomyces cerevisiae (MIC 13 µg mL−1).

Review of Sulfate Removal in Low Concentration Brine Solutions

Sulfate is a common ion present in natural water bodies at low concentrations and as effluent in different metallurgical processes. The discharge of sulfate in rivers and waterbodies can cause direct and indirect damage to the environment. Regulatory agencies have been increasing the constraints in sulfate content limit for discharge focused on human equity and environmental protection. A common practice is the precipitation of sulfate with lime, but the remaining solution still has ca. 1,500 mg L-1 of sulfate, which is not acceptable for disposal or reuse. This work describes the main routes for sulfate removal such as chemical precipitation, biological degradation, ion exchange, and separation through membranes and discusses the main advantages and issues of each approach. One of the main challenges is to scale up the tests and show the performances at the industrial level. The subject must be the focus of constant study to obtain relevant results so that usual technologies are replaced by more innovative, cheap and efficient methods.

Impact of membrane characteristics and chemical ageing on algal protein fouling behaviour of ultrafiltration membranes

Membrane characteristics can exacerbate the prevailing challenges associated with membrane fouling in industry. However, the combined impact of deliberate membrane modifications and the unavoidable effects of chemical ageing on fouling behaviour is still not well understood. In this study, three polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes with different pore size and surface roughness were selected and subject to chemical ageing with 5000 ppm sodium hypochlorite (NaOCl) at pH 10.5, selected to simulate accelerated ageing conditions. The impact of NaOCl on membrane characteristics was assessed for exposure times from 1.2 x 105 to 25.2 x 105 ppm·h using scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, contact angle, and clean water resistance analysis. The fouling behaviour of each pristine and aged membrane was compared using 10 mg C·L−1 dissolved organic carbon algal protein feed containing 18 % biopolymeric compounds. The membrane with intermediate pore size presented lower overall filtration resistance compared to the membrane with smaller pores that developed rapid foulant cake layers. It also displayed less susceptibility to fouling via pore blocking mechanisms compared to membranes with larger pores where greater surface area available in pore walls leads to higher foulant adhesion.

Degradation study and diagnostic technology for Nafion membrane

Developing a fast diagnostic technology for membranes and accurately predicting the lifetime of membranes that can effectively reduce the manufacturing cost and overcome the technical barriers of proton exchange membrane fuel cell (PEMFC) lifetime. This paper focuses on developing an ex-situ accelerated chemical degradation method and investigating the impact of chemical degradation on membrane structure and fuel cell performance. The results show that voltage drop and hydrogen permeation current can detect the state online and predict the remaining lifetime of membrane electrode assembly (MEA). The aging rate is faster by three orders of magnitude than that of the published results by the established aging way. This study provides an additional decision for evaluating performance degradation and fuel cell system optimization, which could potentially lead to further improvements in the efficiency and durability of PEMFC systems.

Mechanothermal-milling-assisted removal of native passivation layer for refreshing lithium metal anodes

Securing the stable and reliable operation of high-energy lithium (Li) metal batteries (LMBs) is crucial for fundamental studies and practical applications. However, commercial Li metal anodes (LMAs) suffer from unreliable pre-passivation during vendor-specific manufacturing, which deteriorates their surface quality and compromises the reproducibility of novel post-treatments and new electrolytes. To avoid chemical and structural degradation originating from the initial LMA, this study presents a mechanothermal milling (MTM) method using heating blades to smoothly peel off the native passivation layer (NPL) on the LMA surface, thereby exposing near-fresh Li. Compared to as-received LMA, the LMA revitalized by the MTM process (MTM-Li) exhibited faster kinetics and less interfacial resistance, promoting spatially uniform, dendrite-less Li plating and pit-less Li stripping. The MTM-guided surface equalization of the LMA enables an accurate comparison of the electrolyte-derived SEI properties, which is essential for identifying an electrolyte that is genuinely compatible with freshly exposed Li. By combining it with highly stable electrolytes, MTM-Li can regulate the structural evolution of LMAs, effectively securing cycling stability for LMBs, even under stringent conditions.

