Gas-phase and aqueous-surface reaction mechanism of Criegee radicals with serine and nucleation of products: A theoretical study.

Criegee intermediates (CIs) are short-lived carbonyl oxides, which can affect the budget of OH radicals, ozone, ammonia, organic/inorganic acids in the troposphere. This study investigated the reaction of CIs with serine (Ser) in the gas phase by using density functional theory (DFT) calculations and at the gas-liquid interface by using Born-Oppenheimer molecular dynamics (BOMD). The results reveal that the reactivity of the three functional groups of Ser can be ordered as follows: COOH > NH2 > OH. Water-mediated reactions of CIs with NH2 and OH groups of Ser on the droplet follow the proton exchange mechanism. The products, sulfuric acids, ammonia, and water molecules form stable clusters within 20 ns. This study shows that hydroperoxide products can contribute to new particle formation (NPF). The result deepens the understanding of the reaction of CIs with multifunctional pollutants and atmospheric behavior of CIs in polluted areas.

Selected Phase Separation Renders High Strength and Toughness to Polyacrylamide/Alginate Hydrogels with Large-Scale Cross-Linking Zones.

High water content usually contradicts the mechanics for hydrogels, and achieving both characteristics is extremely challenging. Herein, a novel confined-chain-aggregation (CCA) strategy is developed to fabricate ultrastrong and tough hydrogels without sacrificing their inherent water capacity. Based on the popular polyacrylamide/alginate (PAAm/Alg) system with a double network (DN), a poor solvent exchange is induced once PAAm is fully cross-linked but prior to ionic cross-linking of alginate. In this case, the alginate chains are restricted by the chemical PAAm network and undergo a confined-chain aggregation, which guarantees an interpenetrating network of both polymers and simultaneously generates micron-scale aggregates. In addition, after the subsequent water uptake, the accompanying formation of hydrogen bonds and metal-ligand coordination stabilizes the newly formed alginate aggregates, serving as large-scale cross-linking zones. However, the PAAm chains are anchored by the preformed cross-linking points and convert back to the uniformly distributed, high-water-content state, achieving a selected phase separation in a DN system. The combined CCA and hybrid cation cross-linking method gives mechanical strength and toughness to the PAAm/Alg hydrogels to reach approximately 30 and 5 times the traditional methods, respectively. This investigation provides a general strategy for the development of a new generation of double-network hydrogels, which will expand their application as structural materials for cartilage and soft robotics.

Simulation Verification of Barrierless HONO Formation from the Oxidation Reaction System of NO, Cl, and Water in the Atmosphere.

Nitrous acid (HONO) is a major source of hydroxyl (OH) radicals, and identifying its source is crucial to atmospheric chemistry. Here, a new formation route of HONO from the reaction of NO with Cl radicals with the aid of one or two water molecules [(Cl) (NO) (H2O)n (n = 1-2)] as well as on the droplet surface was found by Born-Oppenheimer molecular dynamic simulation and metadynamic simulation. The (Cl) (NO) (H2O)1 (monohydrate) system exhibited a free-energy barrier of approximately 0.95 kcal mol-1, whereas the (Cl) (NO) (H2O)2 (dihydrate) system was barrierless. For the dihydrate system and the reaction of NO with Cl radicals on the droplet surface, only one water molecule participated in the reaction and the other acted as the "solvent" molecule. The production rates of HONO suggested that the monohydrate system ([NO] = 8.56 × 1012 molecule cm-3, [Cl] = 8.00 × 106 molecule cm-3, [H2O] = 5.18 × 1017 molecule cm-3) could account for 40.3% of the unknown HONO production rate (Punknown) at site 1 and 53.8% of Punknown at site 2 in the East China Sea. This study identified the importance of the reaction system of NO, Cl, and water molecules in the formation of HONO in the marine boundary layer region.

The homogeneous gas-phase formation mechanisms of PCPTs/PCDTs/PCDFs from the radical/radical cross-condensation of 2-CPR and 2-CTPR: a theoretical, mechanistic and kinetics study.

