Hydrocarbon Radicals Research Articles

Study on the Optimization of Culture Parameters of Oxygen-Consuming Bacterium for Preventing CSC and Its Effect on the Coal Oxidation Characteristic

ABSTRACT Microorganisms can work together to prevent coal spontaneous combustion (CSC) by consuming oxygen and changing coal oxidation characteristics. In order to explore the influence of oxygen-consuming microorganisms on coal spontaneous combustion characteristics, a highly oxygen-consuming bacterium was isolated and identified from the soil near mine drainage, named ZQ-1. The oxygen consumption characteristics of microorganisms were investigated and optimized by single-factor and response surface experiments. Further, the effect of microorganisms on CSC was analyzed from both macroscopic and microscopic perspectives by using programmed warming, simultaneous thermal analysis, and Fourier-transform infrared spectroscopy (FTIR). The results revealed that the isolated bacterium was Pseudomonas aeruginosa. Its optimal culture conditions were pH = 6.98, temperature 28.15°C, and carbon nitrogen ratio (C/N) = 12.94 when the oxygen consumption rate was maximum. After bacterial action, coal showed a decrease in the release of the indicator gas CO during the combustion process, a delay in the cross point temperature (CPT) by 18.63°C, and an increase in the residual mass at the end of combustion. In addition, the average activation energy of the coal samples in the oxidative combustion stage was increased by 2.05721 kJ/mol. Finally, the FTIR results showed that microorganisms were able to destroy the reactive groups in the coal samples, especially hydroxyl, aliphatic hydrocarbon, and oxygen-containing functional groups, which resulted in the inhibition of CSC. This paper has important theoretical research value and practical significance for CSC prevention and control.

Crystallization‐Induced Dimerization and Solution‐Phase Bond Dissociation of Stable Dibenzoolympicenyl Radicals

Crystallization of organic materials can lead to different assembly structure with different reactivity, but this phenomenon is rarely observed for delocalized hydrocarbon radicals. This report introduces a crystallization‐induced radical–radical coupling reaction, which employs a series of stable nonplanar organic π‐radicals as reactants. Six stable radical congeners are synthesized, resulting in radical–radical coupling at the allenyl radical site during crystallization to produce close‐shell dimers. This coupling reaction is absent in the solution phase, which highlights the importance of preorganization in the lattice. Remarkably, the attempts of cocrystallization of different congeners yielded homocoupling products instead of cross‐coupling products. In specific cases, two distinct polymorphs are observed and their reactivity is different according to the distance of the reaction sites. Theoretical calculations indicate that the transition from a metastable preorganized monomer to a dimer is barrierless and spontaneous. The dimer could regenerate free radicals by heating or photoirradiation in the solution phase. This discovery may lead to controllable molecular switches.

Crystallization-Induced Dimerization and Solution-Phase Bond Dissociation of Stable Dibenzoolympicenyl Radicals.

Crystallization of organic materials can lead to different assembly structure with different reactivity, but this phenomenon is rarely observed for delocalized hydrocarbon radicals. This report introduces a crystallization-induced radical-radical coupling reaction, which employs a series of stable nonplanar organic π-radicals as reactants. Six stable radical congeners are synthesized, resulting in radical-radical coupling at the allenyl radical site during crystallization to produce close-shell dimers. This coupling reaction is absent in the solution phase, which highlights the importance of preorganization in the lattice. Remarkably, the attempts of cocrystallization of different congeners yielded homocoupling products instead of cross-coupling products. In specific cases, two distinct polymorphs are observed and their reactivity is different according to the distance of the reaction sites. Theoretical calculations indicate that the transition from a metastable preorganized monomer to a dimer is barrierless and spontaneous. The dimer could regenerate free radicals by heating or photoirradiation in the solution phase. This discovery may lead to controllable molecular switches.

