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13,14-diphenyldibenzo[b,j][4,7]phenanthroline (DBP3) in various solvents was studied by time-resolved fluorescence and fs transient absorption (fs-TA) spectroscopy. An intramolecular benzene excimer is demonstrated to form within DBP3; it exhibits strong redshifted emission with maximum at 540–640 nm. "Intrinsic" fluorescence from DBP3 is dramatically quenched down to τ = 50–400 fs in all the solvents studied. Fs-TA and time-resolved fluorescence spectra have proved that relaxed intramolecular benzene excimer is formed from S1 state via hot excimer state with three lifetime components: 50 fs, ∼3.5 ps, and ∼25 ps, which are of the inertial (electronic) and diffusive parts of the relaxation due to solute–solvent interaction. Formation of triplet states via intersystem crossing was observed directly from the upper excited electronic states of DBP3. [ABSTRACT FROM AUTHOR]

The three-body fragmentation dynamics of benzene trications C 6 H 6 3 + induced by 200 eV electron-impact produced by a photoemission cathode is investigated. All three fragment ions are detected in coincidence, and their momentum vectors are determined by employing a COLTRIMS reaction microscope. The detailed kinematical information of three deprotonation fragmentation channels of H+ + C 3 H 2 + + C 3 H 3 + , H+ + C 2 H 3 + + C 4 H 2 + , and H+ + C 2 H 2 + + C 4 H 3 + are obtained. By analyzing the momentum and energy correlation spectra among all the three fragment ions, we find that all the three channels are primarily generated by sequential fragmentation processes. Each channel has two deprotonation pathways, corresponding to proton emission in the first or second step of sequential fragmentation, respectively. These results provide insight into the mechanisms and dynamics of deprotonation and ring-breaking reactions in the three-body fragmentation processes of aromatic ring molecules. [ABSTRACT FROM AUTHOR]

The double-ion chamber (DIC) method has been used to measure photoabsorption cross sections in the ionization region of the sample gas. In this study, we introduce a method to extend the wavelength region of the DIC measurements beyond the ionization threshold wavelength by using the photoion currents from the impurities in the sample gas. To verify this method, the photoabsorption cross sections of C2H2 (ionization threshold wavelength λth = 108.8 nm) have been measured from 105 to 137 nm. The natural impurity, acetone (λth = 127.8 nm), contained 1% in high-purity grade acetylene (C2H2) sample gas, allowing for measurements in the non-ionizing region of C2H2 up to 127.7 nm. By adding 1% benzene (λth = 134.6 nm) in the sample gas, measurements were possible even further, to 134.5 nm. This new method enables the measurement of the photoabsorption cross section by photoions that are produced from the impurities in the sample gas in a substantial amount. The current measurement methodology aligns well with the previous measurements of Suto and Lee [Suto and Lee, J. Chem. Phys. 80, 4824 (1984)]. [ABSTRACT FROM AUTHOR]

The CH stretch overtone region (5750–6300 cm−1) of benzene and naphthalene is assigned herein using anharmonic quantum chemical computations, and the trend of how this extends to larger polycyclic aromatic hydrocarbons (PAHs) is established. The assignment of all experimental bands to specific vibrational states is performed for the first time. Resonance polyads and the inclusion of 3-quanta vibrational states are both needed to compute accurate vibrational frequencies with the proper density-of-states to match the experimental band shape. Hundreds of 3-quanta states produce the observed band structure in naphthalene, anthracene, and tetracene, and this number is expected to increase drastically for larger PAHs. The width and shape of the main peak are consistent from naphthalene to anthracene, necessitating further exploration of this trend to confirm whether it is representative of all PAHs in the CH stretch overtone region. Understanding observations of PAH sources in the 1–3 μm region from the NIRSpec instrument aboard JWST requires new computational data, and this study provides a benchmark and foundation for their computation. [ABSTRACT FROM AUTHOR]

To fill a research gap on firefighter exposures and breast cancer risk, and guide exposure reduction, we aimed to identify firefighter occupational exposures linked to breast cancer. We conducted a systematic search and review to identify firefighter chemical exposures and then identified the subset that was associated with breast cancer. To do this, we compared the firefighter exposures with chemicals that have been shown to increase breast cancer risk in epidemiological studies or increase mammary gland tumors in experimental toxicology studies. For each exposure, we assigned a strength of evidence for the association with firefighter occupation and for the association with breast cancer risk. We identified twelve chemicals or chemical groups that were both linked to breast cancer and were firefighter occupational exposures, including polycyclic aromatic hydrocarbons, volatile aromatics, per- and polyfluoroalkyl substances, persistent organohalogens, and halogenated organophosphate flame retardants. Many of these were found at elevated levels in firefighting environments and were statistically significantly higher in firefighters after firefighting or when compared to the general population. Common exposure sources included combustion byproducts, diesel fuel and exhaust, firefighting foams, and flame retardants. Our findings highlight breast-cancer-related chemical exposures in the firefighting profession to guide equitable worker's compensation policies and exposure reduction.

We report high-level calculations of the excited states of [2,2]-paracyclophane (PCP), which was recently investigated experimentally by ultrafast pump–probe experiments on oriented single crystals [Haggag et al., ChemPhotoChem 6 e202200181 (2022)]. PCP, in which the orientation of the two benzene rings and their range of motion are constrained, serves as a model for studying benzene excimer formation. The character of the excimer state and the state responsible for the brightest transition are similar to those of the benzene dimer. The constrained structure of PCP allows one to focus on the most important degree of freedom, the inter-ring distance. The calculations explain the main features of the transient absorption spectral evolution. This brightest transition of the excimer is polarized along the inter-fragment axis. The absorption of the light polarized in the plane of the rings reveals the presence of other absorbing states of Rydberg character, with much weaker intensities. We also report new transient absorption data obtained by a broadband 8 fs pump, which time-resolve strong modulations of the excimer absorption. The combination of theory and experiment provides a detailed picture of the evolution of the electronic structure of the PCP excimer in the course of a single molecular vibration. [ABSTRACT FROM AUTHOR]

BackgroundA growing literature has reported associations between traffic-related air pollution and breast cancer, however there are fewer investigations into specific ambient agents and any putative risk of breast cancer development, particularly studies occurring in populations residing in higher pollution areas such as Los Angeles.ObjectivesTo estimate breast cancer risks related to ambient air toxics exposure at residential addresses.MethodsWe examined the relationships between ambient air toxics and breast cancer risk in the Multiethnic Cohort among 48,665 California female participants followed for cancer from 2003 through 2013. We obtained exposure data on chemicals acting as endocrine disruptors or mammary gland carcinogens from the National-Scale Air Toxics Assessment. Cox proportional hazards models were used to estimate breast cancer risk per one interquartile range (IQR) increase in air toxics exposure lagged by 5-years. Stratified analyses were conducted by race, ethnicity, and hormone receptor types.ResultsAmong all women, increased risks of invasive breast cancer were observed with toxicants related to industries [1,1,2,2-tetrachloroethane (hazard ratio [HR] = 4.22, 95% confidence interval [95% CI] 3.18-5.60), ethylene dichloride (HR = 2.81, 95% CI 2.20-3.59), and vinyl chloride (HR = 2.27, 95% CI 1.81, 2.85); these 3 agents were correlated (r2 = 0.45-0.77)]. Agents related to gasoline production or combustion were related to increased breast cancer risk [benzene (HR = 1.32, 95% CI 1.24, 1.41), ethylbenzene (HR = 1.20, 95% CI 1.13-1.28), toluene (HR = 1.29, 95% CI 1.20-1.38), naphthalene (HR = 1.11, 95% CI 1.02-2.22), acrolein (HR = 2.26, 95% CI 1.92, 2.65)]. Higher hazard ratios were observed in African Americans and Whites compared to other racial and ethnic groups (p-heterogeneity

