Acid Dimer Research Articles

Immunotoxicity of legacy and alternative per- and polyfluoroalkyl substances on zebrafish larvae

Hexafluoropropylene oxide dimer acid (HFPO-DA) and perfluoroethylcyclohexane sulfonate (PFECHS) are increasingly used as alternatives for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). However, their immunotoxicity and underlying molecular mechanisms remain poorly understood. Here, to assess immunotoxic effects, zebrafish embryos were exposed to environmentally relevant concentrations of PFOA, PFOS, HFPO-DA, and PFECHS for four days. Results revealed that all four per- and polyfluoroalkyl substances (PFAS) resulted in decreased heart rate and spontaneous movement, and induced oxidative stress in zebrafish larvae. Notably, HFPO-DA exhibited more severe oxidative stress than PFOA. Immune dysfunction was observed, characterized by elevated cytokine, complement factor, nitric oxide, and neutrophil content, along with a significant decrease in lysozyme content. Transcriptomic analysis revealed the activation of Toll-like receptor (TLR)/NOD-like receptor (NLR)/RIG-I-like receptor (RLR) and associated downstream genes, indicating their pivotal role in PFAS-induced immunomodulation. Molecular docking simulations demonstrated stable interactions between PFAS and key receptors (TLR2, NOD2 and RIG-I). Overall, HFPO-DA and PFECHS exhibited immunotoxic effects in zebrafish larvae similar to legacy PFAS, providing important information for understanding the toxic mode of action of these emerging alternatives.

Dimeric piperidinoquinoline alkaloids from the seeds of Chimonanthus salicifolius

A chemical investigation of extracts from the seeds of Chimonanthus salicifolius has led to the isolation of four new dimeric piperidinoquinoline alkaloids (1-4) and one new dimeric tryptamine alkaloid (5), along with five known alkaloids (6-10). Notably, compounds 3 and 4 were identified as two unusual dimeric piperidinoquinoline alkaloid-fatty acid hybrids. The new structures were elucidated using HRESIMS, NMR, and ECD spectroscopic techniques. The isolated compounds were subjected to cytotoxicity testing against HCT-116, HT-1080, and A549 cell lines. Compound 5 exhibited moderate activity against the HCT-116 and HT-1080 cell lines, with IC50 values of 44.59 ± 2.08 μM and 37.39 ± 2.31 μM, respectively.

Quantum Computational and Spectroscopic Investigation of 3-aminosalicylic Acid.

Quantum chemical calculations of3-aminosalicylic acid (3ASA) (monomer and dimer forms) have been performed using DFT and TD-DFT theories with B3LYP/6-311 G(d,p) functional level in the ground and excited states. Using TD-DFT with IEF-PCM model, the electronic spectra of 3ASA in solvents were computed and correlated with the experimental data. The theoretically calculated absorption and emission maxima of 3ASA (monomer) are observed in the range of 343- 347nm (S0 → S1 transition) and 429- 448nm (S1 → S0 transition), respectively. The natural bond orbital (NBO) analysis shows that charge transfer interaction contributes significantly to stabilize the molecular system. In the case of dimer, hydrogen bonding plays a dominant role in stabilizing the molecular framework. Additionally, the obtained nonlinear optical (NLO) properties: polarizability (13.86 × 10-24 e.s.u for monomer and 29.46 × 10-24 e.s.u. for dimer), first-order hyperpolarizability (4.21 × 10-30 e.s.u for monomer and 0.18 × 10-30 e.s.u for dimer) and second-order hyperpolarizability (7.44 × 10-36 e.s.u. for monomer and 14.32 × 10-36 e.s.u. for dimer) were found to be larger than those of standard organic compounds suggesting that 3ASA has a significant NLO character for optoelectronic applications. The NLO properties of dimer may differ from monomer due to dimerization. Further, the radiative lifetime, light harvesting efficiency and band gap energy were calculated, and proposed that 3ASA may be useful in photovoltaics and wide bandgap power devices. HIGHLIGHTS: • DFT and TD-DFT theories were employed to calculate structural and molecular properties of 3ASA (monomer and dimer) in ground and excited states. • HOMO-LUMO study shows monomer and dimer of 3ASA are good reactive. • NBO analysis reflects that charge transfer interactions stabilized the 3ASA molecule. • Electronic absorption/emission spectra in solvents calculated by IEF-PCM/TD-DFT method correlate with experimental results. • Calculated NLO parameters suggested that 3ASA is a potential candidate for NLO material.