Foreign experience in determining the group hydrocarbon composition of petroleum feedstock and petroleum products

Determination of the group hydrocarbon composition (saturated and aromatic hydrocarbons, resins, asphaltenes) of petroleum dispersed systems is predominantly carried out using chromatographic analysis methods: liquid adsorption chromatography, high-performance liquid chromatography, thin-layer chromatography with flame ionization detection. The specificity of standard methods developed for the analysis of petroleum feedstock and petroleum products using a particular method often results in the incompatibility of results both in terms of the nomenclature of the identified hydrocarbon groups and the determined concentration values. This review provides a comparative assessment of chromatographic methods for analyzing the group hydrocarbon composition of petroleum feedstock and petroleum products, their features, advantages, and disadvantages. The main options for modifying standard methods aimed at achieving correlation between the results obtained by different analysis methods are described.

DEVELOPMENT OF DRY BUILDING MIXTURES BASED ON REDISPERSIBLE POWDER FOR REGULATING THE PROPERTIES OF PLASTER MIXTURES

The relevance of the work. The results is theoretically substantiated and experimentally confirmed the possibility of obtaining a dry additive-retarder of gypsum setting based on lime and polyvinyl acetate dispersions due to the formation of polyvinyl alcohol and salts of calcium acetate in the result of alkaline hydrolysis of polyvinyl acetate dispersion (PVAD) with the slaked lime in hydrated lime. The results of the work implemented in the production of dry gypsum mixes. Purpose. The development of dry building mixes based on gypsum and time increase of time of their conformance through adding of complex additives on the basis of burnt lime and polyvinyl acetate dispersions [PVAD]. Methodology. The study used standard research techniques to determine physical and mechanical properties of gypsum binders and quality of complex additives according to ДСТУ Б В.2.7-82:2010, ДСТУ Б В.2.7-23-95, ДСТУ Б В.2.7-171:2008. Study of phase composition of materials, micro – and macrostructure was carried out by x-ray diffraction, electron and light microscopy. The results. The influence of the main components of the additive (polyvinyl acetate dispersion and lime) on the properties of hemihydrate gypsum is investigated. The chemistry of the interaction of components of the complex additive, according to which the result of alkaline hydrolysis of polyvinyl acetate is formed: polyvinyl alcohol, a feature of its molecules structure is the presence of hydrophilic OH−groups and the hydrophobic component − a hydrocarbon radical. The hydrophilic part of the molecule being ion adsorbed on the surface of the particles of the binder, forms a monomolecular layer that is oriented with the hydrophobic part of the gypsum particles. It is also possible the formation of calcium acetate Ca(СН3СОО)2, which increases the concentration of calcium ions in solution. The combined effect of hydrolysis products significantly reduce the solubility of hemihydrate, the rate of formation of crystallization centers, due to the slowing effect of these supplements.

Electronic Spectrum of α-Hydrofulvenyl Radical (C6H7), and a Simple and Accurate Recipe for Predicting Adiabatic Ionization Energies of Resonance-Stabilized Hydrocarbon Radicals.

Using a combination of resonant two-photon two-color ionization (R2C2PI) and laser-induced fluorescence/dispersed fluorescence spectroscopy, we have examined the 2A″ ← 2A″ transition of the resonance-stabilized α-hydrofulvenyl radical, produced from methylcyclopentadiene dimer in a jet-cooled discharge. Like the related 1,4-pentadienyl and cyclohexadienyl radicals, the α-hydrofulvenyl Ã-state lifetime is orders of magnitude shorter than the predicted f-value implies, indicative of rapid nonradiative decay. The transition is fully allowed by symmetry but considerably weakened by transition moment interference. Intensity borrowing among a' modes brings about static (i.e., Condon) and vibronic (i.e., Herzberg-Teller) moments of similar size, the result being a spectrum substantially less origin-dominated than is usually observed for extensively delocalized radicals. Twenty -state modes and twelve -state modes are identified with high confidence and assignments for several others are suggested. In addition, from a series of two-color appearance potential scans with the -state zero-point level serving as an intermediate, we obtain a field-free adiabatic ionization energy (AIE) of 7.012(1) eV. For a set of 21 resonance-stabilized radicals bearing 5 to 11 carbon atoms, it emerges that the field-free AIE obtained by R2C2PI methods under jet-cooled conditions lies very close to the average of B3LYP/6-311G++(d,p) (with harmonic zero-point energy) and CBS-QB3 0 K calculations, with a mean absolute deviation of only 0.010(7) eV (approximately 1 kJ/mol). On average, this represents a nearly 10-fold improvement in accuracy over CBS-QB3 predictions for the same set of radicals.