To spectroscopically qualify strength in the π-electron conjugation, the electronic spectra of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB) in the region of the transition to the lowest excited singlet (S1) 1B1u state are measured by the fluorescence excitation and the single-vibronic-level dispersed fluorescence methods. Strength is defined as the difference in potential energies between the planar and perpendicular conformations. BPEB possesses two large-amplitude torsional motions, out-of-phase 24 and in-phase 29 modes. The most stable is the planar conformation, and barrier heights at the perpendicular conformation are coincident in torsional potentials for the two modes. Torsional levels are successively observed up to 19± and 16− quantum levels in the ground state, respectively. Strength is determined to be 293 cm−1 (3.51 kJmol−1) with an accuracy of an error range smaller than 1 cm−1. In the excited state, strength is estimated to be 1549 ± 73 cm−1. Combination levels of two torsional modes are also measured up to high quantum levels. A systematic decrease in frequencies is observed with increasing the quantum number. Quantum-chemistry calculations of B3LYP, CAM-B3PLYP, WB97XD, and M062X with basis sets of aug-cc-pVDZ are performed, where B3LYP theories are carried out with the dispersion correlation. The calculated strength is 1.1–2.1 times larger than observed. [ABSTRACT FROM AUTHOR]

The Random-Phase approximation (RPA) provides an appealing framework for semi-local density functional theory. In its Resolution-of-the-Identity (RI) approach, it is a very accurate and more cost-effective method than most other wavefunction-based correlation methods. For widespread applications, efficient implementations of nuclear gradients for structure optimizations and data sampling of machine learning approaches are required. We report a well scaling implementation of RI-RPA nuclear gradients on massively parallel computers. The approach is applied to two polymorphs of the benzene crystal obtaining very good cohesive and relative energies. Different correction and extrapolation schemes are investigated for further improvement of the results and estimations of error bars. [ABSTRACT FROM AUTHOR]

While carrying out Beyond Born–Oppenheimer theory based diabatization, the solutions of adiabatic-to-diabatic transformation equations depend on the paths of integration over two-dimensional cross-sections of multi-dimensional space of nuclear degrees of freedom. It is shown that such path-dependent solutions leading to diabatic potential energy surface matrices computed along any two different paths are related through an orthogonal matrix, and thereby, those surface matrices should provide unique observables. While exploring the numerical validity of the theoretical framework, we construct diabatic Hamiltonians for the five low-lying electronic states ( X ̃ 2 E 1 g , B ̃ 2 E 2 g , and C ̃ 2 A 2 u ) of benzene radical cation ( C 6 H 6 + ) along three different approaches of contour integration over two dimensional nuclear planes constituted by seven non-adiabatically active normal modes. Three different diabatic surface matrices are further employed to generate the photoelectron spectra of the benzene molecule (C6H6). It is interesting to note that the spectral peak positions and intensity patterns for all three cases are almost close to each other and also exhibit very good agreement with the experimental results. [ABSTRACT FROM AUTHOR]

We report experimental differential cross sections (DCSs) for electron impact excitation of bands I to V of benzene at incident energies of 10, 12.5, 15, and 20 eV. They are compared to calculations using the Schwinger multichannel method while accounting for up to 437 open channels. For intermediate scattering angles, the calculations reveal that the most intense band (V) emerges from surprisingly similar contributions from all its underlying states (despite some preference for the dipole-allowed transitions). They further shed light on intricate multichannel couplings between the states of bands I to V and higher-lying Rydberg states. In turn, the measurements support a vibronic coupling mechanism for excitation of bands II and IV and also show an unexpected forward peak in the spin-forbidden transition accounting for band III. Overall, there is decent agreement between theory and experiment at intermediate angles and at lower energies and in terms of the relative DCSs of the five bands. Discrepancies between the present and previous experiment regarding bands IV and V draw attention to the need of additional experimental investigations. We also report measured DCSs for vibrational excitation of combined C–H stretching modes. [ABSTRACT FROM AUTHOR]

The combination of aromatic and aliphatic structures can endow polyurea with distinct performance advantages. A one‐step feeding method is used to synthesize linear hybrid aliphatic/aromatic copolyureas by varying the ratio of m‐phenylenediamine (MPD) and polyoxypropylenediamine (D2000) reacting with 4,4′‐diphenylmethane diisocyanate (MDI). Real‐time Fourier‐transform infrared spectrometer monitoring reveals that D2000 exhibits higher reactivity than MPD. Consequently, in the MDI/MPD/D2000 system, D2000 initially reacts with MDI to form an isocyanate‐terminated prepolymer, which subsequently reacts with MPD. Compared with the two‐step feeding method, this approach successfully eliminates biuret formation and enhances tensile strength. Additionally, decreasing the molar ratio of D2000 to MPD (λm) reduces the size and degree of microphase separation in the polyurea by increasing the ordered hydrogen bonding and benzene conjugation, leading to an increase in tensile strength. Specifically, as λm decreases from 70 mol% to 30 mol%, the degree of microphase separation decreases from 0.47 to 0.2, causing the tensile strength to rise from 28 to 48 MPa. Further reducing λm to 30 mol% decreases the degree of microphase separation to 0.16, resulting in an increase in tensile strength to 78 MPa. [ABSTRACT FROM AUTHOR]

The destruction of benzene in a dielectric barrier discharge (DBD) reactor was studied in this work. The effects of specific energy density, initial concentration and oxygen content on benzene degradation efficiency were investigated by experiment and matrix correlation analysis. The results showed that specific energy density was the most important factor on benzene removal with a Pearson's coefficient of 0.7, meanwhile both initial concentration and oxygen content presented the inverse influence. In addition, a model to study the plasma discharge process was developed by COMSOL simulation software and surface reactions were included in the model. The behavior of the plasma was described by the coupled equations of electron density, heavy matter density and electron mean energy, and the drift-diffusion equation was calculated. When the peak voltage is 30 kV, the terminal current obtained by the simulation is 0.03 A, and the corresponding output current measured by the experiment is 0.013 A. Simulated and experimental current change trends are the same, indicating that the method simulation is correct and reasonable. [ABSTRACT FROM AUTHOR]

