We describe the discovery of a series of potent, selective, and orally bioavailable bis-acyl hydrazide inhibitors targeting the PRMT5·MTA complex for the treatment of MTAP-deleted cancers. Key to this discovery was the identification of major metabolite M1, resulting from N-demethylation of lead inhibitor compound 12, as a potent hERG inhibitor. Leveraging the kinetic isotope effect, we generated methyl-d3 analog 16 which reduced the formation of M1 in vivo, resulting in acceptable safety margins and an improved pharmacokinetic profile. Our data suggest this strategy could be employed more broadly to reduce undesirable metabolism of methylated amines.

Introduction Bismuth-based perovskite solar cells are gaining attention as a promising alternative to lead-based solar cells due to environmental concerns. However, the c-axis growth preferred, electrotonic anisotropic and deep-defect nature of Bi-based perovskite materials presents significant challenges in depositing non-(006) orientation and reducing defect density [1]. We have proposed a surface reaction model to better understand the chemical vapor deposition (CVD) growth kinetics of the thin films, as shown in Fig. 1 [2]. Although the bismuth-based perovskite film (CH3NH3)3Bi2I9 (MABI) has been widely studied at a processing temperature of 160 °C, its undesired orientation and high defect density have limited its power conversion efficiency. Fine control of the deposition temperature and rate is crucial to improving thin-film quality. This work aims to investigate the thin film crystal orientation and defect density at unconventional preparation temperature. Experimental Fig. 2. shows the schematic of MABI production by CVD. HI gas was supplied to the reactor tube (SUS316), diluted with helium gas through inlet 1, and reacted with bismuth oxide to generate BiI3 as equation (1) expressed.The remaining HI gas and BiI3 vapor were diluted again with helium gas, added up from inlet 2. Following this, it reacted with helium-diluted methylamine (MA) from inlet 3 at the junction to form methylammonium iodide (MAI) and flowed downstream to the deposition section. The reaction at the mixing junction was expected to be expressed by equations (2) and (3).TiO2 coated FTO substrates (6 mm × 20 mm × 1.1 mm, Asteratec) were placed in the deposition section and deposited at 1.33×103 Pa. MABI was confirmed by the X-ray diffraction (XRD) patterns (Rigaku, UltimaIV). Results and Discussion The XRD patterns of the resulting thin films were compared with theoretical patterns to verify the product. SEM images obtained at 160 °C, 180 °C, and 200 °C are presented in Fig. 3. As the deposition temperature increased, the crystal grain size grew, and higher temperatures promoted the grain boundary merging, forming a more compact thin film.We examined the grain orientations and the crystallite sizes for planes (100), (101), (103), and (006). As shown in Fig. 4, at 200 °C the deposition rate had little effect on the orientation to selected planes, although the texture coefficients (TCs) of the (100) and (101) planes increased slightly, suggesting that most crystal planes were favored at this temperature. Consequently, no single orientation dominated the growth competition, resulting in weakened TCs. In contrast, the (100) plane showed an elevated TC at 160 °C with a low deposition rate (Fig. 4a). The (101) plane, considered as the most compact plane in MABI with low surface energy, exhibited low TCs that decreased further as the deposition rate increased at 160 °C and 180 °C (Fig. 4b). Additionally, increasing the deposition rate favored growth of the (103) plane at 160 °C and 180 °C (Fig. 4c), suggesting that its high reactivity makes this facet in deposition rate limited. In Fig. 4d, the (006) plane displayed dominant TC values as the preferred growth direction for hexagonal crystals, although its dependency on precursor flux remains unclear.The grain sub-crystallite sizes (or crystallite sizes) were determined from the full width at half maximum (FWHM) of the XRD peaks using the Scherrer equation. Table 1 shows that increasing the temperature effectively enlarges the crystallite size and reduces defects within the grains. Higher temperatures facilitate faster precursor migration and promote crystal reconstruction to heal defects. The (101) plane was relatively insensitive to the deposition rate, while the (103) and (006) planes exhibited a slight increase in crystallite size with higher deposition rates, suggesting that unwanted species may form defects and compete with crystal growth. Conclusions Within the studied range, increasing the processing temperature is more effective in enlarging crystallite size than adjusting the deposition rate. However, the texture coefficients were weaken at 200 °C. The growth of the (100) plane was favored at 160 °C with low deposition rate, but it remained less competitive compared to other planes. While the texture coefficient of the (103) plane increased with deposition rate at 180 °C, which may serve as a compromise for depositing thin films that are not predominantly (006)-oriented. Acknowledgment This work was supported by JST SPRING, Grant Number JPMJSP2110. Reference [1] M. Wang, W. Wang, B. Ma et al., Nano-Micro Lett. 13, 62 (2021).[2] Z. Yang, K. Togami, M. Tanabe, S. Kimura and M. Kawase. “Reaction Rate Analysis of Chemical Vapor Deposited Bi-based Perovskite Thin Film”, presented at ISCRE 28, F54, Turku Finland, Jun. 17 – 19, 2024. Figure 1