The Journey for the Synthesis of Large Acenes.

Acenes, the group of polycyclic aromatic hydrocarbons (PAHs) with linearly fused benzene rings, possess distinctive electronic properties with potential applicability in material science. Hexacene was the largest acene obtained and characterized in the last century, followed by heptacene in 2006. Since then, a race for obtaining the largest acene resulted in the development of several members of this family as well as diverse innovative synthetic strategies, from solid-state chemistry to the promising on-surface chemistry. This last technique allows the obtention of large acenes, up to tridecacene, the largest acene so far. This review presents the different methodologies employed for the synthesis of acenes, highlighting the newest studies, to provide a much more thorough understanding of the essence of the electronic structure of this captivating group of organic compounds.

Integrated approach to determining the identity of the pollution of adjacent territories with oil products

The methodology of arranging laboratory studies of oil-contaminated soils, soils and bottom sediments to determine the source and composition of hydrocarbon contamination is described. The complex approach to laboratory analysis of samples of oil-contaminated soils, soils and bottom sediments is proposed, which allows a highly reliable identification of the potential source of contamination and/or making conclusions about the identity of the contamination of adjacent territories. The proposed complex of analytical methods includes infrared spectrometry, gas chromatography with mass-selective detection, thin-layer chromatography with flame ionization detection and elemental analysis (C, H, N, S, O). Application of the proposed integrated approach allows highly reliable determination of the nature of oil contamination of soils, estimation of the total gross content of oil products and their hydrocarbon composition, and identification of the potential source of pollution. Possible errors in the interpretation of the results of determining the identity of contamination of territories and the importance of using an integrated approach in drawing conclusions about the source (culprit) of pollution are shown using real soil samples taken from oil-contaminated objects and adjacent territories. The importance of taking into account the losses of volatile oil products at the stage of sample preparation for soil contamination with light oil fractions is demonstrated. The use of standard methods of sample preparation (drying of the samples under study) leads to errors in assessing the level of contamination of territories with volatile hydrocarbons and in the choice of methods of remediation of contaminated territories. To minimize losses of volatile hydrocarbons (petrol and naphtha fractions) at the stage of soil sampling and transportation the use of sorbent is proposed. Addition of a sorbent to the soil contaminated with oil products can reduce losses of volatile hydrocarbons by 15 – 20% in the analyzed samples. Application of the developed complex approach makes it possible to determine the features of the individual hydrocarbon composition, group and elemental composition of petroleum products and identify hydrocarbon indicators (markers) inherent only to a certain type of petroleum product.

Novel Approach to Organization of Structured Cobalt-Based Fischer–Tropsch Catalyst

Structured Fischer–Tropsch synthesis catalysts were tested in tubular reactors of industry-standard diameters of 0.5 or 0.75 inches. The structured catalyst bed was manufactured by the obturation of a straight bunch of graphite-based extrudates (D = 1.5 mm, L = 30 mm). A conventional loose bed of granulated catalyst (D = 1.5 mm, L = 3 mm) was tested as a reference. In a 1000–3000 h−1 syngas space velocity range, structured and loose catalyst bed testing showed no significant differences in their main catalytic parameters. Nevertheless, their C5+ hydrocarbon group composition was quite different, i.e., the alkene fraction rose from 9 to 23%, while n-alkanes dropped from 81 to 64%. This could be a result of secondary reaction intensification in the conventional loose bed due to its zeolite acid site’s higher availability. Further FTS testing of the structured catalysts in 4000–6000 h−1 manifested distinctive limits in C5+ productivity for 0.5 and 0.75 inches of 512 kg C5+/(m3 reactor·h) and 362 kg C5+/(m3 reactor·h), respectively. This may be explained by limitations in structured bed thermal conductivity. It suggests that the arrangement of extrudates in the structured catalyst can significantly affect the reaction heat and mass transfer conditions and affords new opportunities for group composition control by means of catalyst bed organization.