Impacts of rapidly urbanizing watershed comprehensive management on per- and polyfluoroalkyl substances pollution: Based on PFAS “diversity” assessment

The impact of watershed comprehensive management (WCM) on per- and polyfluoroalkyl substances (PFAS) pollution in rapidly urbanizing areas remains unclear. In a typical rapidly urbanizing watershed of Shenzhen, China, we investigated temporal variations in contamination level, primary source and ecological risk of 50 emerging and legacy PFAS, as well as the replacement trends of emerging PFAS before and after WCM during a six-year sampling campaign. We found that large-scale dredging was a non-negligible factor in abnormally increased PFAS concentrations (6.43 %–456.16 %) during WCM through their release from river sediments. To better characterize the diverse and complex PFAS contamination, a novel pollution assessment method, PFAS “diversity”, was adopted based on a modified Shannon–Weiner diversity index and Pielou evenness index, reflecting numbers of PFAS detected and how evenly each PFAS contributed to the total PFAS concentrations at specific sampling sites. Importantly, we found that the Pielou evenness index can indicate and quantify abnormal pollution sources (especially point sources) along the river. The results revealed that WCM did not effectively reduce total PFAS concentrations and diversity in the rapidly urbanizing watershed but obviously improved point source pollution. Furthermore, 6:2 polyfluorinated phosphate diesters and hexafluoropropylene oxide dimer acid (GenX) that posed high ecological risks emerged and the number of sampling sites with high risk increased from 16 to 20 after WCM. Finally, we summarize several important issues related to PFAS contamination during WCM and propose specific countermeasures, such as adopting environmental dredging and reducing the proportion of ecological water replenished by wastewater treatment plant effluent for better control of PFAS pollution. Our study highlighted the limited effectiveness of WCM in mitigating PFAS pollution and the importance of emerging contaminant regulation in rapidly urbanizing watersheds during WCM.

Oleanolic Acid Dimers with Potential Application in Medicine-Design, Synthesis, Physico-Chemical Characteristics, Cytotoxic and Antioxidant Activity.

The present work aimed to obtain a set of oleanolic acid derivatives with a high level of cytotoxic and antioxidant activities and a low level of toxicity by applying an economical method. Oleanolic acid was alkylated with α,ω-dihalogenoalkane/α,ω-dihalogenoalkene to obtain 14 derivatives of dimer structure. All of the newly obtained compounds were subjected to QSAR computational analysis to evaluate the probability of the occurrence of different types of pharmacological activities depending on the structure of the analysed compound. All dimers were tested for cytotoxicity activity and antioxidant potential. The cytotoxicity was tested on the SKBR-3, SKOV-3, PC-3, and U-87 cancer cell lines with the application of the MTT assay. The HDF cell line was applied to evaluate the tested compounds' Selectivity Index. The antioxidant test was performed with a DPPH assay. Almost all triterpene dimers showed a high level of cytotoxic activity towards selected cancer cell lines, with an IC50 value below 10 µM. The synthesised derivatives of oleanolic acid exhibited varying degrees of antioxidant activity, surpassing that of the natural compound in several instances. Employing the DPPH assay, compounds 2a, 2b, and 2f emerged as promising candidates, demonstrating significantly higher Trolox equivalents and highlighting their potential for pharmaceutical and nutraceutical applications. Joining two oleanolic acid residues through their C-17 carboxyl group using α,ω-dihalogenoalkanes/α,ω-dihalogenoalkenes resulted in the synthesis of highly potent cytotoxic agents with favourable SIs and high levels of antioxidant activity.

Ferulic Acid Dimers as Potential Antiviral Agents by Inhibiting TMV Self-Assembly.