Physio-chemical degradation of single-use plastics in natural weather and marine environments

Plastic pollution has reached concerning levels globally, with single-use plastic products (SUPs) comprising at least 50% of plastic waste. This study investigates the physical and chemical degradation of frequently used SUPs, including petroleum-based and bio-based plastics, in natural Northern European coastal weather and marine environments over a three-year period from 2019 to 2022. Addressing a critical knowledge gap, this research was based on a hypothesis that real-world ageing studies on SUPs would produce more accurate time- and process-lines for their transformation from macro-to microplastics than are available today based on the modeling studies more frequently used. The study employs optical examination, mechanical testing, Fourier Transform Infrared (FTIR) spectroscopy, and Gas Chromatography-Mass Spectrometry (GC-MS) to determine and relate physical and chemical changes with time. The results indicate that SUPs undergo significantly faster degradation in natural weather than predicted to date. Photooxidation emerges as the primary degradation pathway for all SUPs, emphasizing the role of light in plastic breakdown. Importantly, physical degradation to microplastics in natural environments is not always associated with significant chemical changes such as breaking chemical bonds. Black SUPs exhibit greater resistance to visible light and ultraviolet radiation than equivalent white and transparent examples. In marine environments, SUPs degrade measurably slower than in air, their degradation slowing with increasing distance from the water surface. Our findings indicate the urgent need for strategies that mitigate the impacts of photo-oxidation of SUPs. Such strategies may include a focus on the removal of post-use SUPs from pavements, roads, beaches, and water surfaces where photo-oxidation is faster than underwater and underground. Preferential use of black SUPs over white or transparent should also be considered.

Hyaluronic Acid/Chondroitin Sulfate-Based Dynamic Thiol-Aldehyde Addition Hydrogel: An Injectable, Self-Healing, On-Demand Dissolution Wound Dressing.

Frequent removal and reapplication of wound dressings can cause mechanical disruption to the healing process and significant physical discomfort for patients. In response to this challenge, a dynamic covalent hydrogel has been developed to advance wound care strategies. This system comprises aldehyde functionalized chondroitin sulfate (CS-CHO) and thiolated hyaluronic acid (HA-SH), with the distinct ability to form in situ via thiol-aldehyde addition and dissolve on-demand via the thiol-hemithioacetal exchange reaction. Although rarely reported, the dynamic covalent reaction of thiol-aldehyde addition holds great promise for the preparation of dynamic hydrogels due to its rapid reaction kinetics and easy reversible dissociation. The thiol-aldehyde addition chemistry provides the hydrogel system with highly desirable characteristics of rapid gelation (within seconds), self-healing, and on-demand dissolution (within 30 min). The mechanical and dissolution properties of the hydrogel can be easily tuned by utilizing CS-CHO materials of different aldehyde functional group contents. The chemical structure, rheology, self-healing, swelling profile, degradation rate, and cell biocompatibility of the hydrogels are characterized. The hydrogel possesses excellent biocompatibility and proves to be significant in promoting cell proliferation in vitro when compared to a commercial hydrogel (HyStem® Cell Culture Scaffold Kit). This study introduces the simple fabrication of a new dynamic hydrogel system that can serve as an ideal platform for biomedical applications, particularly in wound care treatments as an on-demand dissolvable wound dressing.

Sustainable mortar reinforced with recycled glass fiber derived from pyrolysis of wind turbine blade waste

Pyrolysis technology has recently made significant progress in recycling millions of tons of wind turbine waste (WTB). Short fibers represent its main product (∼70 wt%), which needs further studies to explore its future applications. In this context, this work aims to the valorization of the recycled glass fiber (rGF) derived from pyrolysis of WTB (at 550 °C) in the production of rGF-reinforced mortar composite (rGF/M) for sustainable building applications. The research began by subjecting the derived rGF to sieving (rGFs), washing (rGFw), and oxidation (rGFo) pretreatments for purification and removing any impurities, organic residues, and char particles. Afterward, the chemical degradation of the treated rGF in a strong alkaline cement solution with pH = 14 was studied for up to 90 days. In parallel, the mortar composite samples were fabricated at 1 wt% of the treated rGF batches (rGFr, rGFw, and rGFo) to study the effect of different pretreatments on their microstructure, dispersion, compressive strength, flexural strength, and water absorption capabilities behavior after different curing periods (28 and 90 days). The results showed that rGFo (7.84%) showed a lower degradation rate versus rGFw (16.41%) and rGFr (30.76%). Meanwhile, the highest curing period (90 days) contributed to improving the properties of the mortar composites in general, especially in the case of using rGFo which led to improved compressive strength (15%) and reduced absorption coefficient (38%) and cumulative water content (32%) with a uniform distribution of short fibers in the matrices and a slight increase in flexural strength compared to control mortar sample (8.6 MPa). While rGFs provides better flexural strength (9.3 MPa) with a 12% improvement. Based on these results it can be concluded that rGFo has high potential in sustainable building materials with high competition with virgin glass fiber.