Predicting thermochemical sulfate reduction reaction process and H2S generation in carbonate reservoirs using comprehensive kinetics modeling

Thermochemical sulfate reduction (TSR) is a critical process controlling hydrogen sulfide (H2S) generation in carbonate reservoirs, posing significant economic and safety challenges for the oil and gas industry. This study develops a comprehensive model that integrates detailed thermal, burial, and hydrocarbon generation histories with key TSR kinetic parameters, such as reaction rate constants and activation energies, to predict TSR evolution and H2S generation accurately. A notable feature of the model is to separate and quantify the contributions of different hydrocarbon species (CH4, C2-5, C6-14, and C15+) to the overall TSR process, using the Arrhenius equation to simulate the temperature-dependent behavior of TSR for each hydrocarbon group. The model also accounts for the in-reservoir thermal cracking of heavier hydrocarbons into light hydrocarbons, ensuring predictions closely align with geological processes. Modeling results show that TSR reactions accelerate the depletion of oil and wet gas components. A large amount of CH4 is generated due to both kerogen thermal cracking and alteration of heavy hydrocarbon. Our modeling also allows for accurate prediction of TSR reactions as well as the timing and extent of H2S and CO2 generation over the history of a reservoir. Applications in the Puguang and Hetianhe gas fields validate the model's broad applicability and reliability, capturing extensive TSR activities and being consistent with the observed data. These results underscore the models' robustness in detailed predictions of TSR dynamics across diverse geological settings and its potential as a valuable tool for managing sour gas production, aiding in risk assessment and resource management.

1,1'-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap.

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical 1 using a protection-oxidation-protection strategy. Diradical 1 demonstrated exceptional stability, with a solution half-life time exceeding 3.5 years and a solid state thermal decomposition temperature above 300 °C. X-ray crystallographic analysis revealed its intersected molecular structure and tightly bound dimer configuration. A singlet ground state with a small singlet-triplet energy gap is consistently identified using electron paramagnetic resonance (EPR) and a superconducting quantum interference device (SQUID) in a rigid matrix, and the triplet state is thermally accessible at room temperature. The solution phase properties were systematically examined through EPR, absorption spectroscopy, and cyclic voltammetry, revealing a rotational motion in the slow-motion regime and multistage redox characteristics. This study presents an efficient synthetic and stabilization strategy for organic diradicals, enabling the development of various high-spin functional materials.

Friction Mechanism of Sulfur-Containing Lubricant Additives Confined between Fe(100) Substrates.

Sulfur-containing lubricant additives can chemically react with metal surfaces under extreme conditions, such as high temperature and high pressure, forming protective films on the surfaces. However, the formation mechanisms and the friction-reducing and antiwear properties of these films remain unclear. In this study, we investigated the friction process of sulfur-containing additives confined between two iron surfaces using reactive molecular dynamics simulations. Our research revealed that in systems with a higher S/C ratio, an iron sulfide layer formed on the iron surfaces with Fe-S-Fe bridging bonds at the interface, resulting in relatively smaller friction and wear even under higher loads. However, in systems with lower S/C ratios, the presence of numerous interfacial Fe-Cn-Fe bridging bonds, caused by the hydrocarbon radicals released from the additives, led to the formation of thick amorphous shearing bands at the interface between the two substrates. In this case, the distributed sulfur atoms also exhibited some effect in reducing the shear resistance of the amorphous shearing bands due to the weak strength of S-Fe bonds compared to the strength of C-Fe bonds. These atomic-level insights help understand the antiwear characteristics of sulfur-containing lubricant additives confined between iron substrates.

Preparation of fully physically crosslinked double-network gel and its fire prevention mechanism

