Unexpected enhancement of sulfuric acid-driven new particle formation by alcoholic amines: The role of ion-induced nucleation.

New particle formation (NPF) contributes more than half of the global aerosol. Diethanolamine (DEA) and methyldiethanolamine (MDEA) are the most common amines used to remove CO2 and H2S, which are lost to the atmosphere from CO2 chemical absorbers, livestock and consumer products and are involved in sulfuric acid (SA)-driven NPF. Ion-induced nucleation (IIN) is an important nucleation pathway for NPF. We investigated the role of IIN on DEA and MDEA enhancing SA-driven NPF using density functional method (DFT), molecular dynamics (MD) simulation and atmospheric cluster dynamics code (ACDC). The effects of SO42-, H3O+, NH4+, HSO4-, NO3-, ammonia, methylamine, dimethylamine, trimethylamine and water (W) on the nucleation of SA-DEA were further investigated. The enhancement ability of DEA is greater than that of dimethylamine (DMA) and MDEA. Participation in SA-based NPF is a removal pathway for DEA and MDEA. DEA-SA clusters are generated that not only aggregate DEA and SA molecules, but also increase further growth of atmospheric ions. The very low Gibbs formation free energy highlights the importance of ion-induced nucleation for SA-based NPF. The order of the ability of common atmospheric ions to increase the (SA)(DEA) cluster nucleation is SO42- > H3O+ > NH4+ > HSO4- > NO3-. The addition of 20 water molecules increases the (SA)(DEA)9 cluster from 1.882 nm to 2.053 nm, promoting SA-based NPF. The atmospheric ions accelerate the aggregation rate of the (SA)5(DEA)5 cluster within 15 ns?

Double pH-sensitive nanotheranostics of polypeptide nanoparticle encapsulated BODIPY with both NIR activated fluorescence and enhanced photodynamic therapy.

To achieve accurate fluorescence imaging-guided cancer therapy, intelligent systems with specific responsiveness to the tumor microenvironment need to be designed. Here, we have achieved both enhanced NIR fluorescence and photodynamic therapy by introducing a dimethylamino functional group in BODIPY dyes, which can be used as a pH sensor under acidic conditions by coordinating with the proton. At pH 7.4, the fluorescence is quenched due to the photo-induced electron transfer (PET) process. After the photosensitizer is protonated in tumor cell lysosomes (pH 4.0-5.5), the PET process is inhibited and the fluorophore emission capacity is restored (fluorescence enhancement up to 10-fold), resulting in near-infrared fluorescence with the OFF/ON transition inside the tumor and enhanced singlet oxygen production for lysosome targeting capability. Due to the substitution of heavy atom iodine, the compound has a high singlet oxygen quantum yield of 81.8% in dichloromethane. In addition, using a pH-sensitive amphiphilic polypeptide (POEGMA23-PE9) as a carrier to wrap the photosensitizer BDPI can release enough drug in the acidic environment (pH 5.5-6.5) of intracellular endosomes/lysosomes, which is conducive to more adequate interactions of the photosensitizer with H+ and more effective enhancement of fluorescence emission and 1O2 production, achieving precise fluorescence imaging capability and extremely low background toxicity.

Rapid sulfuric acid-dimethylamine nucleation enhanced by nitric acid in polluted regions.

Recent research [Wang et al., Nature 581, 184-189 (2020)] indicates nitric acid (NA) can participate in sulfuric acid (SA)-ammonia (NH3) nucleation in the clean and cold upper free troposphere, whereas NA exhibits no obvious effects at the boundary layer with relatively high temperatures. Herein, considering that an SA-dimethylamine (DMA) nucleation mechanism was detected in megacities [Yao et al., Science 361, 278-281 (2018)], the roles of NA in SA-DMA nucleation are investigated. Different from SA-NH3 nucleation, we found that NA can enhance SA-DMA-based particle formation rates in the polluted atmospheric boundary layer, such as Beijing in winter, with the enhancement up to 80-fold. Moreover, we found that NA can promote the number concentrations of nucleation clusters (up to 27-fold) and contribute 76% of cluster formation pathways at 280 K. The enhancements on particle formation by NA are critical for particulate pollution in the polluted boundary layer with relatively high NA and DMA concentrations.

