Density functional theoretical calculations have been made on the electronic structure of （CH）n（BCO）6-n（n = 0-6） at B3LYP/6- 311 ＋ G（d） level. The nuclear-independent chemical shifts （NICS） values calculate...Density functional theoretical calculations have been made on the electronic structure of （CH）n（BCO）6-n（n = 0-6） at B3LYP/6- 311 ＋ G（d） level. The nuclear-independent chemical shifts （NICS） values calculated using the gauge-including atomic orbitals （GIAO） method were used to assess on the aromaticities of these molecules. The results shows that （CH）n（BCO）6n（n = 0-6） species are aromatic.展开更多
Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD...Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD（T））, several stable isomers for new three pnictogen dianionic Sb4^2-, Bi4^2-, and （SbBi）2^2- species were determined. For two homoatomic Sb4^2- and Bi4^2- species, there are three stable isomers： square （D4h）, roof-shaped （C2v-1）, and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian- ionic （SbBi）2^2- species, there are also three stable isomers： rhombus （D2h）, roof-shaped （C1）, and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts （NICS） values of roof-shaped isomers for Sb4^2-, Bi4^2-, and （SbBi）2^2- species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.展开更多
This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycy...This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycyclic aromatic hydrocarbons(PAHs)from aqueous solutions.The Chitosan(CS)hydrogel beads were modified with single/twin-tailed anionic surfactants,sodium dodecyl sulfate(SDS)and sodium bis(2-ethylhexyl)sulfosuccinate(AOT),and cationic surfactants,dodecyltrimethylammonium bromide(DTAB)and didodecyldimethylammonium bromide(DDAB),to enhance their adsorption capacity of PAHs.The CS and SMCS beads were evaluated for their structural,mechanical,and adsorption properties using a range of techniques,including infrared spectroscopy(IR),energy-dispersive X-ray spectroscopy(EDX),rheometry,and field emission scanning electron microscopy(FESEM).Adsorption experiments of naphthalene(Nap),acenaphthene(Ace),and phenanthrene(Phe)on SMCS beads demonstrate that they have significantly higher adsorption capacities than CS beads,due to increase in hydrophobic interactions.Adsorption capacity followed the trend,Phen>Ace>Nap for all the beads revealing that twin-tailed SMCS bead possess much higher adsorption capacities(Qmax)compared to single-tailed SMCS beads.For twin tailed surfactants,the maximum adsorption capacities for Nap,Ace and Phe varied as CS-AOT(CS-DDAB):430.0(323.8)611.60(538.18)633.39(536.99)mg/g respectively,outperforming other reported hydrogel beads.The study highlights the simplicity,eco-friendliness,and enhanced performance of surfactant modification for developing high-efficiency adsorbents,paving the way for cost-effective solutions in water re-mediation.展开更多
Along with decrease of fine particulate matter(PM_(2.5))concentration in recent years in China,secondary species become increasingly important.This work focuses on characterizing secondary components,and a few importa...Along with decrease of fine particulate matter(PM_(2.5))concentration in recent years in China,secondary species become increasingly important.This work focuses on characterizing secondary components,and a few important groups of organics including organic nitrogen(ON),organonitrates(OrgN),organosulfates(OS)and polycyclic aromatic hydrocarbons(PAHs),via online measurement of submicron aerosols(PM_(1))in Nanjing,China,during 2022 summer.The average PM_(1) concentration was 15.39μg/m^(3),dominated by secondary components(69.1%),which were even more important at higher PM_(1) levels.The primary organic aerosols(POA)were from traffic,industry and cooking;the two secondary OA factors were both closely linked with photochemistry,with one(OOA1)being relatively fresh and important in early afternoon and another(OOA2)being aged and important in late afternoon.Sulfate formation was also governed by photochemistry but resembled that of OOA2 not OOA1;nitrate formation was associated strongly with heterogeneous hydrolysis and thermodynamic equilibrium.Results also reveal a possible photochemical reaction channel from POA to OOA1,then to OOA2.Case studies show that formations of secondary components responded differently to different weather conditions and governed summer PM_(1) pollution.The average ON,OrgN,OS and PAHs concentrations were determined to be 122.8,84.4,45.6 and 3.3 ng/m^(3),respectively.ON was dominated by primary sources(53.8%).OrgN varied similarly to nitrate.OS formation was linked with aqueous-phase reactions,which were insignificant therefore its level was low.PAHs was mainly from traffic,and photochemical oxidation might be its important sink during afternoon.展开更多
Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure f...Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure from the living environment.This study included 1311 women in late pregnancy from the Zunyi birth cohort and measured the urinary concentrations of 10 hydroxylated PAH metabolites(OH-PAHs).Risk assessment was conducted based on the estimated daily intake to calculate the hazard quotient and hazard index(HI).A linear regression model was used to analyze the relationship between creatinine-adjusted OH-PAHs concentrations and living environment and lifestyle factors,while principal component analysis was applied to trace the sources of PAHs exposure.1-OHPYR was detected in all participants’urine,with naphthalene metabolites having the highest concentrations among creatinine-adjusted PAHs.OH-PAHs concentrations were associated with housing type,room number,cooking frequency,household size,exercise frequency,fuel type,distance from main road,and drinking water source.Pregnant women using traditional fuels and living in bungalows had higher health risks than those using clean energy and living in buildings.Those living within 100 m of a main road had higher HI than those farther away.Coal combustion was identified as the primary source of PAHs exposure.The study emphasizes the importance of reducing PAHs exposure,especially for pregnant women living in polluted environments.It recommends public health interventions such as improving indoor ventilation and providing clean energy to reduce related health risks.展开更多
Nowadays,presynaptic dopaminergic positron emission tomography,which assesses deficiencies in dopamine synthesis,storage,and transport,is widely utilized for early diagnosis and differential diagnosis of parkinsonism....Nowadays,presynaptic dopaminergic positron emission tomography,which assesses deficiencies in dopamine synthesis,storage,and transport,is widely utilized for early diagnosis and differential diagnosis of parkinsonism.This review provides a comprehensive summary of the latest developments in the application of presynaptic dopaminergic positron emission tomography imaging in disorders that manifest parkinsonism.We conducted a thorough literature search using reputable databases such as PubMed and Web of Science.Selection criteria involved identifying peer-reviewed articles published within the last 5 years,with emphasis on their relevance to clinical applications.The findings from these studies highlight that presynaptic dopaminergic positron emission tomography has demonstrated potential not only in diagnosing and differentiating various Parkinsonian conditions but also in assessing disease severity and predicting prognosis.Moreover,when employed in conjunction with other imaging modalities and advanced analytical methods,presynaptic dopaminergic positron emission tomography has been validated as a reliable in vivo biomarker.This validation extends to screening and exploring potential neuropathological mechanisms associated with dopaminergic depletion.In summary,the insights gained from interpreting these studies are crucial for enhancing the effectiveness of preclinical investigations and clinical trials,ultimately advancing toward the goals of neuroregeneration in parkinsonian disorders.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and ...Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallowsurface soils,increasing evidence shows that these compounds can leach into the groundwater.Herein,we compare the leachabilities of PBDEs vs.PAHs from contaminated soils collected at an e-waste recycling site in Tianjin,China.Considerable amounts of BDE-209(0.3–2 ng/L)and phenanthrene(42–106 ng/L),the most abundant PBDE and PAH at the site,are detected in the effluents of columns packed with contaminated soils,with the specific concentrations varying with hydrodynamic and solution chemistry conditions.Interestingly,the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles,whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent,but showing essentially no correlation with the concentration of mineral particles.The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive,as PBDEs and PAHs often co-exist at e-waste recycling sites(particularly at the sites wherein incineration is being practiced)and share many similarities in terms of physicochemical properties.One possible explanation is that due to its extremely low solubility,BDE-209 predominantly exists in free-phase(i.e.,as solid(nano)particles),whereas the more soluble phenanthrene is mainly sorbed to soil organic matter.Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.展开更多
Volatile aromatic aldehydes,including benzaldehyde(BzH),4-fluorobenzaldehyde(4-F-BzH),4-isobutylbenzaldehyde(4-iBu-BzH),3-trifluoromethylbenzaldehyde(3-CF_(3)-BzH),p-methoxybenzaldehyde(4-MeO-BzH),and o-trifluoromethy...Volatile aromatic aldehydes,including benzaldehyde(BzH),4-fluorobenzaldehyde(4-F-BzH),4-isobutylbenzaldehyde(4-iBu-BzH),3-trifluoromethylbenzaldehyde(3-CF_(3)-BzH),p-methoxybenzaldehyde(4-MeO-BzH),and o-trifluoromethylbenzaldehyde(2-CF_(3)-BzH),are crucial raw materials for the synthesis of various pesticides and pharmaceuticals[1].展开更多
P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process o...P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process of aromatic hydroxylation and mechanism of regioselectivity catalyzed by cytochrome P450 monooxygenases remained ambiguous.Here,we have resolved these issues.With a stable chiral organofluorine probe,and especially with X-ray data of two isolated arene oxides derivatives,we demonstrate that an arene oxide pathway is definitely involved in P450-catalyzed aromatic hydroxylation.By the capture,isolation,identification and reactivity exploration of the arene 1,2-oxide and arene 2,3-oxide intermediates,together with advanced QM calculations,the mechanism of how two intermediates go to the same product has been elucidated.In addition to the model substrate,we also confirmed that an arene oxide intermediate is involved in the P450-catalyzed hydroxylation pathway of a natural product derivative methyl cinnamate,which indicates that this intermediate appears to be universal in P450-catalyzed aromatic hydroxylation.Our work not only provides the most direct evidence for the arene oxide pathway and new insights into the regioselectivity involved in P450-catalyzed aromatic hydroxylation,but also supplies a new synthetic approach to achieve the dearomatization of aromatic compounds.展开更多
The associations of polycyclic aromatic hydrocarbon(PAH)exposure with serum uric acid(SUA)or hyperuricemia have been rarely assessed.We aimed to investigate the relationships between urinary PAH metabolites and SUA or...The associations of polycyclic aromatic hydrocarbon(PAH)exposure with serum uric acid(SUA)or hyperuricemia have been rarely assessed.We aimed to investigate the relationships between urinary PAH metabolites and SUA or hyperuricemia among US adults and to explore the mediating role of systemic inflammation in the associations.A total of 10,307 US adults were conducted to assess the associations of seven urinary hydroxy–PAH with SUA and hyperuricemia and evaluate the role of C-reactive protein(CRP),a biomarker of systemic inflammation,in such associations.Results showed that each 1-unit increase in ln-transformed 2-hydroxynaphthalene(2-OHNa),1-hydroxyphenanthrene(1-OHPh),2&3-hydroxyphenanthrene(2&3-OHPh)and total hydroxyphenanthrene(OHPh)was associated with a 1.68(95%confidence interval(CI):0.19 to 3.17),2.46(0.78 to 4.13),3.34(1.59 to 5.09),and 2.99(1.23 to 4.75)μmol/L increase in SUA,and a 8%(odds ratio(OR):1.08,1.02 to 1.15),9%(OR:1.09,1.02 to 1.18),13%(OR:1.13,1.05 to 1.22),and 12%(OR:1.12,95%CI:1.03,1.21)increase in hyperuricemia,respectively.Co-exposure of seven PAHs was positively associated with SUA and hyperuricemia,with 2&3-OHPh showing the highest weight(components weights:0.83 and 0.78,respectively).The CRP mediated 11.47%and 10.44%of the associations ofΣOHPh and 2&3-OHPh with SUA and mediated 8.60%and 8.62%in associations ofΣOHPh and 2&3-OHPh with hyperuricemia,respectively.In conclusion,internal levels of PAH metabolites were associated with elevated SUA levels and the increased risk of hyperuricemia among US adults,and CRP played a mediating role in the associations.展开更多