It is important to gain an in-depth understanding of the structure of fire prevention and extinguishing materials during self-heating of coal. In this paper, an Al3+-CMC/PAM-MMT fire prevention and extinguishing gel with double-network was prepared using sodium carboxymethyl cellulose (CMC) and polyacrylamide (PAM) as raw materials, and aluminum citrate (AlCit) and sodium montmorillonite (Na-MMT) as auxiliary materials, by introducing the fully physically crosslinking effect. The optimal amounts of CMC, PAM, AlCit and MMT were determined to be 2 %, 3 %, 8 %, and 3 %, respectively, based on gelation time, stability, and resistance of the gel. The micromorphological image of the double-network gel exhibited a laminar structure of parallel-aligned fibrous networks, where the pores and channels exhibited more complex shapes and became smaller in size, highlighting the superiority of the double-network architecture. The rheological tests showed that the double-network gel had superior structural stability and viscosity under varying shear rates, making it more effective in covering the fire source, enhancing extinguishing efficiency. Additionally, its higher storage and loss moduli indicated stronger elasticity and mechanical properties compared to the single-network gel, emphasizing its advantages in energy storage and recovery. The characterization of active functional groups showed that there was an effective suppression of reactions involving hydroxyl, hydrocarbon, and carbonyl functional groups, during the spontaneous combustion process of coal, following treatment with the gel. Additionally, a proposed mechanism for the gel formation was presented. In the sealing performance test, the pressure-bearing capacity of the double-network gel was approximately twice that of the single-network gel. It indicated that the multi-level structure formed by the gel led to higher density of physical cross-linking points, which provided better sealing performance. Thermogravimetric analysis showed significant decrease in total calorific value and increase in activation energy of coal, after treatment with the gel, rendering it more difficult for spontaneous coal combustion. In the small-scale fire extinguishing performance test, the double network of Al3+-CMC/PAM-MMT gel demonstrated effective suppression of spontaneous combustion of coal and reduced the susceptibility to re-ignition. The fire prevention mechanism of the gel was further explored experimentally.

Synthesis, Structure, Electrochemical Properties, and Antioxidant Activity of Organogermanium(IV) Catecholate Complexes.

A series of novel organogermanium(IV) catecholates 1-9 of the general formula R'2Ge(Cat), where R' = Ph, Et, have been synthesized. Compounds were characterized by 1H, 13C NMR, IR spectroscopy, and elemental analysis. The molecular structures of 1-3, 6, and 8 in crystal state were established using single-crystal X-ray analysis. The complexes are tetracoordinate germanium(IV) compounds containing a dioxolene ligand in a dianion (catecholato) form. Electrochemical transformations of target germanium(IV) complexes have been studied by cyclic voltammetry. The electro-oxidation mechanism of complexes 1-5, 7, and 10 (the related complex Ph2Ge(3,5-Cat) where 3,5-Cat is 3,5-di-tert-butylcatecholate) involves the consecutive formation of mono- and dicationic derivatives containing the oxidized forms of redox-active ligands. The stability of the generated monocations depends both on the hydrocarbon groups at the germanium atom and on the substituents in the catecholate ring. Compounds 6, 8, and 9 are oxidized irreversibly under the electrochemical conditions with the formation of unstable complexes. The radical scavenging activity and antioxidant properties of new complexes were estimated in the reaction with DPPH radical, ABTS radical cation, and CUPRACTEAC assay. It has been found that compounds 8 and 9 with benzothiazole or phenol fragments are more active in DPPH test. The presence of electron-rich moieties in the catecholate ligand makes complexes 5 and 7-9 more reactive to ABTS radical cation. The value of CUPRACTEAC for organogermanium(IV) catecholates varies from 0.23 to 1.45. The effect of compounds 1-9 in the process of lipid peroxidation of rat liver (Wistar) homogenate was determined in vitro. It was found that most compounds are characterized by pronounced antioxidant activity. A feature of complexes 1, 3, and 5-9 is the intensification of the antioxidant action with the incubation time. In the presence of additives of complexes 3, 5, 6, and 8, an induction period was observed during the process of lipid peroxidation.