Long-term exposure to Volatile Organic Compounds (VOCs) is a health risk for citizens. In this study, the cumulative health risk of exposure to VOCs in Tehran was assessed by investigating the concentration of these pollutants in ambient air in a five-year period. Health risk assessment was calculated by the quantitative method and the carcinogenic risk level was determined using the lifetime carcinogenic risk (LCR) method. The average concentration of benzene, toluene, ortho-xylene, and ethylbenzene was 1.4–1.8, 4.8–5.4, 5–6.5, and 3.6–4 ppb, respectively. Although HQ was not greater than 1, but it was very close in the case of benzene, ortho-xylene, meta-xylene, and para-xylene. Benzene and ethylbenzene had the largest effect in the assessed health risk. So the long-term exposure of Tehran citizens to VOCs has serious health consequences for them, which could be different according to the exposure time and spatial variations. [ABSTRACT FROM AUTHOR]

Intermolecular interactions with polycyclic aromatic hydrocarbons (PAHs) represent an important area of physisorption studies. These investigations are often hampered by a size of interacting PAHs, which makes the calculation prohibitively expensive. Therefore, methods designed to deal with large molecules could be helpful to reduce the computational costs of such studies. Recently we have introduced a new systematic approach for the molecular fragmentation of PAHs, denoted as AROFRAG, which decomposes a large PAH molecule into a set of predefined small PAHs with a benzene ring being the smallest unbreakable unit, and which in conjunction with the Molecules‐in‐Molecules (MIM) approach provides an accurate description of total molecular energies. In this contribution we propose an extension of the AROFRAG, which provides a description of intermolecular interactions for complexes composed of PAH molecules. The examination of interaction energy partitioning for various test cases shows that the AROFRAG3 model connected with the MIM approach accurately reproduces all important components of the interaction energy. An additional important finding in our study is that the computationally expensive long‐range electron‐correlation part of the interaction energy, that is, the dispersion component, is well described at lower AROFRAG levels even without MIM, which makes the latter models interesting alternatives to existing methods for an accurate description of the electron‐correlated part of the interaction energy. [ABSTRACT FROM AUTHOR]

The selective separation of Am(III) over Eu(III) from high-level radioactive liquid waste using four bis-succinamide ligands (THE-BisSCA, L1; THDM-BisSCA, L2; THDPh-BisSCA, L3; THDi−P-BisSCA, L4) was explored with density functional theory. Ligands with phenyl groups near the nitrogen, particularly L3, showed the highest Eu(III) affinity. The π bonds orbitals of the benzene ring may conjugate with the long pair N-2p orbital, and this special p-π conjugation effect can lead to charge transfer from benzene ring to the donor N atoms on L3 ligand, resulting a lower energy and more stable structure of the complex formed with the L3 ligand compared to other complexes. Thermodynamic analysis corroborates L3 has Eu(III) preference, offering valuable guidance for efficient Am(III) and Eu(III) separation with these ligands. [ABSTRACT FROM AUTHOR]

The increasing demand for natural products in the United States reflects a cultural shift towards health and sustainability. This trend infiltrates consumer sectors such as the sunscreen industry, amidst concerns about health and environmental impacts of chemical ingredients. The Hawaii Sunscreen Ban has intensified sunscreen formula safety discussions, particularly regarding butylparaben, oxybenzone, and octinoxate. Even at low concentrations, these compounds bleach hard corals eventually leading to their death. As well, these chemicals pose threats to marine ecosystems and raise concerns about human health, particularly systemic absorption and the possibility of causing endocrine disruption. While some argue for chemical-based sunscreens for skin cancer prevention, others advocate for mineral-based alternatives that avoid harmful ingredients. However, public opinion on sunscreen varies, influenced by adverse reactions, socioeconomic status, gender, and cultural perceptions. Future studies should explore diverse demographic perspectives and long-term health and environmental impacts of products containing potentially toxic ingredients. As well, effective communication strategies to promote sunscreen safety and encourage sustainable sun protection practices is needed. [ABSTRACT FROM AUTHOR]

Supercritical water (SCW) gasification technology can enable the efficient utilization of coal by converting it to hydrogen-rich gas. However, poly-cyclic aromatic hydrocarbons and heavy components, which are intermediates of supercritical water gasification, tend to generate char, hindering the complete gasification of coal. In this work, phenol is recycled to enhance the gasification process and reduce the formation of these intermediates during SCWG, and the regulation mechanism is investigated. The results demonstrate that both gas yield and gasification efficiency increase with the presence of phenol, reaching approximately 98.5% at 750 °C, concentration of 2%with the effect of phenol, which is 27% higher than that in the coal-water system. Organics removal rate reaches about 98% with the addition of phenol. Phenol can enhance the gasification performance by facilitating the conversion of heavy components to lightweight components. The transient reactivity of coal in the poly-condensation stage is increased by about 50 times with the presence of phenol. The regulation mechanism of phenol in the poly-condensation stage during coal gasification involves the decomposition of SCW forming hydroxyl radicals, which replaces the substituents on the benzene ring, facilitating the dissociation of benzene ring into small molecules that are prone to polymerize. The interacting force between phenol and multi-rings disrupts the conjugate structure, aiding in the decomposition of polycyclic organics into small molecules. • Investigated the regulating mechanism of phenol on the gasification process. • Hydrogen yield and gasification efficiency increases with the presence of phenol. • Nearly complete gasification (98.5%) is realized with the presence of phenol. • The organics removal rate reaches about 98% with the presence of phenol. • Reactivity of coal in the polycondensation stage increased by 50 times with phenol. [ABSTRACT FROM AUTHOR]

The spirocyclic framework is found in many natural products, some of which are biologically active. However, It remains a challenge to develop environmentally friendly and atom‐economic synthetic methods. Herein, we report an intramolecular dearomatization reaction of benzene derivatives enabled by electrochemistry‐mediated two successive single‐electron‐transfer (SET) processes, providing an alternative method for the rapid construction of spirocyclic skeletons without using sacrificial reagents. A series of cyclohexadiene products were obtained in 25–81% yields. Furthermore, a proposed mechanism involving a sequential electron transfer event was supported by cyclic voltammetry experiments. This strategy features transition‐metal‐free conditions and easy handling, which will greatly enhance its practical utility. [ABSTRACT FROM AUTHOR]

In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole‐fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative [1,5]‐sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This “walk” shift was confirmed by the isolation of a cycloheptatriene species derived from ring‐expansion of a dearomatized alkynylated heterole‐fused norcaradiene. A following ester‐directed ring‐opening rearomatization of these dearomatized heterole‐fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero) arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole‐fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes. [ABSTRACT FROM AUTHOR]