A series of ferulic acid dimers were designed, synthesized, and evaluated for anti-TMV activity. Biological assays demonstrated that compounds A6, E3, and E5 displayed excellent inactivating against tobacco mosaic virus (TMV) with EC50 values of 62.8, 94.4, and 85.2 μg mL-1, respectively, which were superior to that of ningnanmycin (108.1 μg mL-1). Microscale thermophoresis indicated that compounds A6, E3, and E5 showed strong binding capacity to TMV coat protein with binding affinity values of 1.862, 3.439, and 2.926 μM, respectively. Molecular docking and molecular dynamics simulation revealed that compound A6 could firmly bind to the TMV coat protein through hydrogen and hydrophobic bonds. Transmission electron microscopy and self-assembly experiments indicated that compound A6 obviously destroyed the integrity of the TMV particles and blocked the virus from infecting the host. This study revealed that A6 can be used as a promising leading structure for the development of antiviral agents by inhibiting TMV self-assembly.

Six-membered ring-reinforced flexible high-elongation block polyamide as strong and multi-reusable hot melt adhesive

This study presented the synthesis and characterization of polyester block polyamide hot melt adhesives (PPHMAs) with high adhesion strength and toughness. The PPHMAs demonstrated an adhesion strength of 11.04 MPa and toughness of 22.54 MJ·m−3, making them suitable for various substrates such as aluminum, copper, and stainless steel. The polyamide segments synthesized from dimer acid and 2-methyl-1,5-diaminopentane exhibited characteristics of softness and high elongation. Using isophorone diamine as a reinforcing agent introduced a stable six-membered ring structure, which enhanced the polymer's rigidity and strength, thus meeting the requirements for polyamide segments to function as the hard segments in block polymers. A trace amount of Tris (2-aminoethyl) amine provided the cross-linking sites which are similar to those in neuronal structures. The polyester segments, which were synthesized from poly (propylene glycol) diglycidyl ether and sebacic acid, served as the soft segments in the block polymer and were connected to the hard segment via amide bonds. The addition of the polyester segments enhanced the non-covalent molecular interactions within PPHMAs, leading to dynamic crosslinking properties. The adhesive maintained stable adhesion even after six cycles, which showcased its durability. Furthermore, the PPHMAs exhibited notable chemical resistance. It retained over 60 % adhesion strength after exposure to some chemical solvents including artificial seawater, 5 % NaOH solution, 5 % HCl solution, and DMSO for 24 h. These findings offered a novel approach to enhancing the adhesion strength and toughness of conventional thermoplastic hot melt adhesives.

Revealing the effects and mechanism of wine processing on Corni Fructus using chemical characterization integrated with multi-dimensional analyses

Corni fructus (CF) is always subjected to wine processing before prescription in clinic, for an enhancing effect of nourishing liver and kidney. While, the underlying mechanism for this processing on CF remains obscure. In this study, a sensitive ultra-high-performance liquid chromatography mass spectrometry (UPLC-MS/MS) method combined multi-dimensional analyses was established to monitor chemical characterizations of raw and wine-processed CF (WCF) and hence reveal the effects and underlying mechanism of wine processing on CF. As indicated, a total of 216 compounds were tentatively identified, including 98 structurally complex and variable home/hetero-polymers, that were composed of iridoid glucosides, gallic acids, caffeic acid and/or 5-HMF. Interestingly, 53 of these compounds probably characterized potential novel, including 35 iridoid glucosides or their dimers, 9 iridoid glucoside-gallic acid dimers, 7 gallic acids derivatives and 2 gallic acid-caffeic acid dimers, which provides ideas for natural product researchers. Meanwhile, the multi-dimensional analyses including principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA) and linear regression analysis were used to explore the differences between CF and WCF. The results showed that 23 compounds as chemical markers greatly contributing to the distinction were screened out, and 3 of which (7α/β-O-ethyl-morroniside, gallic acid and 5-HMF) in WCF indicated an increasing trend in intensities in relative to those in CF. Additionally, linear regression analysis showed that in WCF 53 compounds exhibited an increasing in intensities, while 132 ones did a decreasing trend, compared with those in CF. As our investigation demonstrated, acetal reaction of morroniside, ester hydrolysis in different organic acid derivatives as well as glycoside bond cleavage during wine processing probably resulted in the distinctions. The findings of this study provide a further understanding of the effect and mechanism of wine processing on CF.