Study on microstructure evolution and oxidation kinetics in Coal-Oil Symbiosis

Differences in the spontaneous combustion mechanism characteristics of Coal-Oil Symbiosis (COS) significantly affect coal mines' safety management and ecological environment maintenance. Accordingly, this study aims to investigate COS's macroscopic and microstructural characteristics with different oil mass percentage using simultaneous thermal analysis, low-temperature N2 adsorption, scanning electron microscopy (SEM), and in-situ Fourier transform infrared spectroscopy (FTIR). The results showed that with the increase of oil mass percentage, the COS displayed the weakening of oxygen absorption and the advance of some characteristic temperatures, and 11.5 °C advanced the maximum weight loss temperature on average. For the 25 % oil sample, the ignition temperature was 9.5 °C lower than that of the raw coal. Additionally, the apparent activation energy of the high oil mass percentage sample was significantly reduced in the pyrolysis and combustion stages, and when the oil mass percentage was 25 %, the activation energies of the two stages decreased by 89 % and 60.65 %, respectively. Compared to raw coal, COS exhibits fewer macropores and surface pores covered by oil, which limits oxygen adsorption. Moreover, COS with higher oil mass percentage had an increase in hydroxyl and aliphatic hydrocarbon groups, and the CH3 + CH2 content of COS increased by 69.2 % on average, providing more active groups, thereby promoting spontaneous combustion. This study provides an important reference and theoretical support for further understanding the structural evolution and oxidation kinetic behavior of COS, contributing to disaster prevention and ecological environmental protection in coal-oil coexistence mining areas.

Novel sialidase inhibitors suppress mumps virus replication and infection.

The prevalent human pathogen, mumps virus (MuV; orthorubulavirus parotitidis) causes various complications and serious sequelae, such as meningitis, encephalitis, deafness, and impaired fertility. Direct-acting antivirals (DAAs) targeting MuV which can prevent mumps and mumps-associated complications and sequelae are yet to be developed. Paramyxoviridae family members, such as MuV, possess viral surface hemagglutinin-neuraminidase (HN) protein with sialidase activity which facilitates efficient viral replication. Therefore, to develop DAAs targeting MuV we synthesized MuV sialidase inhibitors. It is proposed that the viral HN has a single functional site for N-acetylneuraminic acid (Neu5Ac) binding and sialidase activity. Further, the known MuV sialidase inhibitor is an analog of Neu5Ac-2,3-didehydro-2-deoxy-N-acetylneuraminic acid (DANA)-which lacks potency. DANA derivatives with higher MuV sialidase inhibitory potency are lacking. The MuV-HN-Neu5Ac binding site has a hydrophobic cavity adjacent to the C4 position of Neu5Ac. Exploiting this, here, we synthesized DANA derivatives with increasing hydrophobicity at its C4 position and created 3 novel sialidase inhibitors (Compounds 1, 2, and 3) with higher specificity for MuV-HN than DANA; they inhibited MuV replication step to greater extent than DANA. Furthermore, they also inhibited hemagglutination and the MuV infection step. The insight-that these 3 novel DANA derivatives possess linear hydrocarbon groups at the C4-hydroxyl group of DANA-could help develop highly potent sialidase inhibitors with high specificity for MuV sialidase, which may function as direct-acting MuV-specific antivirals.

The Effect of Individual Hydrocarbons in the Composition of Diesel Fuel on the Effectiveness of Depressant Additives

The use of depressant additives is the most effective and cost-effective way to improve the low-temperature properties of diesel fuels, like the cloud point, cold filter plugging point and pour point. However, the effectiveness of depressant additives depends on the composition of the diesel fuel and the content of certain groups of hydrocarbons in it. In this work, the effect of adding individual hydrocarbons of various groups and structures on the effectiveness of depressant additives is studied. This study is carried out on model aromatic (toluene, tetralin) and n-paraffin hydrocarbons (cetane, heptadecane, heneicosane, docosane) in various concentrations. It is shown that the most negative effect on the depressant additives’ effectiveness is due to the content of the most polar aromatic hydrocarbons and light n-paraffins in the composition of diesel fuel, and the most positive effect is exerted by the content of heavy n-paraffins in small quantities. It is proposed to involve small concentrations (1–3% vol.) of heavy n-paraffin hydrocarbons (heneicosane, docosane) to increase the effectiveness of the depressant additive. It has been established that for the more effective action of the depressant, it is necessary to take into account the content and structure of individual hydrocarbons in the diesel fuel’s composition.

Exploring Favorable Supramolecular Interactions of Multifluorinated Aromatics in Dendronized Push-Pull Chromophores for Electro-Optics.