The bulky monodentate carbazolyl ligand 1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazole (dtbpCbz) was employed in the synthesis of monomeric heteroleptic amido carbazolyl complexes of Ca and Yb. For both central metal atoms, dimeric hydride complexes [(dtbpCbz)Ca(benzene)H]2, [(dtbpCbz)Ca(THF)H]2, [(dtbpCbz)Yb(benzene)H]2 and [(dtbpCbz)Yb(THF)H]2 were obtained, which show remarkably poor solubility in organic solvents. The characteristic hydride 1H NMR resonance of [(dtbpCbz)Ca(benzene)H]2 was observed at 2.07 ppm, and for the first time, characteristic vibrational modes of the Ca2H2 and Yb2H2 moiety are discussed. Despite their poor solubility, the hydride complexes could be reacted with CO to yield the corresponding ethenediolate complexes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Objective To understand the occupational health status of workers in selected industries with key occupational hazards in Guangzhou and to provide a basis for formulating occupational health protection strategies in Guangzhou. Methods A descriptive epidemiological method was used to analyze the occupational health status of workers working with silica dust, benzene, lead, and noise during their on -the -job period in Guangzhou from 2016 to 2023. Results There were 798 869 records of occupational health examinations during this period among the examined workers exposed to silica dust, benzene, lead, and noise in Guangzhou from January 1, 2016 to December 31, 2023. Of them, there were 14 072 examinations for silica dust exposure (1.76%), 99 046 for benzene exposure (12.40%), 10 441 for lead exposure (1.31%), and 675 310 for noise exposure (84.53%). Over the eight years, 566 suspected cases of occupational diseases were detected, with a detection rate of 0.07%. The detection rates of suspected occupational diseases were, in order, 0.09% (13/14 072) for suspected occupational silicosis, 0.07% (501/675 310) for suspected occupational noise-induced hearing loss, 0.05% (50/99 046) for suspected occupational benzene poisoning, and 0.02% (2/10 441) for suspected occupational chronic lead poisoning. A total of 13 619 cases of occupational contraindications were detected, with a detection rate of 1.70%; of these, the higher detection rates were in noise exposure (1.86%, 12 556/675 310), benzene exposure (1.11%, 1 101/99 046), and silica dust exposure (0.50%, 71/14 072). The detected abnormal rates of critical effect indicators in 2016-2023 were as follows: 8.04% for noise exposure (57 917/720 802), 1.54% for benzene exposure (1 503/97 488), 1.31% for lead exposure (79/6 028), and 0.50% for silica dust exposure (61/12 189). The detection rates of leukopenia in benzene-exposed workers and elevated blood lead levels in lead-exposed workers showed an upward trend over time (P < 0.05). Additionally, the exposed workers in manufacturing, small and medium-sized microenterprises, and domestic enterprises had higher rates of occupational health damage. Conclusions The current health status of workers exposed to silica dust, benzene, lead, and noise in Guangzhou was generally acceptable. However, there were still some workers who had suspected occupational diseases and/or occupational contraindications, especially those exposed to noise. Therefore, it is necessary to accurately identify and prevent various occupational diseases through standardized occupational health examinations. [ABSTRACT FROM AUTHOR]

Benzene is a widespread groundwater contaminant that persists under anoxic conditions. The aim of this study was to more accurately investigate anaerobic microbial degradation pathways to predict benzene fate and transport. Preliminary genomic analysis of Geotalea daltonii strain FRC-32, isolated from contaminated groundwater, revealed the presence of putative aromatic-degrading genes. G. daltonii was subsequently shown to conserve energy for growth on benzene as the sole electron donor and fumarate or nitrate as the electron acceptor. The hbs gene, encoding for 3-hydroxybenzylsuccinate synthase (Hbs), a homolog of the radical-forming, tolueneactivating benzylsuccinate synthase (Bss), was upregulated during benzene oxidation in G. daltonii, while the bss gene was upregulated during toluene oxidation. Addition of benzene to the G. daltonii whole-cell lysate resulted in toluene formation, indicating that methylation of benzene was occurring. Complementation of s54- (deficient) E. coli transformed with the bss operon restored its ability to grow in the presence of toluene, revealing bss to be regulated by s54. Binding sites for s70 and the transition state regulator AbrB were identified in the promoter region of the s54-encoding gene rpoN, and binding was confirmed. Induced expression of abrB during benzene and toluene degradation caused G. daltonii cultures to transition to the death phase. Our results suggested that G. daltonii can anaerobically oxidize benzene by methylation, which is regulated by s54 and AbrB. Our findings further indicated that the benzene, toluene, and benzoate degradation pathways converge into a single metabolic pathway, representing a uniquely efficient approach to anaerobic aromatic degradation in G. daltonii. IMPORTANCE The contamination of anaerobic subsurface environments including groundwater with toxic aromatic hydrocarbons, specifically benzene, toluene, ethylbenzene, and xylene, has become a global issue. Subsurface groundwater is largely anoxic, and further study is needed to understand the natural attenuation of these compounds. This study elucidated a metabolic pathway utilized by the bacterium Geotalea daltonii capable of anaerobically degrading the recalcitrant molecule benzene using a unique activation mechanism involving methylation. The identification of aromatic-degrading genes and AbrB as a regulator of the anaerobic benzene and toluene degradation pathways provides insights into the mechanisms employed by G. daltonii to modulate metabolic pathways as necessary to thrive in anoxic contaminated groundwater. Our findings contribute to the understanding of novel anaerobic benzene degradation pathways that could potentially be harnessed to develop improved strategies for bioremediation of groundwater contaminants. [ABSTRACT FROM AUTHOR]

With a warmer and drier climate, there has been an increase in wildfire events in the Northwest U.S., posing a potential health risk to downwind communities. The Lewis–Clark Valley (LCV), a small metropolitan area on the Washington/Idaho border in the United States Intermountain West region, was studied over the time period of 2017–2018. The main objective was to determine the community's exposure to particulate matter (PM2.5) and volatile organic compounds (VOCs) during wildfire smoke events and to estimate the associated health risk. VOCs were analyzed previously in the LCV using sorbent tube sampling and thermal-desorption gas-chromatography mass-spectrometry (TD-GC-MS) during several local smoke events in the 2017–2018 fire seasons. PM2.5 measurements were obtained from nearby agency monitors. PM2.5 reached up to 200 µg/m3 in 2017 and over 100 µg/m3 in 2018 in the LCV, and has been observed to be increasing at a rate of 0.10 µg m−3/yr over the past two decades. Benzene, a carcinogen and air toxic, was measured with concentrations up to 11 µg/m3, over ten times the normal level in some instances, in the LCV. The health risk in the LCV from benzene was calculated at seven extra cancers per million for lifetime exposure and thirteen extra cancers per million considering all air toxics measured. The other cities monitored showed similar lifetime cancer risk, due to benzene of about 6–7 extra cancers per million. This work is important, as it measures ground-level exposures of VOCs and demonstrates decreases in PM2.5 air quality over time in the region. [ABSTRACT FROM AUTHOR]