Synthesis of Gemini-type imidazoline quaternary ammonium salt using by-product fatty acid as corrosion inhibitor for Q235 steel

Gemini-type imidazoline quaternary ammonium salt is a new type of environmentally friendly corrosion inhibitor has been widely used in engineering materials. However, most of them are hazardous/toxic compounds derived from petroleum-based products, which did harm to environment. In this work, an environmentally friendly Gemini-shaped imidazoline quaternary ammonium salt corrosion inhibitor (G211) was synthesized using cheap fatty acid recycled from dimer acid industry as feedstock. The corrosion inhibition effects of G211 on Q235 steel in 1 M HCl solution were investigated through weight loss experiments, potential polarization curves, and alternating current impedance spectroscopy experiments. The results show that the inhibition rate of G211 as a mixed-type inhibitor is up to 94.4% and the concentration drop as low as 500 ppm at 25 ℃. The adsorption of G211 on Q235 surface follows Langmuir adsorption isothermal curve. The chemical composition of the Q235 steel surface was analyzed through scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Furthermore, the possible corrosion inhibition mechanism of G211 on the surface of Q235 steel is proposed. This article not only presents an outstanding solution for safeguarding Q235 steel against corrosion but also introduces a feasible method for high-value utilization of monomer acid (MA).

[4+2] Dimerization of Arylmaleic Acids Imides on Solid Media

[4+2] Dimerization of Arylmaleic Acids Imides on Solid Media

A quick paster type of soluble nanoparticle microneedle patch for the treatment of obesity

Obesity is a major public burden on the working population and induces chronic diseases. Its treatment often requires long-term medication, which makes patient compliance difficult. In this study, we reported the value of HORN-MN, which comprised a fast-soluble hyaluronic acid microneedle matrix and a weak acid-degradable oleanolic acid dimer of rosiglitazone nanoparticles. The results showed that the microneedles easily punctured the stratum corneum and dissolved in the dermis of the abdominal wall within 5 min, followed by the release of rosiglitazone nanoparticles. Thereafter, the nanoparticles were endocytosed by macrophages and white adipocytes, then degraded to oleanolic acid in the lysosomes, thereby, releasing rosiglitazone. Oleanolic acid significantly improved the inflammatory status of obese adipose tissue and promoted white adipocyte browning, and rosiglitazone significantly potentiated WAC browning. Accordingly, the patch demonstrated a remarkable obesity-reducing efficacy in mice. In conclusion, this study developed a quick paster type of soluble rosiglitazone nanoparticle microneedle for the treatment of obesity. This patch can be suitable for working people, with an evident obesity-reducing efficacy but no effect on skin integrity despite multiple administrations.

Legacy and emerging per- and polyfluoroalkyl substances (PFASs) in agricultural soils affected by fluorochemical manufacturing facilities, North China: Occurrence, region-specific distribution, substitution trend and source appointment

Accompanied with restriction of legacy per- and polyfluoroalkyl substances (PFASs), numbers of emerging PFASs are widely detected in the environment. However, information on environmental occurrences and behaviors of emerging PFASs were scarce in agricultural soils. In this study, the spatial distributions, sources, substitution trends and ecological risk assessment of 31 legacy and emerging PFASs were investigated in 69 agricultural soils from Fuxin, North China. The 26 out of 31 PFASs were detected with concentrations of 57.36 - 1271.06 pg/g dry weight. Perfluorooctanoic acid (PFOA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were predominant in legacy and emerging PFASs, respectively. Based on principal component and dual carbon-nitrogen stable isotope analysis, atmosphere, fluorochemical activities and river irrigation were main sources of PFASs. Substitution trends indicated HFPO-DA and short chain perfluoroalkyl carboxylic acids (C4 - C7) as main alternatives of PFOA, and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) as major substitutes to perfluorooctanesulfonic acid (PFOS). The calculated risk quotient values (< 0.006) only indicated potential low ecological risk of 7 target PFASs in agricultural soils. The results of this study broadened out the information of PFAS contamination in agricultural soils, which were significant for PFAS supervision in China.