Multifluorinated aromatics serve as supramolecular synthons in the research of organic electro-optic (EO) materials by exploiting π-π stacking interaction between the aromatic hydrocarbon and multifluorinated aromatic groups for performance improvement. However, non-classical hydrogen bonding remains largely unexplored in fluorinated EO dendrimers. In this study, three Fréchet-type generation 1 benzyl ether co-dendrons were synthesized by replacing one benzyl group with 2,3,5,6-tetrafluorobenzyl (p-HF4Bz), pentafluorobenzyl (C6F5Bz), and 2,3,4,5-tetrafluorobenzyl (o-HF4Bz) groups, to afford the benzoic acid derivatives D1, D2, and D3, which were further bonded to the donor and π-bridge moieties to afford three co-dendronized push-pull phenyltetraene chromophores EOD1, EOD2, and EOD3, respectively. The weak C-H⋅⋅⋅X (X=O, F) interactions in the crystal structure of D1 cumulatively add to the benzoic acid dimers to form an extended hydrogen-bonded network, while D2 is crystallized into a centric one-dimensional chain with strong intermolecular interactions. The poled films of EOD1 with PMMA exhibited the largest and most stable EO activity with optical homogeneity among the series. The results identify the effectiveness of weak but favorable hydrogen bonds enabled by the enhanced carbon acidity of p-HF4Bz synthon in D1, over the interactions in D2 and D3, for the rational design of supramolecular EO dendrimers.

Peri-Benzo-Diindenotetracenyl: Helically π-Extended Allyl Radical with Robust Stability.

Here is described the synthesis and characterization of a stable hydrocarbon radical, peri-benzo-diindenotetracenyl, with a helical structure. Although the helical π-radical has no peripheral substituents, it was stable in the solid and solutions. According to the X-ray diffraction analysis and quantum chemical calculations, the radical was best described as an allyl radical fused by five Clar's sextets. The optically resolved enantiomers exhibited mirror image CD spectra with |gCD| of 2.4×10-4 at 522 nm. The racemization barrier was determined to be 95.9 kJ/mol at 298 K, which is compatible with that of [5]helicene (108 kJ/mol).

Au-TiO2 nanoparticles enabled catalytic treatment of oil and gas produced water in slurry and vacuum membrane distillation systems

Produced water (PW) treatment and reuse provide a promising alternative to address freshwater scarcity and reduce the environmental impacts associated with PW disposal. Efficient treatment of PW is challenging due to its complex matrix and hypersalinity. This study developed innovative gold-doped titania (Au-TiO2) nanoparticles to enable effective treatment of PW collected from the Permian Basin with salinity of ∼118 g/L. The mechanisms of removing organics and ammonia in PW in slurry and vacuum membrane distillation (VMD) systems were investigated via thermocatalysis, photocatalysis, and photo-thermocatalysis. Photocatalysis and photo-thermocatalysis were found more effective for organic removal than thermocatalysis. A baseline study using glucose as a representative of easily degradable organic carbon showed that thermocatalysis and photocatalysis mineralized 23.2 % and 93.1 % glucose, respectively. However, photo-thermocatalysis and thermocatalysis degraded only 17.4 % and 7.5 % dissolved organic carbon (DOC), and 56.2 % and 49.2 % NH3-N in PW, respectively. Au-TiO2 coating on ceramic membranes improved the distillate flux of photo-thermocatalytic membrane distillation (PMD) compared to no catalysts coating in VMD (7.14 versus 6.75 kg per hour per m2). Both PMD and VMD rejected >99.9 % of salts and >96 % DOC, and PMD had slightly higher DOC and salt removal rates. In contrast, normalized permeate flux using pristine membranes (hydrophobically modified without catalysts coating) decreased to zero after 29 h of operation while normalized flux with TiO2-coated membranes under UV on and UV off were 57.5 % and 53.7 % on average, which is much lower than that with Au-TiO2 coated membranes in both UV on (91.3 %) and UV off (88.1 %) cases, indicating Au-TiO2 coating significantly improved membrane anti-fouling propensity and durability during treatment of complex PW. Targeted analysis of three groups of petroleum hydrocarbons and 70 volatile organic compounds showed that only 2-butanone and acetone were detected in the distillates with removal efficiencies of 80 % for 2-butanone in both PMD and VMD, and acetone was removed by 75.4 % in PMD and 69.2 % in VMD. Au-TiO2 nanoparticles demonstrated excellent catalytic performance for PW treatment in slurry and immobilized PMD systems.