Polychlorinated phenoxathiins (PCPTs) are one group of dioxin-like compounds, which can be considered to be one-oxygen-substituted polychlorinated thianthrene (PCTA) compounds or one-sulfur-substituted polychlorinated dibenzo-p-dioxin (PCDD) compounds. Owing to their high toxicity and wide distribution, clarifying the formation and emission of PCPTs due to combustion and thermal processes can deepen our understanding of the dioxin formation mechanism and allow reduced-emission and dioxin-control strategies to be established. Chlorophenols (CPs) and chlorothiophenols (CTPs) are direct precursors in PCPT formation. In this paper, the homogeneous gas-phase formation mechanisms of PCPTs, as well as polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzothiophenes (PCDTs), from the cross-condensation of 2-chlorophenoxy radicals (2-CPRs) and 2-chlorothiophenoxy radicals (2-CTPRs) under thermal and combustion conditions were investigated theoretically using a density functional theory (DFT) method. The reaction priorities and effects of water molecules on the formation mechanisms were discussed. The rate constants of crucial elementary steps were calculated from 600-1200 K. The acute and chronic toxicities of the main products were predicted at three trophic levels. This study shows that routes starting with oxygen-carbon condensation are favored over those starting with sulfur-carbon condensation for PCPT formation, and routes ending with Cl loss can occur more easily than those ending with H loss. Water molecules have a negative catalytic effect on CH-S H-transfer steps but a positive catalytic effect on CH-O H-transfer steps.

Mechanism and kinetic properties for the complete series reactions of chloro(thio)phenols with O(3P) under high temperature conditions.

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs) are two groups of dioxin-like compounds with oxygen and sulfur substitution, respectively. Chlorophenols (CPs) and chlorothiophenols (CTPs) are direct precursors in PCDD/F and PCDT/TA formation. The formation of chlorophenoxy radicals (CPRs) and chlorothiophenoxy radicals (CTPRs) from chlorophenols (CPs) and chlorothiophenols (CTPs) with O(3P) is an important initial step for the formation of PCDD/Fs and PCDT/TAs, respectively. In this paper, the formation of CPRs/CTPRs from the complete series reactions of 19 CP/CTP congeners with O(3P) was studied using the density functional theory (DFT) method. The rate constants of each reaction were calculated using canonical variational transition state (CVT) theory along with a small-curvature tunneling (SCT) contribution over a wide temperature range of 600-1200 K. The effect of the chlorine substitution pattern on the structural parameters, thermochemical properties and rate constants in both CPs and CTPs was discussed. This study shows that the reactions between CPs and O(3P) can be affected by the chlorine substitution at the para-position, and the reactions between CTPs and O(3P) are mostly influenced by both ortho-substitutions. The thiophenoxyl-hydrogen abstraction from CTPs by O(3P) is more likely to occur than the phenoxyl-hydrogen abstraction from CPs by O(3P). Comparison of the reactivity of CP/CTPs with O(3P) with our previous work on CP/CTPs with H and OH shows that the order for phenoxyl-hydrogen abstraction potential is CP + OH > CP + O(3P) > CP + H, and the order for thiophenoxyl-hydrogen abstraction potential is CTP + O(3P) > CTP + H > CTP + OH.

A self-reinforcing strategy enables the intimate interface for anisotropic alginate composite hydrogels.

Natural-derived hydrogels are expected as promising structural biomaterials, but the soft character severely limits their applications. Here, a facile yet effective strategy was developed to fabricate super-strong and tough alginate composite hydrogels via a self-reinforcing method. The strategy was based on the incorporation of alginate materials with distinctive anisotropic features (fibers, fabrics and aerogels) into the precursor solution of congeneric hydrogels, followed by the in situ ionic-crosslinking. Interestingly, triggered by the concentration difference, the cations-Ca2+ in reinforcing phase could diffuse into the interface and simultaneously chelate with alginate chains of both reinforcing phase and hydrogel matrix, acting as self-generating interfacial binders. Contributed by the intimate interface, the load was effectively transferred into the rigid reinforcing phase, and the hydrogels integrated them into a mechanical network. This research offers a new path to design the interface of polysaccharide composites without extra coupling agents.