Propeller shaped triarylamine acid: An ultra-sensitive fluorescence probe for distinguishing propanol isomers and water sensing in organic solvents

The photophysical properties of conformationally flexible (TPA-C) and partially rigidified (Cz-C) triarylamine acids were explored in solid as well as solution state and correlated with the structure. TPA-C and Cz-C exhibited moderate solid-state fluorescence (Φf = 6.2 % (TPA-C) and 5.6 % (Cz-C)) and self-reversible mechanofluorochromism. TPA-C produced fluorescent polymorphs (TPA-C-1 and TPA-C-2) with tunable fluorescence. TPA-C-1 showed unusual carboxylic acid intermolecular interactions whereas TPA-C-2 and Cz-C showed usual carboxylic acid dimer. TPA-C exhibited strong solvent polarity dependent tunable fluorescence (Φf = 0.01 to 0.11 compared to quinine sulphate standard) but Cz-C was non-emissive in the solution state. The dual emissive TPA-C showed highly sensitive fluorescence changes in organic solvents (CH3CN, THF, DMF, EtOH) when trace amount of water was added. In CH3CN, TPA-C showed weak fluorescence at 474 nm and addition of water (1 %) exhibited significant blue shift (λmax = 416 nm). The fluorescence intensity was gradually decreased with blue shifting in DMF, THF and EtOH with water addition. Importantly, TPA-C showed drastically different fluorescence in n-propanol (n-PA) and iso-propanol (IPA). TPA-C in n-PA showed fluorescence at 408 nm that was clearly red shifted to 438 nm with 0.1 % addition of IPA. The limit of detection (LOD) of water in CH3CN, DMF, THF and EtOH by TPA-C revealed 0.02, 0.7, 0.08 and 0.77 %, respectively. The LOD of IPA sensing in n-PA is 0.05 % and indicated the very efficient sensing and distinguishing propanol isomers. Thus, simple triphenylamine acid showed excellent water sensing and propanol isomers discrimination that could be attributed to the twisted intramolecular charge transfer (TICT) formation.

Thyroid disrupting effects and the developmental toxicity of hexafluoropropylene oxide oligomer acids in zebrafish during early development

As perfluorooctanoic acid (PFOA) alternatives, hexafluoropropylene oxide dimeric acid (HFPO-DA) and hexafluoropropylene oxide trimeric acid (HFPO-TA) have been increasingly used and caused considerable water pollution. However, their toxicities to aquatic organisms are still not well known. Therefore, in this study, zebrafish embryos were exposed to PFOA (0, 1.5, 3 and 6 mg/L), HFPO-DA (0, 3, 6 and 12 mg/L) and HFPO-TA (0, 1, 2 and 4 mg/L) to comparatively investigate their thyroid disrupting effects and the developmental toxicity. Results demonstrated that waterborne exposure to PFOA and its two alternatives decreased T4 contents, the heart rate and swirl-escape rate of zebrafish embryos/larvae. The transcription levels of genes related to thyroid hormone regulation (crh), biosynthesis (tpo and tg), function (trα and trβ), transport (transthyretin, ttr), and metabolism (dio1, dio2 and ugt1ab), were differently altered after the exposures, which induced the thyroid disrupting effects and decreased the heart rate. In addition, the transcription levels of some genes related to the nervous system development were also significantly affected, which was associated with the thyroid disrupting effects and consequently affected the locomotor activity of zebrafish. Therefore, HFPO-DA and HFPO-TA could not be safe alternatives to PFOA. Further studies to uncover the underlying mechanisms of these adverse effects are warranted.

Biodegradable Hydrogenated Dimer Acid-Based Plasticizers for PLA with Excellent Plasticization, Thermal Stability and Gas Resistance.