Raman spectroscopy allows for the unambiguous identification of materials through the inelastic scattering of light. This technique has a great many uses in various aspects of society from academic, scientific, and industry. This paper explores a specific type of Raman spectrometer called a spatial heterodyne Raman spectrometer (SHRSy), which is a variation of an interferometric spectrometer. It utilizes a Michelson interferometer and replaces the mirrors with gratings that transform it from a time-domain spectrometer to a spatial-domain spectrometer, allowing for the entirety of the spectrum to be captured at once. This study specifically tests a half-inch two-grating monolithic SHRS (½-in. 2g-mSHRS), which has a weight of <60 g and a size of 2.2 × 2.2 × 1.3 cm. To do this we excite a variety of organic liquids with a 532 nm neodymium-doped yttrium aluminum garnet (Nd:YAG) pulsed laser, using an excitation energy of 6.5 mJ/pulse and distance of 3 m in conjunction with an intensified charge-coupled device camera. This is the first time that the SHRS has been used for investigating polarized Raman spectra of liquids. We discuss and contrast the instrumental properties such as resolution, spectral range, étendue, and field of view with previously tested mSHRS to give context to the instrument's performance. [ABSTRACT FROM AUTHOR]

Benzene is one of the most ubiquitous structural motifs in chemistry. The valence isomers of benzene have also attracted synthetic chemists' attention due to their unique structures, bonding, and reactivity. We have been investigating boron‐nitrogen‐containing benzene valence isomers via photoisomerization of 1,2‐azaborines. In this contribution, we summarize recent developments of these highly strained BN‐heterocyclic compounds including their synthesis, characterization, proposed mechanism of formation, and their potential applications. [ABSTRACT FROM AUTHOR]

Metabolic conversion of benzene (Bz) is thought to be required for the hematotoxic effects observed following Bz exposures. Most safe exposure limits set for Bz utilize epidemiology data on the hematotoxic effects of Bz for the dose–response assessments. These hematotoxic effects occurred among workers exposed to elevated Bz levels, thus dose extrapolation is required for assessing relevant risks for populations exposed orders of magnitude lower. Thus, understanding how Bz is metabolized over a wide range of air Bz levels is an important topic for risk assessments for Bz. Here, we analyze biomonitoring data for workers exposed to Bz to make evaluations of how the metabolism of Bz varies across a wide range of exposures. Our analysis indicates that the presence of metabolites derived from exposures to sources other than Bz (nonspecific metabolites of Bz) are significant confounders among biomonitoring studies and this precludes making any assessments of how Bz metabolism differs below approximately 3 ppm air Bz exposures using such nonspecific metabolites. [ABSTRACT FROM AUTHOR]

According to the International Agency for Research on Cancer, leukemia ranks 14th in incidence and 11th in mortality and has a 5-year prevalence of approximately 1300,000 cases. Acute lymphoblastic leukemia is the most common hematopoietic syndrome in children during the first 5 years of life and represents approximately 75 % of all neoplasms among the pediatric population. The development of leukemia is strongly governed by DNA alterations that accelerate the growth of bone marrow cells. Currently, the most examined factor in pediatric leukemia is exposure to multiple compounds, such as hydrocarbons. Benzene, an aromatic hydrocarbon, can cause health challenges and is categorized as a carcinogen. Benzene toxicity has been widely associated with occupational exposure. Importantly, studies are underway to generate evidence that can provide clues regarding the risk of environmental benzene exposure and hematological problems in children. In this review, we summarize the existing evidence regarding the effects of benzene on pediatric leukemia, the associations between the effect of benzene on carcinogenesis, and the presence of certain molecular signatures in benzene-associated pediatric leukemia. Although there is sufficient evidence regarding the effects of benzene on carcinogenesis and leukemia, epidemiological research has primarily focused on occupational risk. Moreover, most benzene-induced molecular and cytogenetic alterations have been widely described in adults but not in the pediatric population. Thus, epidemiological efforts are crucial in the pediatric population in terms of epidemiological, clinical, and biomedical research. [Display omitted] • Pediatric leukemia incidence, mortality, and long-term prevalence represents a global health concern. • Acute lymphoblastic leukemia is the most frequent hematopoietic neoplasia in children. • Benzene, a carcinogenic aromatic hydrocarbon, represents a risk factor in hematopoietic tumors. • Evidence regarding the effects of benzene on pediatric leukemia is increasing, but still limited. • Future epidemiological efforts may provide insight into the mechanisms of benzene on pediatric leukemia. [ABSTRACT FROM AUTHOR]

A 14-day rat study with plasma metabolomics was conducted to evaluate the toxicity of Benzene. Wistar rats were orally administered Benzene daily at doses of 0, 300 and 1000 mg/kg bw. The study identified liver and kidneys as target organs of Benzene toxicity and found reductions in total white blood cells, absolute lymphocyte and eosinophil cell counts, and increased relative monocyte counts suggesting bone marrow as a target organ. The study also confirmed liver as a target organ using metabolomics, which showed indications of a stress reaction in rats and changes in metabolites suggestive of a metabolic disorder. The metabolomics investigations did not find any other toxicologically relevant modes of action, and the observed metabolite changes were not associated with markers for mitochondrial dysfunction. The study concludes that integration of omics technologies, such as metabolomics, in regulatory toxicity studies is possible, confirms existing knowledge and adds additional information that can be used for mechanistic understanding of observed toxicity. • Target organs after 14-day exposure to benzene are liver, kidney, bone marrow. • Metabolomics and toxicity parameters sufficient to identify subchronic toxicity. • Metabolomics indicates stress reaction and metabolic disorder in rats. • "smart" in vivo studies are a NAM that can reduce the need for subchronic in vivo testing. [ABSTRACT FROM AUTHOR]

The synthesis of silanes starting from multifunctionalized precursors often suffers from low chemoselectivity due to the similar kinetic reaction profiles, leading to the formation of difficult to separate side products. The opposite approach, which is an access based on unreactive tetraalkylsilanes as starting materials, is far less developed. Making use of the silylium-ion-initiated chemoselective halodealkylation of tetraalkylsilanes recently developed by our laboratory, an extension of this protocol, namely the direct synthesis of dihalosilanes from tetraalkylsilanes, is reported. Following a sequence of halodehydrogenation and halodealkylation, trialkylhydrosilanes can also be converted into dihalosilanes. Commercially available 1,2-dihaloethane acts as the halogen source and is involved in the generation of the catalytically active arenium ion by an SE Ar substitution of the benzene solvent. The formation of an uncommon halogen-substituted silylium ion as an intermediate is assumed, likely accounting for the need of an elevated reaction temperature. [ABSTRACT FROM AUTHOR]