Solvent-Free Fabrication of Self-Regenerating Antibacterial Surfaces Resisting Biofilm Formation.

Biofilm formation on indwelling medical devices is a major cause of hospital-acquired infections. Monofunctional antibacterial surfaces have been developed to resist the formation of biofilms by killing bacteria on contact, but the adsorption of killed bacterial cells and debris gradually undermines the function of these surfaces. Here, we report a facile approach to produce an antibacterial surface that can regenerate its function after contamination. The self-regenerating surface was achieved by sequential deposition of alternating antibacterial and biodegradable layers of coating using a solvent-free initiated chemical vapor deposition method. As the top antibacterial layer gradually loses its killing ability due to the accumulation of debris, the underlying biodegradable layer degrades, shedding off the top surface layers and exposing another fresh antibacterial surface. Urinary catheters coated with monofunctional and self-regenerating antibacterial coatings both showed more than 99% bacterial killing ability at the initial antibacterial test, but the monofunctional surface lost its killing ability after continued exposure to concentrated bacterial solution, whereas the self-regenerating surfaces regained strong bacterial killing ability after prolonged exposure. Employing poly(methacrylic anhydride) and its copolymers with varied composition as the degrading layer, the degradation kinetics can be well-tailored and the self-regeneration duration spanned from minutes to days. The designed self-regenerating antibacterial surfaces could provide an effective approach to resist biofilm formation and extend the service life of indwelling medical devices.

Sterically Facilitated Intramolecular Nucleophilic NMe2 Group Substitution in the Synthesis of Fused Isoxazoles: Theoretical Study.

The influence of steric repulsion between the NMe2 group and a second ortho-(peri-)substituent in the series of 1-dimethylaminonaphthalene and N,N-dimethylanilene ortho-oximes on the ease of the NMe2 group's intramolecular nucleophilic substitution is studied. Possible reaction intermediates for three mechanisms are calculated (ωB97xd/def-2-TZVP), and their free Gibbs energies are compared to model reaction profiles. Supporting experiments have proved the absence of studied reactivity in the case of simple 2-dimethylaminobenzaldoxime, which allowed us to establish reactivity limits. The significant facilitation of NMe2 group displacement in the presence of bulky substituents is demonstrated. The possibility of fused isoxazoles synthesis via the intramolecular nucleophilic substitution of a protonated NMe2 group in the aniline and naphthalene series is predicted.

DDAO Controlled Synthesis of Organo-Modified Silica Nanoparticles with Encapsulated Fluorescent Boron Dipyrrins and Study of Their Uptake by Cancerous Cells.

The design of cargo carriers with high biocompatibility, unique morphological characteristics, and capability of strong bonding of fluorescent dye is highly important for the development of a platform for smart imaging and diagnostics. In this paper, BODIPY-doped silica nanoparticles were prepared through a "one-pot" soft-template method using a sol-gel process. Several sol-gel precursors have been used in sol-gel synthesis in the presence of soft-template to obtain the silica-based materials with the most appropriate morphological features for the immobilization of BODIPY molecules. Obtained silica particles have been shown to be non-cytotoxic and can be effectively internalized into the cervical cancer cell line (HeLa). The described method of synthesis allows us to obtain silica-based carriers with an immobilized fluorescent dye that provide the possibility for real-time imaging and detection of these carriers.

Bound detergent molecules in bacterial reaction centers facilitate detection of tetryl explosive.

Bacterial reaction centers (BRC) from Rhodobacter sphaeroides were found to accelerate, about 100-fold, the reaction between tetryl (2,4,6-trinitrophenylmethylnitramine) explosive and n-lauryl-N-N-dimethylamine-N-oxide (LDAO) that results in the formation of picric acid-like product with characteristic UV-VIS absorption spectrum with peaks at 345 and 415 nm. Moreover, this product also affects the spectra of BRC cofactors in the NIR spectral region and stabilizes the conformational changes associated with slow charge recombination. The evolution of the NIR absorption changes correlated with the kinetics of the product formation. Comparison between the wild-type and the R26 carotenoid-less strain indicates that tetryl-LDAO reaction is roughly five times faster for R26, which allows for identifying the carotenoid binding site as the optimal reaction site. Another, less-defined reaction site is located in the BRC's hydrophobic cavity. These effects are highly selective for tetryl and not observed for several other widespread nitric explosives; slowed-down charge recombination allows for distinguishing between tetryl and QB-site herbicides. The current limit of detection is in the ppb range or ~ 100 nM. Details of the molecular mechanisms of the reactions and perspectives of using these effects in bioassays or biosensors for explosives detection are also discussed.