The use of vegetable oil-dervied plasticizers to enhance the flexibility of polylactic acid (PLA) has received much attention due to their renewability, inexpensiveness and biodegradation. However, the double bonds in vegetable oil-based plasticizers limit their compatibility with PLA, resulting in PLA-derived products with reduced flexibility. Herein, we examined soybean oil-derived hydrogenated dimer acid-based polyethylene glycol methyl ether esters (HDA-2n, 2n = 2, 4, 6 or 8, referring to the ethoxy units) developed via the direct esterification of saturated hydrogenated dimer acid and polyethylene glycol monomethyl ethers. The resulting HDA-2n was first used as a plasticizer for PLA, and the effects of the ethoxy units in HDA-2n on the overall performance of the plasticized PLA were systematically investigated. The results showed that, compared with PLA blended with dioctyl terephthalate (DOTP), the PLA plasticized by HDA-8 with the maximum number of ethoxy units (PLA/HDA-8) exhibited better low-temperature resistance (40.1 °C vs. 15.3 °C), thermal stability (246.8 °C vs. 327.6 °C) and gas barrier properties. Additionally, the biodegradation results showed that HDA-8 could be biodegraded by directly burying it in soil. All results suggest that HDA-8 could be used as green alternative to the traditional petroleum-based plasticizer DOTP, which is applied in the PLA industry.

Ion Mobility Mass Spectrometry-Based Disaccharide Analysis of Glycosaminoglycans.

Glycosaminoglycans (GAGs) are linear and acidic polysaccharides. They are ubiquitous molecules, which are involved in a wide range of biological processes. Despite being structurally simple at first glance, with a repeating backbone of alternating hexuronic acid and hexosamine dimers, GAGs display a highly complex structure, which predominantly results from their heterogeneous sulfation patterns. The commonly applied method for compositional analysis of all GAGs is "disaccharide analysis." In this process, GAGs are enzymatically depolymerized into disaccharides, derivatized with a fluorescent label, and then analysed through liquid chromatography. The limiting factor in the high throughput analysis of GAG disaccharides is the time-consuming liquid chromatography. To address this limitation, we here utilized trapped ion mobility-mass spectrometry (TIM-MS) for the separation of isomeric GAG disaccharides, which reduces the measurement time from hours to a few minutes. A full set of disaccharides comprises twelve structures, with eight possessing isomers. Most disaccharides cannot be differentiated by TIM-MS in underivatized form. Therefore, we developed chemical modifications to reduce sample complexity and enhance differentiability. Quantification is performed using stable isotope labelled standards, which are easily available due to the nature of the performed modifications.

Occurrence of legacy and Emerging per- and polyfluoroalkyl substances (PFASs) in indoor dust from office environment in south china

Per- and polyfluoroalkyl substances (PFASs) constitute a broad group of fluorinated organic chemicals that are widely used in consumer products and industrial applications due to their excellent physicochemical properties. Given that people spend a significant portion of their time in office environments, our understanding of the environmental presence and human exposure to these chemicals is crucial. In this study, we conducted a targeted analysis of 24 PFASs in office indoor environments. The ΣPFAS concentrations ranged from 51.6 to 219 ng/g with mean (±SE) and median concentrations of 114 (±5.75) and 107 ng/g, respectively. Hexafluoropropylene oxide dimer acid (HFPO-DA) was the most abundant emerging PFAS detected in the dust, with mean and median concentrations of 40.5 (±1.62) and 40.4 ng/g, respectively, comprising 34.2 % of the ΣPFAS concentrations. Notably, HFPO-DA exhibited a positive correlation with perfluorooctane sulfonate (PFOS) (r: 0.427, p < 0.01), suggesting a potential common source for these two compounds. Our findings underscore the significant contribution of emerging PFASs to total PFAS concentrations and raise concerns about their chronic toxicity and potential health risks to humans in office indoor environments.