Underground storage tanks (USTs) primarily store and dispense fuel products (petroleum hydrocarbons) such as gasoline and diesel as well as some hazardous substances. When a release occurs from an UST, it must be cleaned up and remediated as necessary. As part of the site characterization process, monitoring wells are installed to measure petroleum hydrocarbon concentrations, such as benzene, to help site managers make decisions on remediation strategies and effectiveness, determine site status, and whether sites pose a risk to local receptors—with implications to human health and the environment. Previous studies have used various approaches to estimate benzene plume lengths using these monitoring well data. Examining one state's large database of monitoring well data from leaking underground storage tank (LUST) cleanup sites, and through statistical and spatial analysis, we find that studies that used existing monitoring well data may have underestimated plume lengths. Our study identified elevated benzene concentrations at the boundaries of monitoring well extents, including at the leading edge of plumes. For example, in 3,495 LUST sites, 83% exceeded a selected threshold concentration of 5 ug/L in a monitoring well at the site boundary, and 76% of sites exceeded 5 ug/L at the monitoring well furthest from a defined source, the point used to delineate length. Of the total 17,816 monitoring wells that delineated UST site boundaries, 47% had concentrations exceeding 5 ug/L. These data analyses and results are done over the lifetime of a monitored UST site, not targeted over time periods when decisions are being rendered. However, results suggest that studies to date using existing monitoring well data may have underestimated plume lengths and extents. Furthermore, results suggest monitoring wells in combination with other site information, such as modeling, should be used to guide site managers in their decisions regarding leaked UST products, the area and extent of contamination, risks to receptors, and remedial approaches. Practical Applications: USTs, which store fuel at locations such as gas stations, are known to leak fuel products into soil and groundwater. Fuel products contain petroleum hydrocarbons like benzene, a cancer-causing chemical. Previous studies that have attempted to identify the maximum distance benzene plumes travel have been hampered by a bias in available data—specifically, that monitoring wells are often not placed at far enough distances to be able to map a plume to concentrations below concerning levels. This paper identifies this bias and provides insight into how it may be considered in the future to more effectively map plumes and identify potential biases that can lead to inconclusive results related to plume behavior. While traditional physics-based models remain useful, they can be augmented with data-driven models to more accurately estimate plume extents, especially when real-world data are lacking. [ABSTRACT FROM AUTHOR]

[Display omitted] Porous carbon materials are highly desirable for removing benzene due to their low energy for capture and regeneration. Research has demonstrated that narrow microporous volume is crucial for effective adsorption of benzene at ultra-low concentration. Unfortunately, achieving directional increase in the narrow microporous volume in porous carbon remains a challenge. Here, nitrogen-doped hydrothermal carbon was prepared using urea-assisted hydrothermal method, and then porous carbon (PUC800) was prepared by KOH activation. The resulting material had 180 % higher pore volume and 179 % higher surface area compared to non-nitrogen activation methods. Then, using mechanochemical (mechanical compaction and KOH activation) approach to produce PUC800-3T, which had a 30 % increase in pore volume and a 33 % increase in surface area compared to PUC800. PUC800-3T showed benzene adsorption capacity of 4.2 mmol g−1 at 1 Pa and 5.8 mmol g−1 at 5 Pa. Experimental and molecular simulation indicate that the benzene adsorption at 1 and 5 Pa is determined by pore volume of less than 0.8 and 0.9 nm, respectively. Density functional theory calculations provided insight into the C H⋯X (X = N/O) interactions drive benzene adsorption on the carbon framework. This work provides valuable theoretical and experimental support for designing, preparing, and applying adsorbents for trace removal of benzene vapor. [ABSTRACT FROM AUTHOR]

This study was conducted to investigate the presence of benzene in the ground and drinking water in the eastern Niger Delta, where multiple oil and gas production facilities are present. Samples from drinking water wells were collected for measurements of benzene, toluene, ethylbenzene, and xylenes (BTEX). Additionally, the dissolved organic carbon (DOC) concentration was determined for the first time to establish the groundwater's total hydrocarbon and non-hydrocarbon load. The groundwater BTEX and benzene levels were up to 3904 µg/L and 3500 µg/L, respectively. DOC concentrations were up to 49 mg/L. The highest benzene concentrations were detected in wells near an underground petroleum pipeline. However, the concentrations decreased with distance from the pipeline to levels less than 0.1 µg/L. Despite benzene contamination, the aquifer has shown promising aerobic attenuation potential, having up to a 7.5 (95%) mg/L DO level and 2.11 mg/L BTEX biodegradation capacity for DO. However, the high groundwater temperature of up to 32.5 °C may weaken attenuation. The benzene and BTEX point attenuation rates ranged from 0.128 to 0.693 day−1 and 0.086 to 0.556 day−1, respectively. Hence, by natural attenuation alone, up to 66.5 and 85 years would be required to reach Nigeria's groundwater benzene and BTEX remediation goals, respectively. [ABSTRACT FROM AUTHOR]

The coexistence of various organic pollutants in soil always draws extensive attention because of their difficulties and complexity for remediation. Especially, the impacts of bioremediation on soil co-contaminated with benzene, toluene, and trichloroethylene (TCE) have seldom been comprehensively evaluated yet. In this study, the contributions of biostimulation, bioaugmentation, and their combination for the bioremediation of the co-contaminated soil containing benzene, toluene, and TCE were systematically investigated. The addition of nutrients ((NH4)2SO4 (as N source), K2HPO4 (as P source), vegetable oil and CH3COONa (as C sources)) enhanced the degradation efficiency of the co-contaminated soil by 10.19% to 49.62%. The optimal biostimulation condition involved using vegetable oil as the carbon source with a C: N: P ratio of 100: 10: 1. Meanwhile, the addition of the microbial cultures screened and domesticated from the co-contaminated soil, named B-T, effectively enhanced the removal rate of contaminants by 33.02% to 37.55%. The genera comprising Pseudomonas, Stenotrophomonas, and Chryseobacterium in B-T exhibited the highest relative abundance, suggesting their potential for the removal of benzene, toluene, and TCE. Besides, the coupling of biostimulation and bioaugmentation enhanced the degradation efficiency by 62.38% to 68.84%, showing the most effective biodegradation effects. The coupled strategy showed synergistic effects of both, increasing the quantity and activity of microorganisms and accelerating the biodegradation of target contaminants. The findings indicated that the coupling of bioaugmentation and biostimulation treatment strategy holds promise for the bioremediation of benzene, toluene, and TCE from co-contaminated soil. [ABSTRACT FROM AUTHOR]

Triton X-100 (TX-100) is a commonly used surfactant in the manufacture of biosensors. The factors limiting the use of TX-100 in biosensors are environmental concerns. In this study, the binary system of sodium dodecyl benzene sulfonate (SDBS) and fatty alcohol-polyoxyethlene ether (AEO) was investigated from the physicochemical principle of surfactant interaction and its application in biosensors. The results demonstrated that a mixture of SDBS and AEO at an appropriate molar ratio had a comparable activity to TX-100 in terms of surface activity, micelle formation, dynamic adsorption, foaming, emulsifying, and cell permeability. Theory and experimentation support the idea that SDBS-AEO might take the place of TX-100 in the manufacturing of biosensors. This study contributes to the development of alternatives to TX-100 and provides a new perspective for an in-depth study of the interaction mechanism of additives in biosensor design. [ABSTRACT FROM AUTHOR]