Solubilisation of model membrane by DDAO surfactant - partitioning, permeabilisation and liposome-micelle transition.

Solubilisation of model membranes of dioleoylphosphatidylcholine (DOPC) and DOPCcholesterol (CHOL) induced by surfactant N,N-dimethyl-1-dodecanamine-N-oxide (DDAO) was studied. At the maintained pH ~ 7.5, the DDAO molecules are in their neutral state with respect to the pK ~ 5. Pore formation in lipid bilayer was studied by fluorescence probe leakage method. The changes in the size of lipid aggregates upon increasing DDAO concentration were followed turbidimetrically. Effective ratio Re at different steps of the solubilisation process was determined. The molar partition coefficient of DDAO in case of the DOPC membrane is Kp = 2262 ± 379, for DOPC-CHOL membrane Kp = 2092 ± 594. Within the experimental error, the partition coefficient, as well as effective ratios Re, are not considerably influenced when one third of DOPC molecules is substituted with CHOL (DOPC:CHOL = 2:1). Constituents of buffer (50 mmol/dm3 PBS, 150 mmol/dm3 NaCl) caused aggregation of DOPC and DOPC-CHOL unilamellar liposomes at zero and low DDAO concentration, as was shown by SANS, turbidimetry and DIC microscopy. After solubilisation of bilayer structures by surfactant, mixed DOPC-DDAO and DOPC-CHOL-DDAO micelles with the shape of cylinders with elliptical cross section were detected.

Characterization and Dimethyl Phthalate Flocculation Performance of the Cationic Polyacrylamide Flocculant P(AM-DMDAAC) Produced by Microwave-Assisted Synthesis.

A composite flocculant P(AM-DMDAAC) was synthesized by the copolymerization of acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC). By using microwave (MV) assistance with ammonium persulfate as initiator, the synthesis had a short reaction time and yielded a product with good solubility. Fourier-transform infrared spectroscopy, scanning electron microscopy, and differential thermal analysis-thermogravimetric analysis were employed to determine the structure and morphology of P(AM-DMDAAC). The parameters affecting the intrinsic viscosity of P(AM-DMDAAC), such as MV time, mass ratio of DMDAAC to AM, bath time, reaction temperature, pH value, and the dosages of ammonium persulfate initiator, EDTA, sodium benzoate, and urea were examined. Results showed that the optimum synthesis conditions were MV time of 1.5 min, m(DMDAAC):m(AM) of 4:16, 0.5 wt‱ initiator, 0.4 wt‱ EDTA, 0.3 wt‱ sodium benzoate, 2 wt‱ urea, 4 h bath time, reaction temperature of 40 °C, and pH of 2. The optimal dimethyl phthalate (DMP) removal rate can reach 96.9% by using P(AM-DMDAAC), and the P(AM-DMDAAC) had better flocculation than PAM, PAC, and PFS.

Fast and Robust Quantification of Detergent Micellization Thermodynamics from Isothermal Titration Calorimetry.

Detergents are widely used in modern in vitro biochemistry and biophysics, in particular to aid the characterization of integral membrane proteins. An important characteristic of these chemicals in aqueous solutions is the concentration above which their molecular monomers self-associate to form micelles, termed the critical micellar concentration (CMC). Micelles are supramolecular assemblies arranged with the hydrophobic portions oriented inward and the hydrophilic head groups positioned outward to interact with the aqueous solvent. Knowledge of the CMC is not only of practical relevance but also of theoretical interest because it provides thermodynamic insights. Isothermal titration calorimetry (ITC) is a powerful method to determine CMCs, as it furnishes additional information on the enthalpy and entropy of micellization. Here we describe our extension of previous methods to determine CMCs and other thermodynamic parameters from ITC demicellization curves. The new algorithm, incorporated into the stand-alone software package D/STAIN, analyzes ITC demicellization curves by taking advantage of state-of-the-art thermogram-integration techniques and automatically providing rigorous confidence intervals on the refined parameters. As a demonstration of the software's capabilities, we undertook ITC experiments to determine the respective CMCs of n-octyl ß-d-glucopyranoside (OG), n-dodecyl ß-d-maltopyranoside (DDM), and lauryldimethylamine N-oxide (LDAO). Motivated by the fact that in vitro membrane protein studies often require additives such as precipitants (e.g., polyethylene glycol (PEG)), we also carried out ITC demicellization studies in the presence of PEG3350, finding in all cases that PEG had significant effects on the thermodynamics of detergent micellization.