Rogersonins C-F, 9H-Imidazo[2,1-i]purine-Incorporating Adenine-Polyketide Hybrids from an Ophiocordyceps-Associated Clonostachys rogersoniana.

Rogersonins C-F (1-4), four unprecedented adenine-polyketide hybrids featuring a rare 9H-imidazo[2,1-i]purine (1,N6-ethenoadenine) moiety, were isolated from an Ophiocordyceps-associated fungus, Clonostachys rogersoniana. Their structures were elucidated primarily by NMR experiments. The absolute configurations of 1-4 were assigned by a combination of the modified Mosher method, chemical degradation, electronic circular dichroism (ECD) calculations, and X-ray crystallography using Cu Kα radiation. Compound 3 downregulated the expression of PD-L1 protein in MDA-MB-231 and A549 cells, but did not show detectable effect on mRNA transcription of the PD-L1-encoding gene CD274.

Raman spectroscopy assisted by other analytical techniques to identify the most deteriorated carbonate‐stones to be consolidated in two monuments of Vitoria‐Gasteiz (Spain)

AbstractThis work describes the diagnostic study on the building materials, mostly carbonated, belonging to Santa Maria Cathedral and the Medieval Wall of Vitoria‐Gasteiz (Spain) with the aim to design the best conservation procedure. Both the studies of the lithology and the secondary compounds originated by environmental impacts on the Cathedral and on the Medieval Wall were carried out using laboratory instruments (μ‐Raman and micro‐energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and ion chromatography) on selected samples provided by the restorers. The systematic presence of black crusts in the stones of the Cathedral was related to the growth of microcrystalline structures of secondary compounds and biological patinas and the deposition of atmospheric particles from traffic and house heating systems. In fact, the main components identified were carbon, and iron compounds such as hematite, goethite, magnetite and lepidocrocite. In addition, the detection of lead compounds (lead‐rich hydroxyapatite) suggested in the same way the impact of the urban environment on the degradation and blackening of stone materials. The presence of sulfates, mainly gypsum, and, to a lesser extent, epsomite, anhydrite and bloedite could be caused by the sulfation of carbonated compounds as a result of an acid attack of atmospheric pollutants. The results on the secondary products of the Medieval Wall showed a greater presence of degradation by microorganisms compared to the Cathedral. This is probably related to the large garden surrounding the fortification, where the grass is in direct contact to the lower part of the structure. Markers of biological activity, such as carotenoid pigments and calcium oxalate weddellite, together with other soluble oxalates were identified. The presence of ammonium nitrate, characterised by means ion chromatography, causes a chemical degradation of carbonate stone materials over time, due to the acidic nature of the ammonium ion. In both cases considered in this study, the presence of nitrate compounds, nitratine and potassium nitrate, was attributed to both natural factors (ammonium nitrate is coming from the decomposition of plant and animal excretions), and anthropogenic contamination.

The Effect of Implantoplasty on the Fatigue Behavior and Corrosion Resistance in Titanium Dental Implants.

Implantoplasty is a technique increasingly used to remove the biofilm that causes peri-implantitis on dental implants. This technique of mechanization of the titanium surface makes it possible to eliminate bacterial colonies, but it can generate variations in the properties of the implant. These variations, especially those in fatigue resistance and electrochemical corrosion behavior, have not been studied much. In this work, fatigue tests were performed on 60 dental implants without implantoplasty, namely 30 in air and 30 in Hank's solution at 37 °C, and 60 with implatoplasty, namely 30 in air and 30 in Hank's solution at 37 °C, using triaxial tension-compression and torsion stresses simulating human chewing. Mechanical tests were performed with a Bionix servo-hydraulic testing machine and fracture surfaces were studied by scanning electron microcopyElectrochemical corrosion tests were performed on 20 dental implants to determine the corrosion potentials and corrosion intensity for control implants and implantoplasty implants. Studies of titanium ion release to the physiological medium were carried out for each type of dental implants by Inductively Coupled-Plasma Mass Spectrometry at different immersion times at 37 °C. The results show a loss of fatigue caused by the implantoplasty of 30%, observing that the nucleation points of the cracks are in the areas of high deformation in the areas of the implant neck where the mechanization produced in the treatment of the implantoplasty causes an exaltation of fatigue cracks. It has been observed that tests performed in Hank's solution reduce the fatigue life due to the incorporation of hydrogen in the titanium causing the formation of hydrides that embrittle the dental implant. Likewise, the implantoplasty causes a reduction of the corrosion resistance with some pitting on the machined surface. Ion release analyses are slightly higher in the implantoplasted samples but do not show statistically significant differences. It has been observed that the physiological environment reduces the fatigue life of the implants due to the penetration of hydrogen into the titanium forming titanium hydrides which embrittle the implant. These results should be taken into account by clinicians to determine the convenience of performing a treatment such as implantoplasty that reduces the mechanical behavior and increases the chemical degradation of the titanium dental implant.