Hydroxyl‐terminated polybutadiene(HTPB) propellants cross‐linked by dimer acid diisocyanate (DDI): Cross‐linking network and properties

AbstractConsidering the high toxicity of toluene diisocyanate (TDI) and the low reactivity of isophorone diisocyanate (IPDI), a low‐toxicity curing agent, dimer acid diisocyanate (DDI), was used to cross‐link HTPB elastomers and propellants. The unique long‐chain structure of DDI not only ensures the elastic modulus and tensile strength of the elastomer, but also improves the flexibility to some extent. The long flexible chains promote the segment movement, which is very important for the formation of hydrogen bonds between segments. The chemical cross‐linking network and hydrogen bonding association play a significant role in the mechanical properties of the HTPB/DDI system. The relationship between the mole ratio of ‐NCO to ‐OH (R‐value) and the mechanical properties of HTPB/DDI elastomers were also investigated. In the range of R‐value from 0.85 to 1.2, the elastic modulus and tensile strength first increase and then decrease, and the elongation at break first decreases and then increases. Under the same curing conditions, the elastic modulus and tensile strength of the HTPB/DDI propellant are similar to the HTPB/TDI propellant. For the HTPB/AP/Al propellants and HTPB/AP/RDX/Al propellants, the HTPB/DDI system has lower burning rates in the range of 5–19 MPa than the HTPB/TDI system and HTPB/IPDI system. The application of DDI can reduce the burning rates of the propellant without adding any burning rate modifiers. It is considered that DDI can replace TDI and IPDI as a new curing agent with low toxicity and moderate reactivity for HTPB systems.

Biobased partially crosslinked polyβ-hydroxyesters synthesized from low-melt carboxyl-polyamides and a dicyclocarbonate

A new kind of biobased partially crosslinked polyβ-hydroxyesters (cPHEs) was synthesized through the ring-opening polymerization of a five-membered dicyclocarbonate and carboxyl-terminated dimer acid (DA) oligopolyamides (DAPAcs). The DAPAcs provided carboxyl groups and attacked the cyclocarbonate groups to form β-hydroxyester units, which was confirmed by a model reaction. DAPAcs were synthesized from hexamethylenediamine and excess DA. Their structure and properties were confirmed by FTIR, 1H NMR, and DSC. cPHEs exhibited semicrystalline characters with good thermal properties evidenced by wide-angle X-ray scattering, DSC, and TGA. Introducing DAPA sequences improved intermolecular interactions and tensile strength. The attack of pendent hydroxy groups to remaining cyclocarbonate groups led to crosslinked cPHEs. Dynamic β-hydroxylester segments impart the reprocessability of cPHEs, and stress relaxation experiments were conducted at different temperatures to evaluate the exchange kinetics. A new synthetic route different from normal epoxy-carboxyl route was established. This method broadens the research of polyβ-hydroxylesters and their application range.

Multiple effects of relative humidity on heterogeneous ozonolysis of cooking organic aerosol proxies from heated peanut oil emissions

The exposure to cooking organic aerosols (COA) is closely related to people's daily lives. Despite extensive investigations into COA's model compounds like oleic acid, the intricacies of heterogeneous ozonolysis of real COA and the effects of ambient conditions like humidity remain elusive. In this work, the ozonolysis of COA proxies from heated peanut oil emissions was investigated using diffuse reflectance infrared Fourier transform (DRIFTS) spectroscopy, and proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). We found that humidity hinders the reaction between ozone and CC double bonds due to the competitive adsorption of water and ozone on COA. Although visible light has little influence on the ozonolysis of COA in the absence of humidity, the ozonolytic CO production is significantly promoted by visible light in the presence of humidity. It may be attributed to the formation of water-derived reactive oxygen species (ROS, mainly HO•) from the photosensitization of polycyclic aromatic hydrocarbons (PAHs) in COA. We also found that humidity can enhance the depolymerization of carboxylic acid dimers and hydrolysis of intrinsic acetals in the COA. Moreover, humidity promotes the release of VOCs during both the dark and light ozonolysis of COA. This work reveals the important roles of humidity-responsive and photo-responsive components in COA during its ozonolysis, and the change in VOC release may guide the control of human VOC exposure in indoor air.