Covalent immobilization of biomolecules on stent materials through mussel adhesive protein coating to form biofunctional films.

It is widely accepted that surface biofunctional modification may be an effective approach to improve biocompatibility and confer new bioactive properties on biomaterials. In this work, mussel adhesive protein (MAP) was applied as a coating on 316 L stainless steel substrates (316 L SS) and stents, and then either immobilized VEGF or CD34 antibody were added to create biofunctional films. The properties of the MAP coating were characterized by scanning electron microscope (SEM), atomic force microscope (AFM) and a water contact angle test. Universal tensile testing showed that the MAP coating has adequate adhesion strength on a 316 L stainless steel material surface. Subsequent cytotoxicity and hemolysis rate tests showed that the MAP coatings have good biocompatibility. Moreover, using N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N-hydroxysulfosussinimide (EDC/NHS) chemistry, VEGF and CD34 antibody were immobilized on the MAP coatings. The amount and immobilized yield of VEGF on the MAP coatings were analyzed by enzyme-linked immuno-assays (ELISA). Finally, an endothelial cells culture showed that the VEGF biofunctional film can promote the viability and proliferation of endothelial cells. An in vitro CD34+ cells capturing test also verified the bioactive properties of the CD34 antibody coated stents. These results showed that the MAP coatings allowed effective biomolecule immobilization, providing a promising platform for vascular device modification.

Influence of atmospheric conditions on sulfuric acid-dimethylamine-ammonia-based new particle formation.

A recent quantitative measurement of rates of new particle formation (NPF) in urban Shanghai showed that the high rates of NPF can be largely attributed to the sulfuric acid (SA)-dimethylamine (DMA) nucleation due to relatively high DMA concentration in urban atmosphere (Yao et al., Science. 2018, 361, 278). In certain atmospheric conditions, the release of DMA is accompanied with the emission of high concentration of ammonia. As a result, the ammonia (A) may participate in SA-DMA-based NPF. However, the main sources of DMA and A can be different, thereby leading to different mechanism for the SA-DMA-A-based nucleation under different atmospheric conditions. Near industrial sources with relatively high DMA concentration of 108 molecules cm-3, the contribution of binary SA-DMA nucleation to cluster formation is 61% at 278 K, representing a dominant pathway for NPF. However, in the region not too close to major source of DMA emission, e.g., near agriculture farmland, the routes involving ternary SA-DMA-A nucleation make a 64% contribution at 278 K with DMA concentration of 107 molecules cm-3, showing that A has marked impact on the cluster formation. Under such a condition, we predict that coexisting DMA and A could be detected in the process of NPF. Moreover, at winter temperatures or at higher altitudes, our calculations suggest that the clustering of initial clusters likely involve ternary SA-DMA-A clusters rather than binary SA-DMA clusters. These new insights may be helpful to analyze and predict atmospheric-condition-dependent NFP in either urban or rural regions and/or in different season of the year.

Cinnamil- and Quinoxaline-Derivative Indicator Dyes for Detecting Volatile Amines in Fish Spoilage.