Self-crosslinking poly(acrylamide-co-dimethylaminoethyl methacrylate) hydrogel with antibacterial property constructed via controlling the tertiary amine methylene radical formation as a potential tissue compensator in radiotherapy

Information about the optical properties of atmospheric molecular clusters is scarce as they are challenging to measure using current experimental techniques. Here we explore the absorption and Rayleigh scattering properties of acid-base molecular clusters using quantum chemical methods. We studied 127 small (acid)1-2(base)1-2 cluster systems, with the acids sulfuric acid (SA), methanesulfonic acid (MSA), nitric acid (NA), and formic acid (FA) in all combinations of the bases ammonia (AM), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA). To further explore the effect of cluster size on the optical properties, we studied the large (SA)n(AM)n cluster systems, with n up to 15 acid-base pairs. We calculated the polarizability tensors and the 10 lowest excitation energies at the CAM-B3LYP/aug-cc-pVTZ level of theory. We find that the isotropic polarizability is almost linearly dependent on the cluster size, with small variations depending on the cluster composition. The anisotropic polarizability is plateauing as a function of cluster size. The larger the cluster, the more dominant the isotropic contribution becomes in the calculation of the Rayleigh light scattering activity. As a consequence, the Rayleigh scattering activity will increase quadratically as a function of cluster size. We stress that future studies on the scattering properties should be evaluated as effective scattering, taking the concentrations of the clusters into account. We find that the clusters absorb infrared (IR) radiation in the atmospheric spectral window region but speculate that their lifetime is too short to be competitive with common greenhouse gases. Due to the lack of strong chromophores in the studied acid-base clusters, the ultraviolet-visual (UV-vis) absorption is found to occur in the deep UV. Hence, clusters with more organic content should be studied in the future. Finally, we outline several directions in which the field of studying the optical properties of clusters and aerosols using response theory methods could evolve.

Anlotinib (Focus V) is approved by the China Centre for Drug Evaluation in 2018 as a third-line treatment for patients with certain advanced cancers. This study aimed to develop a specific, fast, reliable, and sustainable ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) approach for estimating anlotinib (ANB) in the human liver microsomes (HLMs) matrix, with the application for the assessment of ANB metabolic stability. The validation processes for the UPLC-MS/MS system complied with US Food and Drug Administration regulations following bioanalytical method validation. The established approach was validated using the HLMs matrix over the range of 1.0 to 4000 ng mL-1 within 1 min. The precision (%RSD) and accuracy (%E) rates for intra-day and inter-day measurements ranged from -6.33% to 4.91% and -6.67% to 5.26%, respectively. The StarDrop software package involved P450 and Deductive Estimation of Risk from Existing Knowledge modules that were applied for assessing metabolic lability and characterizing ANB structural alarms, respectively. The invitro half-life (t½) was computed at 44.72 min, while the clearance intrinsic (Clint) of ANB was calculated at 18.13 mL min-1 kg-1. In silico evaluations suggest that minor structural alterations to the methyl group (62%), amine group (37%), and methoxy group (1%) in drug design may increase the ANB metabolic stability.