A theoretical study of hydrogen-bonded molecular clusters of sulfuric acid and organic acids with amides.

Amides, a series of significant atmospheric nitrogen-containing volatile organic compounds (VOCs), can participate in new particle formation (NPF) throught interacting with sulfuric acid (SA) and organic acids. In this study, we investigated the molecular interactions of formamide (FA), acetamide (AA), N-methylformamide (MF), propanamide (PA), N-methylacetamide (MA), and N,N-dimethylformamide (DMF) with SA, acetic acid (HAC), propanoic acid (PAC), oxalic acid (OA), and malonic acid (MOA). Global minimum of clusters were obtained through the association of the artificial bee colony (ABC) algorithm and density functional theory (DFT) calculations. The conformational analysis, thermochemical analysis, frequency analysis, and topological analysis were conducted to determine the interactions of hydrogen-bonded molecular clusters. The heterodimers formed a hepta or octa membered ring through four different types of hydrogen bonds, and the strength of the bonds are ranked in the following order: SOH•••O > COH•••O > NH•••O > CH•••O. We also evaluated the stability of the clusters and found that the stabilization effect of amides with SA is weaker than that of amines with SA but stronger than that of ammonia (NH3) with SA in the dimer formation of nucleation process. Additionally, the nucleation capacity of SA with amides is greater than that of organic acids with amides.

2-Methyltetrol sulfate ester-initiated nucleation mechanism enhanced by common nucleation precursors: A theory study.

Aerosol samples from all over the word contained 2-methyltetrol sulfate ester (MTS). We investigated the role of MTS in new particle formation (NPF) with aerosol nucleation precursors, including sulfuric acid (SA), water (W), ammonia (N), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA). The analysis was performed using quantum chemical approach, kinetic calculation and molecular dynamics (MD) simulations. The results proved that the molecular interactions in the clusters were mainly H-bonds and electrostatic interaction. The negative Gibbs free energy changes for all the studied MTS-containing clusters indicated that the formation of these clusters was thermodynamically favorable. The stability of the clusters was evaluated according to the total evaporation rate. Here, (MTS)(SA) and (MTS)(W) were the most and least stable cluster, respectively. MD simulations were used for time and spatial analysis of the role of the MTS-SA system. The results indicated that MTS can self-aggregate or absorb SA molecules into clusters, larger than the size of the critical cluster (approximately 1 nm), suggesting that MTS can initiate NPF by itself or together with SA.

Determination of the amine-catalyzed SO3 hydrolysis mechanism in the gas phase and at the air-water interface.

New particle formation (NPF) involving amines in the atmosphere is considered an aggregation process, during which stable molecular clusters are formed from amines and sulfuric acid via hydrogen bond interaction. In this work, ab initio dynamics simulations of ammonium bisulfate formation from a series of amines, SO3, and H2O molecules were carried out in the gas phase and at the air-water interface. The results show that reactions between amines and hydrated SO3 molecules in the gas phase are barrierless or nearly barrierless processes. The reaction rate is related to the basicity of gas-phase amines-the stronger the basicity, the faster the reaction. Furthermore, SO3 hydrolysis catalyzed by amines occurs simultaneously with H2SO4-amine cluster formation. At the air-water interface, reactions between amines and SO3 involve multiple water molecules. The reaction center's ring structure (amine-SO3-nH2O) promotes the transfer of protons in the water molecules. The formed ammonium cation (-RNH3+) and the bisulfate anion (HSO4-) are present and stable by means of hydrogen bond interaction. The cluster formation mechanism provides new insights into NPF involving amines, which may play an important role in the formation of aerosols in some heavily polluted areas - e.g., those with a high amine concentration.

Effect of multifunctional compound monoethanolamine on Criegee intermediates reactions and its atmospheric implications.