AbstractSynthesis and illicit use of designer benzodiazepines are growing concerns, with these new psychoactive substances (NPS) posing serious health consequences and new hurdles for toxicologists. Consumption marker identification and characterization is paramount in confirming their use. The benzodiazepine core structure is a fusion of benzene and a seven-membered heterocycle with two nitrogen atoms forming the diazepine ring. Minor variations on the core structure produce different classes of benzodiazepines with marked differences in physiological effects. The present review provides a comprehensive designer benzodiazepines metabolism overview and suggests suitable human consumption biomarkers for toxicology casework. A systematic literature search of PubMed®, ScopusTM, Web of ScienceTM, and Cochrane databases was conducted independently by two coauthors adhering to PRISMA guidelines. Data from 30 in vitro and in vivo models of designer benzodiazepines metabolism from January 2007 to February 2023 were included. 1,4-benzodiazepines (n = 10), 2,3-benzodiazepines (n = 1), triazolo-benzodiazepines (n = 9), and thieno-triazolo-benzodiazepines (n = 3) study design, sample pretreatment, analytical techniques, and major metabolites detected in various matrices are addressed. Metabolites following hydroxylation and phase II glucuronide conjugation were the most prevalent analytes. N-Glucuronidation of parent azole-fused benzodiazepines, and nitro-reduced and N-acetylated metabolites of nitro-containing designer benzodiazepines were also common. From these data, we propose a generic metabolic pathway for designer benzodiazepines. The sporadic illicit market presents challenges in toxicological casework and necessitates comprehensive biomarker investigations, especially in cases with legal implications. There are few metabolism data for many designer benzodiazepines, emphasizing the need for research focusing on closing these gaps. [ABSTRACT FROM AUTHOR]

Embryo implantation is a tightly regulated process, critical for a successful pregnancy. After attachment of the blastocyst to the surface epithelium of the endometrium trophoblast migrate from the trophectoderm and invade into the stromal component of endometrium. Alterations on either process will lead to implantation failure or miscarriage. Volatile organic compounds (VOCs) such as benzene induce pregnancy complications, including preterm birth and miscarriages. The mechanism of this effect is unknown. The objective of this study was to elucidate the impact of benzene metabolite, Hydroquinone, on trophoblast function. We tested the hypothesis that Hydroquinone activates the Aryl hydrocarbon receptor (AhR) pathway modulating trophoblast migration and invasion. First-trimester trophoblast cells (Sw.71) were treated with hydroquinone (6 and 25 μM). Trophoblast migration and invasion was evaluated using a 3D invasion/migration model. Gene expression was quantified by q-PCR and Western blot analysis. Hydroquinone impairs trophoblast migration and invasion. This loss is associated with the activation of the AhR pathway which reduced the expression of Twist1and IFITM1. IFITM1 overexpression can rescue impaired trophoblast migration. Our study highlights that hydroquinone treatment induces the activation of the AhR pathway in trophoblast cells, which impairs trophoblast invasion and migration. We postulate that activation of the AhR pathway in trophoblast suppress Twist1 and a subsequent IFITM1. Thus, the AhR-Twist1-IFITM1 axis represent a critical pathway involved in the regulation of trophoblast migration and it is sensitive to benzene exposure. These findings provide crucial insights into the molecular mechanisms underlying pregnancy complications induced by air pollution. [Display omitted] • Benzene exposure affects pregnancy outcome. • Hydroquinone treatment inhibits trophoblast migration and invasion. • The AhR pathway is functional in trophoblast cells. • Hydroquinone activates the Ahr pathway in trophoblast. • Twist1 and IFITM1 are major regulators of trophoblast migration. [ABSTRACT FROM AUTHOR]

The ubiquitous chemistry of benzene led us to explore ways to stabilise analogous borozene, by capping them with appropriate groups. The mismatch in overlap of ring‐cap fragment molecular orbitals in [(HB)2B6H6]2− is overcome by replacing the two BH caps with higher congeners of boron. We calculated the relative energies of all the polyhedral structural candidates for [(HE)2B6H6]2− (E=Al−Tl) and found hexagonal bipyramid (HBP) to be more stable with Al−H caps. A global minimum search also gives HBP as the most stable structure for [Al2B6H8]2−. The capped B6H6 ring in [(HAl)2B6H6]2− has aromaticity comparable to that of benzene. [ABSTRACT FROM AUTHOR]

The one‐step synthesis of tetra‐substituted benzenes was accomplished via gold‐catalyzed diyne‐ene annulation. Distinguished from prior modification methods, this novel strategy undergoes formal [3+3] cyclization, producing polysubstituted benzenes with exceptional efficiency. The critical factor enabling this transformation was the introduction of amides, which were reported for the first time in gold catalysis as covalent nucleophilic co‐catalysts. This interesting protocol not only offers a new strategy to achieve functional benzenes with high efficiency, but also enlightens potential new reaction pathways within gold‐catalyzed alkyne activation processes. [ABSTRACT FROM AUTHOR]

This work reports for the first time, the experimental densities and sound speeds for the ternary system {methyl tert-butyl ether + benzene + cyclohexane} within the temperature range (293.15 to 313.15) K and under ambient pressure conditions. The related binary subsystems have also been reported. Experimental data were used to derive excess molar volumes and excess isentropic compressibilities. Redlich-Kister and Cibulka’s equations correlated the binary and ternary excess properties, respectively, with standard deviations falling below the estimated uncertainties of the corresponding properties. The results have been interpreted in terms of molecular interactions between mixtures’ components and structural effects. Additionally, two symmetric (Kohler and Muggianu) and two asymmetric (Hillert and Toop) binary contribution models have been tested for their ability to predict the excess properties of the ternary excess properties. [ABSTRACT FROM AUTHOR]

The hydroxylation of benzene to phenol in presence of hydrogen peroxide was performed using a new biphasic system consisting of a solid phase, a photocatalytically active monolithic polymer composite, immersed in an aqueous phase in which H2O2 is dissolved. In detail, ZnO photocatalytic particles were embedded into the hydrophobic syndiotactic polystyrene (sPS) polymer. Zinc oxide nanostructures (ZnO NSs) were synthesized by an electrochemical procedure. The surface morphology and structure of ZnO nanoparticles and ZnO‐sPS monolithic aerogel composite (ZnO/sPS) were investigated by scanning electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy analysis. Photocatalytic results evidenced that, under UV irradiation, both ZnO NSs and biphasic system water‐photocatalytic composites had a high benzene oxidative property but with very low phenol yield (<2 %) at pH=7. To enhance the phenol selective formation, the pH of the aqueous solution surrounding the photocatalytic polymer composite was modified. A phenol yield of about 94 % and benzene conversion higher than 99 % was obtained in alkaline conditions (pH=11). [ABSTRACT FROM AUTHOR]