Colorimetric indicators are versatile for applications such as intelligent packaging. By interacting with food, package headspace, and/or the ambient environment, color change in these indicators can be useful for reflecting the actual quality and/or monitoring distribution history (e.g., time and temperature) of food products. In this study, indicator dyes based on cinnamil and quinoxaline derivatives were synthesized using aroma compounds commonly present in food: diacetyl, benzaldehyde, p-tolualdehyde and p-anisaldehyde. The identities of cinnamil and quinoxaline derivatives were confirmed by Fourier transform infrared (FT-IR) spectroscopy, mass spectrometry (MS), 1H nuclear magnetic resonance (NMR) and 13C NMR analyses. Photophysical evaluation showed that the orange-colored cinnamil derivatives in dimethylsulfoxide (DMSO) turned to dark brownish coloration when exposed to strong alkalis. The cinnamil and acid-doped quinoxaline derivatives were sensitive to volatile amines commonly present during the spoilage in seafood. Quinoxaline derivatives doped by strong organic acid were effective as pH indicators for volatile amine detection, with lower detection limits than cinnamil. However, cinnamil exhibited more diverse color profiles than the quinoxaline indicators when exposed to ammonia, trimethylamine, triethylamine, dimethylamine, piperidine and hydrazine. Preliminary tests of acid-doped quinoxaline derivatives on fresh fish demonstrated their potential as freshness indicators in intelligent packaging applications.

pH and deuterium isotope effects on the reaction of trimethylamine dehydrogenase with dimethylamine.

The flavoprotein trimethylamine dehydrogenase is a member of a small class of flavoproteins that catalyze amine oxidation and transfer the electrons through an Fe/S center to an external oxidant. The mechanism of amine oxidation by this family of enzymes has not been established. Here, we describe the use of pH and kinetic isotope effects with the slow substrate dimethylamine to study the mechanism. The data are consistent with the neutral amine being the form of the substrate that binds productively at the pH optimum, since the pKa seen in the kcat/Kamine pH profile for a group that must be unprotonated matches the pKa of dimethylamine. The D(kcat/Kamine) value decreases to unity as the pH decreases. This suggests the presence of an alternative pathway at low pH, in which the protonated substrate binds and is then deprotonated by an active-site residue prior to oxidation. The kcat and Dkcat values both decrease to limiting values at low pH with similar pKa values. This is consistent with a step other than amine oxidation becoming rate-limiting for turnover.

A faster and simpler UPLC-MS/MS method for the simultaneous determination of trimethylamine N-oxide, trimethylamine and dimethylamine in different types of biological samples.

Gut microbiota-dependent metabolites trimethylamine N-oxide (TMAO), trimethylamine (TMA) and dimethylamine (DMA) from dietary methylamines have recently gained much attention due to their high association with chronic kidney disease risk. Hence a simpler and faster performance liquid chromatography-tandem mass spectrometry method was developed and validated. The quantitative analysis was achieved within 6 min by using Agilent 6460C UPLC-MS/MS with 10% methyl alcohol isocratic elution and was more simple, convenient and rapid than that of previously reported methods. Furthermore, method verification results showed that the method correlation coefficient was 0.99978293, 0.99997514 and 0.98784721, and the detection limit was 0.121, 8.063 and 0.797 µg L-1, and the precision of the retention time and peak area of analytes was less than 0.331 and 3.280, respectively. The method was applied to simultaneously determine TMAO, TMA and DMA in the urine and serum from mice treated with normal, high l-carnitine, or high choline diet. Quantitative recoveries of TMAO, TMA and DMA were in the range of 94.2%-101.0%, and the RSD values were lower than 5.17%. The proposed UPLC-MS/MS-based assay should be of value for further evaluating TMAO as a risk marker and for examining the effect of dietary factors on TMAO metabolism.

Endotoxin removal from aqueous solutions with dimethylamine-functionalized graphene oxide: Modeling study and optimization of adsorption parameters.

Novel graphene oxide (GO)-based adsorbent embedded with epichlorohydrin (ECH) as a coupling agent and dimethylamine (DMA) as a ligand (GO-ECH-DMA) were prepared and employed for endotoxin removal from aqueous solutions. The physicochemical properties of nanocomposite were fully characterized. The model attributed to batch adsorption process was optimized employing response surface methodology (RSM) via various parameters such as pH, GO-ECH-DMA dosage, and contact time and endotoxin concentration. The p-value with low probability (<0.00001), determination coefficient (R2=0.99) and the non-significant lack of fit (p > 0.05) showed a quadratic model with a good fit with experimental terms. The synergistic effects of the linear term of contact time and GO-ECH-DMA dosage on endotoxin removal were significant. The optimum condition for endotoxin removal was obtained at pH of 5.52, GO-ECH-DMA dosage of 21 mgL-1, contact time of 56 min and endotoxin concentration of 51.3 endotoxin units per milliliter (EUmL-1). The equilibrium was the better explained by Langmuir isotherm with the maximum monolayer adsorption capacity of 121.47 EUmg-1, while the kinetics of the endotoxin adsorption process was followed by the pseudo-second-order model. The adsorbent could be recycled with NaOH. The possible mechanisms of endotoxin adsorption were proposed by hydrogen-bonding, π-π stacking, and electrostatic interaction.