The reactions of Criegee intermediates with trace gases (such as alcohols, amines, and acids) are primarily dependent on the trace gases' functional group activity. In this study, we used density functional theory calculations and ab initio dynamics simulation methods to explore the synergistic effect of NH2 and OH groups, in the multifunctional compound monoethanolamine (MEA), on the Criegee reaction. The results showed that among the four evaluated MEA configurations, two functional groups in the g'Gg' and tGg' configurations, -NH2 and -OH, have the synergistic effect on the C2 stabilized Criegee intermediates (sCIs). At the gas-liquid interface, sCIs react with NH2 groups of MEA molecules directly or are mediated by water molecules, resulting in additional product formation. The rate calculation indicated that the reaction of sCIs with NH2 groups of MEA molecules is prior to that with OH groups. In addition, OH groups promote the reactions between sCIs and NH2 groups of MEA, while the presence of NH2 groups weakens the reactions of sCIs and OH groups of MEA to some extent. At 298 K, the total rate constant of anti-CH3CHOO with NH2 group of MEA is 4.26 × 10-11 cm3 molecule-1 s-1, which is four orders of magnitude higher than that of anti-CH3CHOO hydration. Under low humidity conditions, the reactions between sCIs and MEA could contribute to the removal of sCIs.

Propionamide participating in H2SO4-based new particle formation: a theory study.

Propionamide (PA), an important pollutant emitted into the atmosphere from a variety of sources, is abundant in many areas worldwide, and could be involved in new particle formation (NPF). In this study, the enhancement of the H2SO4 (SA)-based NPF by PA was evaluated through investigating the formation mechanism of (PA) m (SA) n (m = 0-3 and n = 0-3) clusters using computational chemistry and kinetics modeling. Our study proved that the formation of all the PA-containing clusters is thermodynamically favorable. Furthermore, the [double bond, length as m-dash]O group in PA plays an important role in the clusters with more PA than SA, and the basicity of bases exerts a greater influence with an increasing amount of SA. We demonstrate that although the enhancing potential of PA is lower than that of the strongest enhancers of SA-based NPF such as methylamine (MA) and dimethylamine (DMA), PA can enhance the SA-based NPF at the parts per billion (ppb) level, which is typical for concentrations of C3-amides in, for example, urban Shanghai (China). The monomer evaporation is the dominant degradation pathway for the (PA) m (SA) n clusters, which differs from that of the SA-DMA system. The formation rate of PA-containing clusters is comparable to the rate coefficients for PA oxidation by hydroxyl (OH) radicals, indicating that participating in the SA-based NPF is a crucial sink for PA.

Determination of reactions between Criegee intermediates and methanesulfonic acid at the air-water interface.

In recent years, Criegee chemistry has become an important research focus due to its relevance in regulating concentrations of tropospheric OH radicals, hydroperoxides, sulfates, nitrates, and aerosols. However, to date, its interface behavior remains poorly understood. Thus, in this study, we used the Born-Oppenheimer molecular dynamics (BOMD) simulation method to explore the reaction mechanisms between Criegee intermediates (CIs) and methylsulfonic acid (MSA) at the air-water interface, then compared the observed behaviors with those in the gas phase. The addition of Criegee intermediates to MSA is nearly a barrierless reaction and follows a loop-structure mechanism in the gas phase. The high rate constants indicate that the Criegee intermediates and MSA reactions are the main acid removal channels. At the water's surface, the interaction of Criegee intermediates with MSA includes three main channels: 1) direct addition reaction, 2) H2O-mediated hydroperoxide formation, and 3) MSA-mediated Criegee hydration. These reaction channels follow a loop-structure or a stepwise mechanism and proceed at the picosecond time-scale. The results of this work broaden our understanding of Criegee atmospheric behaviors in polluted urban and marine areas, which in turn will aid in developing more effective pollution control measures.

Design of mechanically strong and tough alginate hydrogels based on a soft-brittle transition.

This study reveals the water-induced mechanical transition of alginate hydrogels and the corresponding mechanism, through which, mechanically strong and tough hydrogels are fabricated. It is found that in the water content (CW, wt%) range of 62 < CW < 93, the alginate hydrogels exhibit soft material properties with low modulus and fracture stress, but high extendability. However, within range of 19 < CW < 48, ultrahigh modulus and fracture stress but low strain are observed for the hydrogels, suggesting brittle behavior. At intermediate CW, the maximum fracture energy is obtained. The soft-brittle transition of alginate hydrogels arises from the aggregation of polymer chains upon dehydration, which transforms the inactive hydrogen bonding interaction sites into active ones. Through facile control of the dehydration degree, a very wide range of supramolecular interactions and hence of mechanical properties can be accessible, which renders the alginate hydrogels ideal candidates for further development of load-bearing materials.