Aerosols are thelargest source of uncertainty in modern globalradiative forcing modeling. Atmospheric molecular clusters are importantintermediates in atmospheric new particle formation (NPF). The evaporationrate of clusters can be calculated using quantum chemical methods,with an exponential dependence on the free energy. Hence, for simulatingaccurate NPF rates, high-accuracy calculations are needed. We haveconstructed a versatile benchmark set of 218 conformers of atmosphericmolecular dimer clusters consisting of sulfuric acid (SA), formicacid (FA), nitric acid (NA), methanesulfonic acid (MSA), water (W),ammonia (AM), methylamine (MA), dimethylamine (DMA), trimethylamine(TMA), and ethylenediamine (EDA) molecules. Using this test set, webenchmark the local coupled cluster methods, DLPNO–CCSD­(T0) and LNO–CCSD­(T), using different basis sets and localitysettings, and test extrapolation procedures to the complete basisset (CBS), local approximation free (LAF), and complete PNO space(CPS) limits. The extrapolations are tested against the binding energiesof high-level CCSD­(F12*)­(T+)/cc-pVTZ-F12 reference calculations. Wefind that the LNO–CCSD­(T) methods offer a better accuracy-to-costratio for atmospheric molecular clusters than the usually employedDLPNO–CCSD­(T0) method. Furthermore, the CBS limitextrapolation using the aug-cc-pVTZ and aug-cc-pVQZ basis sets shouldbe readily attainable for the LNO–CCSD­(T) method on the usuallystudied cluster sizes (4–8 monomers). Simulating the new particleformation rate of the (SA)1–4(AM)1–4 and (SA)1–4(DMA)1–4 systemsusing the Atmospheric Cluster Dynamics Code, we find an increasedsensitivity to the locality settings for larger clusters, but thebasis set error is still the most dominant. Hence, simulated clusterformation rates would also benefit from doing LAF extrapolation. Finally,we illustrate the calculations of LNO–CCSD­(T)/CBS binding energiesof a large (SA)15(TMA)15 cluster (300 atoms).Hence, the application of LNO–CCSD­(T) allows for significantlymore accurate binding energies of much larger clusters than previouslypossible.

Recently, the atmospheric aerosol surface, which is reported to be quite acidic, is recognized as an important microreactive medium for atmospheric chemistry, profoundly impacting air quality and global climate. Nevertheless, the molecular-level understanding of the effect of surface-bound acids on atmospheric chemical reactions remains limited. Herein, the reactions between CO2 and NH3/amines at the air-water interface with organic acids are investigated using combined molecular dynamic simulations and quantum chemical calculations. The results show that the reactions of CO2-NH3/amines predominantly occur at the interface of water droplets since CO2/NH3/amines show a surface tendency. At the surface with formic acid (HCOOH), the barrier of C-N compound formation from the CO2-NH3 reaction catalyzed by HCOOH is calculated to be 6.8 kcal/mol, which can be easily overcome at ambient temperature and is significantly decreased in comparison to both gas phase and surface without organic acid. Furthermore, the HCOOH-mediated mechanism can also promote CO2 reactions with alkylamines (methylamine (MA) and dimethylamine (DMA)), as the nucleophilicity of the N-site in these amines is significantly stronger than that in NH3. Overall, the results highlight the significance of organic acid on the aerosol surface in efficient capture of gaseous CO2 and uncover the catalytic role of interfacial organic acid for assessing the potential contribution of gas-particle partitioning of pollutants to aerosol formation.

Due to the band offset, there is significant interfacial recombination between the tin-based perovskite and C60, which exhibits excellent electron transport capability. Here, we introduce a novel strategy leveraging surface self-passivation through controlled thermal decomposition to reduce the level of interfacial recombination substantially. By carefully tuning the annealing temperature (70 vs 100 °C) and organic cation composition (diethylammonium (DEA) vs methylamine (MA)), we achieve selective surface restructuring and SnI2 formation, effectively suppressing interfacial recombination at the perovskite/C60 interface. Detailed characterization using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of a stable SnI2 passivation layer. At the same time, photoluminescence and quasi-Fermi level splitting (QFLS) analyses revealed a notable reduction in the interfacial recombination losses. Consequently, this surface self-passivation strategy significantly improved the power conversion efficiency (PCE) by approximately 1%, primarily through an open-circuit voltage (VOC) increase of around 50 mV. Our findings underscore the critical role of interface engineering and thermal control in advancing the efficiency of Sn-based perovskite solar cells.