Compared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high‐performance MOF platform may have higher probability of achieving targeted properties. Multi‐modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi‐modular platform is challenging due to multiple interconnected pathways. Here on the multi‐modular pacs (partitioned acs) platform, we demonstrate accessibility to a new regime of pore geometry using two independently adjustable modules (framework‐forming module 1 and pore‐partitioning module 2). A series of new pacs materials have been made. Benzene/cyclohexane selectivity is tuned, progressively, from 4.5 to 15.6 to 195.4 and to 482.5 by pushing the boundary of the pacs platform towards the smallest modules known so far. The exceptional stability of these materials in retaining both porosity and single crystallinity enables single‐crystal diffraction studies of different crystal forms (as‐synthesized, activated, guest‐loaded) that help reveal the mechanistic aspects of adsorption in pacs materials. [ABSTRACT FROM AUTHOR]

To improve the thermodynamic and mechanical properties of asymmetric polyimide (PI), a method to enhance the linearity of PI by using a structural reorganization approach was designed. First, two novel diamines containing benzimidazole and benzoxazole groups, namely PADBZ and PDBOA, were constructed and synthesized. Thereafter, two new kinds of PI films (PADBZ‐PMDA and PDBOA‐PMDA) were prepared and polymerized with 1,2,4,5‐benzenetetracarboxylic anhydride (PMDA). Based on structural reorganization, PADBZ‐PMDA and PDBOA‐PMDA had repeating units of the same chemical composition and different linearity with PABZ‐BPDA and BOA‐BPDA, respectively. Comparing PADBZ‐PMDA and PABZ‐BPDA, due to the transfer in the position of benzene, PADBZ‐PMDA with high linearity showed the improved heat resistance (Tg up to 448°C), dimensional stability (CTE down to 2.3 ppm/K) and mechanical properties. PDBOA‐PMDA and BOA‐BPDA had the same situation. This study provided a unique solution to enhance the performances of PI by increasing the linearity using a structural reorganization approach. [ABSTRACT FROM AUTHOR]

The enantioselective mechanism of the esterase QeH against the two enantiomers of quizalofop–ethyl (QE) has been primitively studied using computational and experimental approaches. However, it is still unclear how the esterase QeH adjusts its conformation to adapt to substrate binding and promote enzyme–substrate interactions in the catalytic kinetics. The equilibrium processes of enzyme–substrate interactions and catalytic dynamics were reproduced by performing independent molecular dynamics (MD) runs on the QeH-(R)/(S)-QE complexes with a newly developed residue-specific force field (RSFF2C). Our results indicated that the benzene ring of the (R)-QE structure can simultaneously form anion–π and cation–π interactions with the side-chain group of Glu328 and Arg384 in the binding cavity of the QeH-(R)-QE complex, resulting in (R)-QE being closer to its catalytic triplet system (Ser78-Lys81-Tyr189) with the distances measured for the hydroxyl oxygen atom of the catalytic Ser78 of QeH and the carbonyl carbon atom of (R)-QE of 7.39 Å, compared to the 8.87 Å for (S)-QE, whereas the (S)-QE structure can only form an anion–π interaction with the side chain of Glu328 in the QeH-(S)-QE complex, being less close to its catalytic site. The computational alanine scanning mutation (CAS) calculations further demonstrated that the π–π stacking interaction between the indole ring of Trp351 and the benzene ring of (R)/(S)-QE contributed a lot to the binding stability of the enzyme–substrate (QeH-(R)/(S)-QE). These results facilitate the understanding of their catalytic processes and provide new theoretical guidance for the directional design of other key enzymes for the initial degradation of aryloxyphenoxypropionate (AOPP) herbicides with higher catalytic efficiencies. [ABSTRACT FROM AUTHOR]

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We present the systematic exploration of various potential energy surfaces for systems with C6H6-x (x = 0, 1, 2, or 3) empirical formula using an automatic search approach. The primary objective of this study is to identify reaction pathways that lead to the creation of benzene, o-benzyne, and other rings. These pathways initiate with a barrierless recombination reaction and involve subsequent isomerization reactions with submerged transition states until the final product is reached. The reported reaction profiles are consistent with the existing conditions in the interstellar medium if the hot complex formed can cool down through radiative relaxation. Recent studies on the deactivation of polyaromatic hydrocarbons (PAHs) support the possibility of these reactions taking place. The C6-membered rings are considered precursors of PAHs, and our focus is on identifying pathways originating from the barrierless recombination of reactive molecules known to exist in the interstellar medium, with potential implications in other environments. [ABSTRACT FROM AUTHOR]

Two sets of co-formers, polyfluorinated arylenediamines with variable structural elements and macrocyclic ethers of different sizes, were used to study the patterns of self-assembly of co-crystals and to rank the intermolecular interactions. The co-crystallization stoichiometry was found to increase from 1 : 1 to 2 : 1 in the series trifluoro-1,3-phenylenediamine, 2,4-diaminotrifluoropyridine, and 2,4-diaminotrifluoronitrobenzene and with decreasing crown ether size due to restructuring of guest--host interactions and forming guest-guest interactions. 18-Crown-6 and 15-crown-5 ethers form the typical N--H...Ocr H-bonds connecting two Ocr atoms with one bifunctional proton donor NH2; when going to 12-crown-4, two Ocr atoms become connected with the Hamino atoms of two arylenediamine molecules. Modes of guest--guest bonding and supramolecular motifs in 2 : 1 co-crystals are determined by HB acceptors and p + π systems in arylenediamine: o-N--H...Nhet and p-N--H...F interactions form face-to-face dimers united in a chain; p-N-H...Onitro and o-N--H...Onitro contacts generate head-to-tail and head-to-side chains; π...π and X...π (X = F, O, N) electron interactions form off-set stacks. Quantum chemical calculations reveal an increase of the packing enthalpies and bonding energies with increasing arylenediamine electron affinity and crown ether size. According to MEP, BCP and NCI analyses, these effects are caused either by strengthening of the interactions due to a greater electrostatic contribution, or by multiplying bonding contacts. Quantifying the interactions allowed us to identify the key supramolecular synthons and related elements of the co-former structure, which can serve as tools in the molecular crystal design. [ABSTRACT FROM AUTHOR]

This review article discusses the emerging amino‐terephthalonitrile (Am‐TN) and amino terephthalate‐based single benzene fluorophores (SBFs) for their highly emissive nature and potential for numerous technical applications. Am‐TN‐SBFs are a new class of SBFs having amine as the electron donating (EDG) and dinitrile as the electron withdrawing group (EWG). The beauty of these Am‐TN‐SBFs lies in excellent intramolecular charge transfer between the EDG and EWG. The placement of two nitrile groups in para‐position on the benzene ring allows better charge transfer from the donating amines to the linear nitrile group leading to the strongly emissive nature. We also outline here the latest developments in the well‐known family of amino terephthalate SBFs reported in the last 2 to 3 years. Amino terephthalate SBFs have esters as the EWG and amine as the EDG. These have intramolecular H‐bonding between the EDG and EWG which is responsible for their emissive behavior. [ABSTRACT FROM AUTHOR]