Cooking-Inspired Versatile Design of an Ultrastrong and Tough Polysaccharide Hydrogel through Programmed Supramolecular Interactions.

Simultaneously achieving strength and toughness in soft materials remains a challenge, especially for physically crosslinked hydrogels with many inactive interaction sites. In this work, inspired by the cooking of thick soup in China, a facile method that includes free water evaporation of the diluted pregel solution followed by crosslinking (WEC) is proposed to fabricate polysaccharide hydrogels. Herein, without the constraints of viscosity and crosslinking, polymer chains can homogenously approach as much as possible, thereby enabling the transformation of inactive supramolecular interaction (H-bonding and ionic coordination) sites into active sites until reaching the maximum level. Through facilely tuning the concentrating degree, programmed supramolecular interactions, serving as energy-dissipating sacrificial bonds, impart the hydrogels with strength and toughness over a very wide range, where a "ductile-to-tough" transition is discovered to occur first. Using WEC in alginate, the concentration can be as high as 25 wt% without sacrificing processing ability, a result that is significantly beyond common value (3-7 wt%), and the extremely stiff and tough hydrogels are obtained, superior to isotropic alginate hydrogels ever reported. This research offers a facile and versatile strategy to fabricate isotropic polysaccharide hydrogels, which become ideal matrix materials for further fabrication of hybrid or anisotropic hydrogels.

Theoretical study of the cis-pinonic acid and its atmospheric hydrolysate participation in the atmospheric nucleation.

cis-Pinonic acid (CPA), one of the major photooxidation products of α-pinene, is believed to contribute to the formation of aerosols formed over forested areas. In the current study, we implement quantum chemical calculation to investigate the interaction between sulfuric acid (SA) and CPA as well as the hydrolysate of CPA (HCPA) in the presence of water or ammonia in the atmosphere. The lowest free energy configurations, reactants, transition states, intermediates, and products were optimized at 298/278K and 1atm at the M06-2X/6-311+G(3df,3pd) level. Our results show that one CPA molecule might initially nucleate with SA molecules and subsequently participate in the formation and growth of the new particle in the form of HCPA. More than one HCPA molecule may be involved in the critical nuclei. Furthermore, the hydrolysis reaction of CPA can be effectively catalyzed by SA and nitric acid (NA) in presence of water, which significantly increases the HCPA content in the atmosphere and subsequently promotes the particle nucleation. Overall, the current study elucidates a new mechanism of atmospheric nucleation driven by CPA and its hydrolysate.

A molecular understanding of the interaction of typical aromatic acids with common aerosol nucleation precursors and their atmospheric implications.

Aromatic acids, which are generated from numerous anthropogenic emissions and secondary transformations, have been considered to play a crucial role in new particle formation. In this study, we performed theoretical calculations at the PW91PW91/6-311++G(3df,3pd) level to investigate the interaction between typical aromatic acids namely benzoic acid (BA), phenylacetic acid (PAA), phthalic acid (PA), isophthalic acid (mPA), and terephthalic acid (PTA) and common atmospheric nucleation precursors namely sulfuric acid (SA), water (H2O), ammonia (NH3), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA). The geometric analysis, Gibbs free energy analysis, OH/NH-stretching vibrational frequency calculation, and atoms in molecules (AIM) analysis were conducted to determine the interactions in the complexes. The heterodimers formed a six to eight membered ring through four types of hydrogen bond, and the bond strength could be ranked in descending order: SO-H⋯O > O-H⋯O/N > N-H⋯O. The BA/PAA/mPA/PTA-SA complexes had the lowest Gibbs free energy values. PA was more likely to interact with NH3 or amines rather than SA due to an intra-molecular hydrogen bond. Additionally, the aromatic acids have similar ability to interact with SA and NH3 as monocarboxylic/dicarboxylic acid. The formation potential of the heterodimers from aromatic acids with common nucleation precursors in ambient atmosphere was investigated.