CsSnI3 perovskite is a thin-film semiconductor with high intrinsic conductivity for various device applications (thermoelectric, photovoltaics, etc.). Stoichiometric CsSnI3 has high-density defects and structural imperfections affecting device performance. In this work, we made an investigation on A-site cation engineering to evaluate the correlation between structural and transport parameters for effective operation in rectifying devices. Here, we analyzed CsSnI3 thin films modified with methylamine (MA), formamidine (FA), guanidine (GuA), and 5-ammonium valeric acid (AVA) cations, correlating structural parameters obtained by Rietveld refinement with their optoelectronic and diode characteristics. MA-, FA-, and GuA-substituted films exhibited low sheet resistance (∼450–2200 Ω/sq); however, strain-induced lattice distortions and accumulated defects in GuA-substituted films significantly hindered effective charge collection and increased recombination losses. AVA substitution formed low-conductivity 2D interlayers, increasing resistance (>105 Ω/sq) and altering transient response characteristics, yet provided minimal reverse switching losses (∼100 μW/cm2), beneficial for high-frequency applications. FA substitution emerged as optimal, balancing structural stability, conductivity, minimal defects, and relevant diode properties. The obtained results highlight that targeted lattice modifications strongly influence the practical performance of rectifying p–i–n diodes based on CsSnI3.

Abstract. When simulating new particle formation rates, collisions in the system are approximated as hard spheres without long-range interactions. This simplification may lead to an underestimation of the actual formation rate. In this study, we employ semi-empirical molecular dynamics (SEMD) at the GFN1-xTB level of theory to probe the sticking process of the monomers sulfuric acid (SA), methanesulfonic acid (MSA), nitric acid (NA), formic acid (FA), ammonia (AM), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) onto freshly nucleated particles (FNPs). The FNPs considered are (SA)10(AM)10, (SA)10(MA)10, (SA)10(DMA)10, and (SA)10(TMA)10. In general, we find that the hard-sphere kinetic approximation, which neglects long-range interactions, significantly underestimates the number of collisions leading to sticking. By calculating the sticking coefficient from SEMD simulations, we obtain enhancement factors of 2.3 and 1.5 for the SA + (SA)10(AM)10 and AM + (SA)10(AM)10 collisions, respectively. A comparison with OPLS (optimized potentials for liquid simulations) all-atom force field simulations shows similar enhancement factors of 2.4 and 1.6 for the SA + (SA)10(AM)10 and AM + (SA)10(AM)10 collisions, respectively. Compared to the force field simulations, SEMD exhibits a more isotropic sticking behavior, with the probability remaining near unity for small offsets before rapidly dropping to 0 % beyond a certain offset. In contrast, the force field simulations show a more gradual decline in sticking probability due to certain orientations still leading to sticking. The largest discrepancy between the two methods occurs at lower collision velocities – below 200 m s−1 for SA and below 400 m s−1 for AM – where force field simulations, even for head-on collisions, predict low or zero sticking probability. This has previously been attributed to periodic repulsions between the rotating collision partners caused by fluctuations in their charge distributions. In contrast, SEMD simulations do not exhibit this behavior. Since these low velocities are not significantly populated in our simulations, both methods yield similar enhancement factors. However, for systems with larger effective masses, where such velocities are more prevalent, we would expect the two methods to diverge.

Uterotibb is one of the potent Unani medicines that offers a natural solution to various human health issues. The present investigation explores the active phytochemical constituents of Unani medicine Uterotibb using GC-MS analysis. This study further evaluated the antioxidant potential and antimicrobial activity against a panel of human pathogens such as Staphylococcus aureus, Bacillus Subtilis, E. coli, and Klebsiella pneumonia. GC-MS studies revealed the presence of 388 phytochemical compounds in the alkali aqueous extract of Uterotibb. The main active biomolecules were stigmast-5– en-3-0l, and oleate (2.84%). Cyclotrisiloxane, hexamethyl (1.74%). 1,2,5-oxadiazole-3-carboxamide4-amino-N-(2-methoxyethyl)-(1.75%). Arsenous acid (1.48%). Pentane,1,1-thiobis (1.46%). 7,7,9,9,11,11-hexamethyl-3,6,8,10,12,15hexaoxa-7,9,11-trisilaheptadecane (1.46%). 4-(1,1dimethylpropyl-phenol, trimethylsilyl ether (1.43%). 1,2-bis (trimethyl silyl) benzene (1.36%). Adamantane methyl amine (1.32%). 1,4-benzenediole,2,5-bis(1,1 dimethyl ethyl)-(1.29%). 2-chloro aniline-5-sulphonic acid (1.28%); Acetic Acid, nitro-, methyl ester (1.24%) and Caprolactone oxime, (NB)-O-[(diethylboryloxy) (ethyl)boryl] (1.21%). Notably, Uterotibb extract exhibited antimicrobial activity in a concentration-dependent manner, where the highest concentration of 5 mg/mL showed a maximum zone of growth inhibition of 14.95±0.35 mm against Staphylococcus aureus, and the lowest zone of inhibition was 13.26±0.88 mm against Bacillus subtilis at the same concentration. The lowest MIC value was exhibited at 2 mg/mL concentration against Staphylococcus aureus where the highest MIC value of 4 mg/mL was observed against K. Pneumoniae. Further, the antioxidant potential of the extract exhibited scavenging activity of 67.115 ± 0.05 and 73.67 ± 0.09 using DPPH and ABTS assays, respectively. Finally, GC-MS profiling and bioactivity studies of the present work validate Uterotibb's potential as a natural Unani medicine for human care.