Stereochemical Assignment of the 36-Membered Macrolide Ring Portion of Poecillastrin C.

Absolute configuration at 12 stereocenters in the 36-membered macrocyclic ring portion of poecillastrin C (1) was disclosed by chemical degradation and NMR analyses of 1, chemical synthesis, and molecular modeling techniques.

Exosomal noncoding RNAs: decoding their role in thyroid cancer progression.

Exosomes, as pivotal entities within the tumor microenvironment, orchestrate intercellular communication through the transfer of diverse molecules, among which non-coding RNAs (ncRNAs) such as miRNAs, lncRNAs, and circRNAs play a crucial role. These ncRNAs, endowed with regulatory functions, are selectively incorporated into exosomes. Emerging evidence underscores the significance of exosomal ncRNAs in modulating key oncogenic processes in thyroid cancer (TC), including proliferation, metastasis, epithelial-mesenchymal transition (EMT), angiogenesis, and immunoediting. The unique composition of exosomes shields their cargo from enzymatic and chemical degradation, ensuring their integrity and facilitating their specific expression in plasma. This positions exosomal ncRNAs as promising candidates for novel diagnostic and prognostic biomarkers in TC. Moreover, the potential of exosomes in the therapeutic landscape of TC is increasingly recognized. This review aims to elucidate the intricate relationship between exosomal ncRNAs and TC, fostering a deeper comprehension of their mechanistic involvement. By doing so, it endeavors to propel forward the exploration of exosomal ncRNAs in TC, ultimately paving the way for innovative diagnostic and therapeutic strategies predicated on exosomes and their ncRNA content.

Simulation of fuel cell membrane durability under vehicle operation

In this work, a statistical fuel cell chemo-mechanical membrane degradation model is developed based on the ionomer fibrillar morphology as a framework for use-level membrane durability prediction for fuel cell electric vehicles. The mechanical and chemical degradation modes are separately calibrated with pressure differential-accelerated mechanical stress tests and accelerated membrane durability tests, respectively. Finite element simulations are used to estimate the initial stress distribution across the membrane, while the genetic algorithm with the least squares method is employed to calibrate the model parameters with experimental results, thus reaching a good agreement. Next, the validated model is utilized for a case study of fuel cell electric transit bus operation in the city of Victoria, B.C., Canada. The initial cell voltage profile is obtained using a dynamic fuel cell power system model applied to the transit bus drive cycle recorded during real-world operation. According to the model predictions, reducing the stack nominal power from 396 to 132 kW results in a 148% membrane lifetime enhancement, whereas decreasing the cell temperature from 90 to 70°C results in an 11-fold increase in the membrane lifetime under simulated transit bus operation, thereby exceeding the 25,000-h lifetime target for this application.

Diffusion and Chemical Degradation of Vitamin B6 in Chickpeas (Cicer arietinum L.) during Hydrothermal Treatments: A Kinetic Approach.

Chickpeas are more sustainable than other food systems and have high a nutritional value, especially regarding their vitamin composition. One of the main vitamins in chickpeas is vitamin B6, which is very important for several human metabolic functions. Since chickpeas are consumed after cooking, our goal was to better understand the role of leaching (diffusion) and thermal degradation of vitamin B6 in chickpeas during hydrothermal processing. Kinetics were conducted at four temperatures, ranging from 25 to 85 °C, carried out for 4 h in an excess of water for the diffusion kinetics, or in hermetic bags for the thermal degradation kinetics. Thermal degradation was modeled according to a first-order reaction, and diffusion was modeled according to a modified version of Fick's second law. Diffusivity constants varied from 4.76 × 10-14 m2/s at 25 °C to 2.07 × 10-10 m2/s at 85 °C; the temperature had an impact on both the diffusivity constant and the residual vitamin B6. The kinetic constant ranged from 9.35 × 10-6 at 25 °C to 54.9 × 10-6 s-1 at 85 °C, with a lower impact of the temperature. In conclusion, vitamin B6 is relatively stable to heat degradation; loss is mainly due to diffusion, especially during shorter treatment times.