Procalcitonin, C-Reactive Protein, and Neutrophil Ratio Contribute to the Diagnosis and Prognosis of Severe Acute Pancreatitis.

BACKGROUND: We aimed to explore the significance of procalcitonin (PCT), C-reactive protein (CRP) and neutrophil ratio (N%) in the early diagnosis, treatment, and prognosis of severe acute pancreatitis (SAP). METHODS: A total of 104 patients with SAP (SAP group) and 101 patients with mild acute pancreatitis (MAP) (MAP group) admitted to Affiliated Hospital of Jining Medical University, Jining, China were enrolled. The PCT and CRP in serum were detected by a full-automatic biochemical analyzer, and N% in peripheral blood was measured by a hemocyte analyzer. RESULTS: The peripheral blood PCT, CRP, and N% in the SAP group were significantly higher than those in the MAP group (P<0.001). Multivariate Logistic regression analysis showed that acute physiology and chronic health evaluation II (APACHE II) score, Ranson score, PCT, CRP, and N% were independent risk factors for SAP. The receiver operating characteristic (ROC) curve showed that the area under curve (AUC) of PCT, CRP, and N% in diagnosing SAP were 0.906, 0.840, and 0.834 respectively, while that of combined detection was 0.972. The AUC of PCT, CRP, and N% in diagnosing SAP death were 0.907, 0.900, and 0.894, respectively. CONCLUSIONS: Peripheral blood PCT, CRP, and N% contribute to the diagnosis and prognosis of SAP.

Investigating the composition characteristics of dissolved and particulate/colloidal organic matter in effluent-dominated stream using fluorescence spectroscopy combined with multivariable analysis.

Fluorescence excitation-emission matrix (EEM) spectroscopy combined with principal component analysis (PCA) and parallel factor analysis (PARAFAC) were used to investigate the compositional characteristics of dissolved and particulate/colloidal organic matter and its correlations with nitrogen, phosphorus, and heavy metals in an effluent-dominated stream, Northern China. The results showed that dissolved organic matter (DOM) was comprised of fulvic-like, humic-like, and protein-like components in the water samples, and fulvic-like substances were the main fraction of DOM among them. Particulate/colloidal organic matter (PcOM) consisted of fulvic-like and protein-like matter. Fulvic-like substances existed in the larger molecular form in PcOM, and they comprised a large amount of nitrogen and polar functional groups. On the other hand, protein-like components in PcOM were low in benzene ring and bound to heavy metals. It could be concluded that nitrogen, phosphorus, and heavy metals in effluent had an effect on the compositional characteristics of natural DOM and PcOM, which may deepen our understanding about the environmental behaviors of organic matter in effluent.

[Diversity of associated nitrogen-fixing bacteria isolated from the pioneer plants-Vetiver zizanioides].

OBJECTIVE: Vetiver zizanioides is a perennial grass of the Poaceae family, known of its silage, soil and water conservation role. The aim of the study was to collect and identify the resources of the nitrogen-fixing bacteria associated with Vetiver zizanioides. METHODS: Associated nitrogen-fixing bacteria isolated from Vetiver zizanioides were studied by SDS-PAGE whole-cell protein patterns, insert sequence (IS)-PCR finger printing, utilization of sole carbon sources and 16S rRNA gene sequence analysis. RESULTS: Based on the results of finger printing analysis, protein patterns and biological test, isolates were grouped into 6 clusters, except 4 single strains. Phylogenetic analysis of 16S rDNA sequences indicated that isolates belonged to Herbaspirillum frisingense, Enterobacter ludwigii, Pseudacidovorax intermedius, Mitsuaria chitosanitabida, Pseudomonas putida, Pseudomonas fluorescens, Burkholderia vietnamiensis and Enterobacter cloacae. CONCLUSION: The nitrogen fixers associated with Vetiver zizanioides showed great diversity and may have a potential application for the grass forage and agriculture.