Abstract The dehydrogenation mechanism of allyl alcohols catalyzed by the phosphine‐free Mn‐NNS complexes was computed (M06L‐GD3‐SCRF) and special attention was payed to the hemilability of sulfur‐arm ligand in the backbone. For the amido complex N(N)SMn(CO)2, the dehydrogenation of allyl alcohols undergoes more preferred the inner sphere mechanism via β‐hydride elimination compared to the outer sphere mechanism through bifunctional metal‐ligand cooperation. The computed kinetic isotope effect for both mechanisms for 1‐phenyl‐1‐allyl‐alcohol agrees with the kinetic study. For the methylated amine hydrido complex N(NMe)SMn(CO)2(H), only inner sphere mechanism via the de coordination of the hemilabile sulfur‐arm ligand is possible and H2 elimination (or metathesis) is the rate‐determining step. The experimentally reported higher activity of N(N)SMn(CO)2 compared to N(NMe)SMn(CO)2(H) was confirmed and rationalized.

ABSTRACTThe study investigated the contribution of hydroxymethanesulfonic acid (HMSA) to the formation of new particles in the presence of atmospheric bases such as ammonia (A), methylamine (MA), dimethylamine (DMA) and water (W) by DLPNO‐CCSD(T)/aug‐cc‐pVTZ//B3LYP‐D3/aug‐cc‐pVTZ(aug‐cc‐pV(T+d)Z for sulfur) level. Clusters containing HMSA were found easily to form six− or eight−membered ring structures via SO—H⋯O (HMSA donor), O—H⋯O/N (W donor), N—H⋯O/N (A/MA/DMA donor), and C—H⋯O (MA/DMA donor) hydrogen bonds. Due to the synergistic interaction between X and Y molecules, the stability of HMSA−X−Y trimers is thermodynamically more favorable than HMSA−X dimers, and proton transfer was found to be exothermic and barrier−free in HMSA−X−Y trimers. Moreover, the stability of HMSA−X−Y trimers increased with higher alkalinity of X and Y, leading to decreased evaporation rates. The study highlights the significance of HMSA−containing trimers in nucleation processes for new particle formation, suggesting their potential role as nucleation centers in atmospheric conditions.

BackgroundThis study assessed the long-term metabolic effects of prenatal nutrition in Nelore bulls through an integrated analysis of metabolome and microbiome data to elucidate the interconnected host-microbe metabolic pathways. To this end, a total of 126 cows were assigned to three supplementation strategies during pregnancy: NP (control)– only mineral supplementation; PP– protein-energy supplementation during the last trimester; and FP– protein-energy supplementation throughout pregnancy. At the end of the finishing phase, blood, fecal, and ruminal fluid samples were collected from 63 male offspring. The plasma underwent targeted metabolomics analysis, and fecal and ruminal fluid samples were used to perform 16 S rRNA gene sequencing. Metabolite and ASV (amplicon sequence variant) co-abundance networks were constructed for each treatment using the weighted gene correlation network analysis (WGCNA) framework. Significant modules (p ≤ 0.1) were selected for over-representation analyses to assess the metabolic pathways underlying the metabolome (MetaboAnalyst 6.0) and the microbiome (MicrobiomeProfiler). To explore the metabolome-metagenome interplay, correlation analyses between host metabolome and microbiome were performed. Additionally, a holistic integration of metabolic pathways was performed (MicrobiomeAnalyst 2.0).ResultsA total of one and two metabolite modules associated with the NP and FP were identified, respectively. Regarding fecal microbiome, three, one, and two modules for the NP, PP, and FP were identified, respectively. The rumen microbiome demonstrated two modules correlated with each of the groups under study. Metabolite and microbiome enrichment analyses revealed the main metabolic pathways associated with lipid and protein metabolism, and regulatory mechanisms. The correlation analyses performed between the host metabolome and fecal ASVs revealed 13 and 12 significant correlations for NP and FP, respectively. Regarding the rumen, 16 and 17 significant correlations were found for NP and FP, respectively. The NP holistic analysis was mainly associated with amino acid and methane metabolism. Glycerophospholipid and polyunsaturated fatty acid metabolism were over-represented in the FP group.ConclusionsPrenatal nutrition significantly affected the plasma metabolome, fecal microbiome, and ruminal fluid microbiome of Nelore bulls, providing insights into key pathways in protein, lipid, and methane metabolism. These findings offer novel discoveries about the molecular mechanisms underlying the effects of prenatal nutrition.Clinical trial numberNot applicable.