The effect of structural retrofitting and ventilation scenarios on the indoor microclimate of a historical library: The Necip Pasa Library, Turkiye

Structural retrofitting in buildings may result in changes in the indoor microclimate. Chemical, mechanical and biological deterioration can be seen in the cultural properties as a consequence of substrates and inappropriate microclimatic conditions such as high indoor temperature, relative humidity and fluctuations of them. The primary aim of the study is to evaluate the effect of the structural retrofitting, that the building underwent, on the chemical degradation risk of the library collection based on two different ventilation scenarios. One is natural ventilation which is an existing situation since the building is free-floating. The other one implementing a mechanical ventilation system into the building. To be able to compare the microclimate that affects the library collection pre- and post-retrofitting, two models are developed in DesginBuilder and simulated for both scenarios. According to the results of the post-retrofitting model, mechanical ventilation reduced the risk of chemical degradation by 38 %, while natural ventilation did not cause any effect. Natural ventilation gives a similar output in the pre-retrofitting model as in the post-retrofitting model. Mechanical ventilation in the pre-retrofitting model achieves a 33 % reduction in chemical degradation risk. Structural retrofitting only achieves a 1 % reduction in the chemical risk level for both ventilation scenarios. Thus, its effect on the indoor microclimate is insignificant. This study shows that creating simulation models effectively assesses potential risks pre-post-structural retrofitting or any retrofitting in historical buildings. Simulations reveal that mechanical ventilation is a better choice for decreasing chemical degradation risks for the library.

Assessing Photostability of mAb Formulations In Situ Using Light-Coupled NMR Spectroscopy.

Biopharmaceuticals, such as monoclonal antibodies (mAbs), need to maintain their chemical and physical stability in formulations throughout their lifecycle. It is known that exposure of mAbs to light, particularly UV, triggers chemical and physical degradation, which can be exacerbated by trace amounts of photosensitizers in the formulation. Although routine assessments of degradation following defined UV dosages are performed, there is a fundamental lack of understanding regarding the intermediates, transient reactive species, and radicals formed during illumination, as well as their lifetimes and immediate impact post-illumination. In this study, we used light-coupled NMR spectroscopy to monitor in situ live spectral changes in sealed samples during and after UV-A illumination of different formulations of four mAbs without added photosensitizers. We observed a complex evolution of spectra, reflecting the appearance within minutes of transient radicals during illumination and persisting for minutes to tens of minutes after the light was switched off. Both mAb and excipient signals were strongly affected by illumination, with some exhibiting fast irreversible photodegradation and others exhibiting partial recovery in the dark. These effects varied depending on the mAb and the presence of excipients, such as polysorbate 80 (PS80) and methionine. Complementary ex situ high-performance size-exclusion chromatography analysis of the same formulations post-UV exposure in the chamber revealed significant loss of purity, confirming formulation-dependent degradation. Both approaches suggested the presence of degradation processes initiated by light but continuing in the dark. Further studies on photoreaction intermediates and transient reactive species may help mitigate the impact of light on biopharmaceutical degradation.

DLP 3D Printing of Levoglucosenone-Based Monomers: Exploiting Thiol-ene Chemistry for Bio-Based Polymeric Resins.

Additive manufacturing (AM) is a well-established technique that allows for the development of complex geometries and structures with multiple applications. While considered a more environmentally-friendly method than traditional manufacturing, a significant challenge lies in the availability and ease of synthesis of bio-based alternative resins. In our endeavor to valorize biomass, this work proposes the synthesis of new α,ω-dienes derived from cellulose-derived levoglucosenone (LGO). These dienes are not only straightforward to synthesize but also offer a tunable synthesis approach. Specifically, LGO is first converted into diol precursor, which is subsequently esterified using various carboxylic acids (in this case, 3-butenoic, and 4-pentenoic acids) through a straightforward chemical pathway. The resulting monomers were then employed in UV-activated thiol-ene chemistry for digital light process (DLP). A comprehensive study of the UV-curing process was carried out by Design of Experiment (DoE) to evaluate the influence of light intensity and photoinitiator to find the optimal curing conditions. Subsequently, a thorough thermo-mechanical characterization highlighted the influence of the chemical structure on material properties. 3D printing was performed, enabling the fabrication of complex and self-stain structures with remarkable accuracy and precision. Lastly, a chemical degradation study revealed the potential for end-of-use recycling of the bio-based thermosets.