Regeneration of aged DMF for use in solid-phase peptide synthesis.

Dimethylformamide (DMF), which is still the most commonly used solvent for Fmoc-SPPS, has the potential for degradation over time on exposure to air (and water vapour) and storage, to give dimethylamine and formic acid impurities. In particular, dimethylamine can lead to unwanted deprotection of the fluorenylmethyloxycarbonyl (Fmoc) group during, for example, the initial loading of Fmoc amino acids in SPPS, which leads reduced calculated loading values. We have found that treatment of such aged DMF by simple sparging with an inert gas (N2 ), or vacuum sonication, can regenerate the DMF in order to restore loading levels back to those found for newer, fresh, DMF samples.

Research on adsorption of Cr(â ¥) by Poly-epichlorohydrin-dimethylamine (EPIDMA) modified weakly basic anion exchange resin D301.

A novel composite, EPIDMA/D301, with high adsorption capacity and particular affinity toward Cr(Ⅵ) was well prepared utilizing cationic polyelectrolyte poly-epichlorohydrin-dimethylamine (EPIDMA) impregnated in the networking pores of the styrene macroporous weak basic anion exchange resin D301. The physicochemical characteristics of EPIDMA/D301 were characterized by the Brunauer-Emmett-Teller (BET), zeta potential, FTIR, SEM-Mapping and XPS. The adsorption properties were researched via the influence of the concentration of EPIDMA, adsorbent dose, pH, the initial concentration of Cr(Ⅵ) solution, contact time and temperature. Results presented that the weakly basic anion exchange resin supported cationic polymer showed the excellent potential of removing Cr(VI) ions primarily due to the nonspecific Cr(VI) adsorption resulted from the polymeric host D301, the electrostatic attraction of amino groups fixed on the D301 matrix and the embedded EPIDMA with Cr(VI) ions and the ion exchange by the displacement of Cl- mainly derived from EPIDMA with Cr(VI) ions. The kinetic data were best fitted by the pseudo-second-order kinetic model. The batch equilibrium data followed Langmuir isotherm model well with the maximum adsorption capacity of 194 mg g-1 at 25 °C, which demonstrated that the styrene anion exchange resin modified with EPIDMA might be an efficient approach to eliminate potentially toxic metals.

Preparation and Application of a New Crosslinked Polyammonium as a Shale Inhibitor.

BACKGROUND: Despite the fact that a number of traditional shale inhibitors have been utilized widely in drilling operations, the same additive may be unfavorable for different drilling due to environmental protection requirements which limit scales of use. Hence, a series of polyammonium compounds was prepared from dimethylamine, epichlorohydrin, and melamine (DEM). METHODS: To concentrate our efforts, we used both standard and extra methods to investigate the inhibitive properties of a melamine crosslinking agent using mud balls immersion tests, linear expansion measurements, laser particle distribution measurements, thermogravimetric analysis, and scanning electron microscopy. RESULTS: The anti-swelling rate of DEM-8 reached up to 92.3% when its concentration reached 0.8%. DEM-8 has strong inhibitive capability to bentonite hydration swelling. DEM-8 can affect the bentonite particle size at a large scale. It may adsorb on the surface of clay through hydrogen bonds and electrostatic interaction by an anchoring effect and a hydrophobic effect. CONCLUSIONS: Compared with a blank solution, DEM-8 displays high inhibitive ability against the hydration and swelling of clay. The mud ball is more stable in DEM-8 solution and its swelling degree is very low compared with that of the control test. The inhibition mechanism of DEM-8 to shale can be deduced in that hydrogen bonding, ion exchange, and anchoring effect help to control the hydration and swelling.