Purpose We found that during TFA-mediated cleavage of azide-containing peptides during solid-phase peptide synthesis a byproduct characterized by a difference of 12 mass units is formed. This study identifies this byproduct, provides a rationale for its formation and a solution for its inhibition. Method NMR and HRMS analyses as well as chemical synthesis is employed to identify the byproduct and probe the mechanism of its formation. Results Data is consistent with the conversion of azide to methylamine which occurs during peptide cleavage likely via a Schmidt rearrangement involving nucleophilic azide attack of t-butyl cations generated during side chain deprotection of Boc- and t-butyl ether groups. Conclusion Installing azide-containing residues using the newly reported 2-(trimethylsilyl)ethoxycarbonyl (Teoc)-protected compound 3a proved effective at significantly thwarting the formation of methyl amine byproduct.

Pink Pigmented Facultative Methylotrophs (PPFMs) belong to a diverse group of methylotrophic bacteria predominantly in the genus Methylobacterium, and are known for their beneficial interactions with plants. They can use single-carbon compounds, such as methanol, formate, formaldehyde and methyl amines as well as various multi-carbon substrates as sources of carbon and energy. PPFMs are characterized by their distinctive pink pigmentation and are commonly found in the phyllosphere, where they play a major role in promoting plant growth through various mechanisms; These mechanisms include the production of phytohormones, enhancing nutrient acquisition, mitigating abiotic stresses and providing biocontrol of phytopathogens. Due to their eco-friendly nature PPFMs are viewed as promising alternatives to synthetic fertilizers and pesticides in green agriculture. Furthermore, the ecological significance of PPFMs extends beyond their direct interactions with host plants. They also contribute to the resilience of ecosystems by participating in the cycling of nutrients in the environment. As the importance of the plant microbiome in agriculture becomes more recognized, the potential of PPFMs to support sustainable farming practices and contribute to environmental health is increasingly evident. This underscores their relevance in addressing global agricultural challenges.

Abstract. Sulfuric acid, ammonia, and amines are believed to be key contributors to the initial steps in new particle formation in the atmosphere. However, other compounds such as organic compounds or nitric acid are believed to be important for further growth at larger sizes. In this study, we investigate the potential uptake of first-generation oxidation products from α-pinene (pinic and pinonic acid) and isoprene (trans-β-IEPOX, β4-ISPOOH, and β1-ISOPOOH), a potential highly oxidised molecule (HOM), formic acid, and nitric acid. The uptake is probed onto (SA)10(base)10 freshly nucleated particles (FNPs), where SA denotes sulfuric acid, and the bases are ammonia (AM), methylamine (MA), dimethylamine (DMA), or trimethylamine (TMA). The addition free energies were calculated at the ωB97X-D3BJ/6-311++G(3df,3pd)//B97-3c level of theory. We find favourable addition free energies of −8 to −10 kcal mol−1 for the HOM, pinic acid, and pinonic acid on the less sterically hindered (SA)10(AM)10 and (SA)10(MA)10 FNPs. This suggests that isoprene oxidation products do not contribute to the early growth of FNPs, but the α-pinene products do, in accordance with their expected volatilities. Calculating the second addition of a pinic acid molecule or pinonic acid molecule on the (SA)10(AM)10 FNPs, we find that pinic acid maintains its large addition free energy decrease due to its two carboxylic acid groups interacting with the other monomer, as well as the FNP. The pinonic-acid addition free energy drops to −3.9 kcal mol−1 due to the weak interactions between the FNP and its carbonyl group and the lack of monomer–monomer interactions. Calculating the addition free energy under realistic atmospheric conditions, we find that the FNPs studied are too small (1.4 nm) to support the growth of the studied uptake monomers. We find that the accretion product pinyl diaterpenylic ester (PDPE; C17H26O8) yields an addition free energy value of −17.1 kcal mol−1. This suggests that PDPE can overcome the strong Kelvin effect of a 1.4 nm FNP and lead to spontaneous uptake under ambient conditions.

The stability constants of proton transfer complex formation of N-phenyl thio barbituric acid (NPTBA). N-o-tolyl thio barbituric acid (NOTTBA). N-m-tolyl thio barbituric acid (NMTTBA) and N-p-tolyl-thio barbituric acid [NPTTBA] with methyl amine dimethyl amine, trimethly amine, ethyl amine, diethyl amine, triethyl amine, n-butyl amine, di-n-butyl amine and tri-n-butyl amine have been determined spectroscopically in 95%(v/v) ethanol-water mixtures. The stabilities of the proton transfer complexes of these N-substituted thio barbituric acids with amine bases have been correlated with the base strength of amines. The composition of proton transfer complexes is determined in solution potentiometrically and spectrophotometrically and substantiated by the element analysis and IR spectra of the isolated complexes. The correlation between mode of enolization in N-substituted thio barbituric acids and the structure of the proton transfer complex is discussed.

The development of advanced functional soft materials for applications in preserving food quality and detecting spoilage is in focus today. While various smart food packaging options are available, there are still challenges to be addressed due to several limitations of current food quality sensors, such as a lack of multifunctionality, use of potentially harmful synthetic sensing molecules or short shelf life of natural analogues. Herein, we present a dual-functional hydrogel-polymersome composite (HPC) system that integrates two complementary sensing functionalities into a single platform. As a model for dual-functionality, we successfully incorporated dye-loaded polymersomes into a poly(N-isopropylacrylamide)-based hydrogel. This approach enables temperature-triggered cargo release, while the encapsulated dyes serve as pH-reporting molecules for monitoring food freshness. The first functionality was demonstrated by hydrogel shrinkage and subsequent release of dye upon increasing the temperature from 25 °C to 40 °C. The second functionality was probed by decreasing the pH to 6.2 or exposure to methylamine (MA), a representative volatile amine, which shifted the local pH to basic values. The HPCs remained stable under hydrated conditions, and their dual-functionality was proved using fluorescence spectroscopy and light scattering. Our system exhibited a detection limit of 1 mM MA-2.5 times lower than the threshold classified as acutely toxic by the Centers for Disease Control and Prevention-highlighting its relevance for spoilage detection. These findings demonstrate that combining functional polymersomes with stimuli-responsive hydrogels offers a promising approach for developing multifunctional, compartmentalized composite sensors suitable for integration into food packaging to efficiently monitor its freshness.

Abstract Volatile amines in breath act as biomarkers for kidney and liver diseases. Monitoring these amines, especially when present as a mixture, provides insights into the metabolic state of the body. This study focuses on differentiating volatile amines by systematically modulating the conductivity and sensitivity of WSe2/Multiwalled Carbon Nanotubes composite‐based sensors. The fabricated chemiresistive sensor array demonstrates high selectivity, sensitivity (7.67% ppm−1), fast response and recovery kinetics (32 s/137 s), and accurate discrimination among target amines, even in the presence of other VOCs (volatile organic compounds). The sensor array operates at room temperature and achieves a theoretical limit of detection (LOD) of 387 ppt, 206, 157, and 202 ppb for triethylamine (TEA), dimethylamine (DMA), methylamine (MA), and ammonia (NH3), respectively, demonstrating its suitability for breath sensing and diagnostics. Machine learning (ML) analysis is employed to differentiate between the volatile amines and mixtures with 94% accuracy. The ability to detect these amines at such low ppt and ppb levels underscores the potential of this e‐nose technology for high‐performance applications in early‐stage disease diagnostics.