This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high con...This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high concentrations of 16 EPA PAHs(∑Parent-PAHs)in smelting subarea of studied petroleum refinery facility,total derivatives of PAHs[named as XPAHs,including nitro PAHs(NPAHs),chlorinated PAHs(Cl-PAHs),and brominated PAHs(Br-PAHs)]in gas(mean=1.57×10^(4)ng/m^(3)),total suspended particulate(TSP)(mean=4.33×10^(3) ng/m^(3))and soil(mean=4.37×10^(3) ng/g)in this subarea had 1.76-6.19 times higher levels than those from other subareas of this facility,surrounding residential areas and reference areas,indicating that petroleum refining processes would lead apparent derivation of PAHs.Especially,compared with those in residential and reference areas,gas samples in the petrochemical areas had higher∑NPAH/∑PAHs(mean=2.18),but lower∑Cl-PAH/∑PAHs(mean=1.43×10^(-1))and∑Br-PAH/∑PAHs ratios(mean=7.49×10^(-2)),indicating the richer nitrification of PAHs than chlorination during petrochemical process.The occupational exposure to PAHs and XPAHs in this petroleum refinery facility were 24-343 times higher than non-occupational exposure,and the ILCR(1.04×10^(-4))for petrochemical workers was considered to be potential high risk.Furthermore,one expanded high-resolution screening through GC Orbitrap/MS was performed for soils from petrochemical area,and another 35 PAHs were found,including alkyl-PAHs,phenyl-PAHs and other species,indicat-ing that profiles and risks of PAHs analogs in petrochemical areas deserve further expanded investigation.展开更多
Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy convers...Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.展开更多
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for...Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.展开更多
Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)...Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.展开更多
Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-ar...Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1).The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.展开更多
Diradicaloid polycyclic hydrocarbons(PHs)own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics.Herein,we disclose precise fusion of B/O-heterocy...Diradicaloid polycyclic hydrocarbons(PHs)own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics.Herein,we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties.We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluoreneπ-skeletons,respectively.The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties,such as diradical and aromatic structures,energy levels and band gaps,as well as magnetic,electrochemical and photophysical properties.Notably,the mode A may decrease the open-shell extent,whereas the mode B can enhance the diradical nature,leading to their well-tuned diradical characters in the range of0.46-0.70.Moreover,the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels,which are remarkably contributed by the B and O atoms,respectively,further giving rise to the decreased band gaps and redshifted absorptions.This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids.These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.展开更多
Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated el...Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.展开更多
Dion-Jacobson (DJ) phase hybrid perovskites have been proven to improve the photovoltaic performance of the devices due to its unique structure.At present,some DJ hybrid perovskites have been reported and used for pho...Dion-Jacobson (DJ) phase hybrid perovskites have been proven to improve the photovoltaic performance of the devices due to its unique structure.At present,some DJ hybrid perovskites have been reported and used for photodetection filed,but most of them are based on lead-bromide systems,which is not conducive to construct broadband photodetection devices due to the limitation of intrinsic absorption.Herein,we constructed a bilayered DJ hybrid perovskite (3AMPY)(EA)Pb_(2)I_(7)(3AMPY^(2+)is 3-(aminomethyl)pyridinium,EA^(+)is ethylammonium) using an aromatic spacer,which exhibit large current on/off ratios of 10~4under 520 and 637 nm illumination.In particular,the single crystal device based on (3AMPY)(EA)Pb_(2)I_(7)shows a distinguished detectivity of 7.4×10^(12)Jones and a high responsivity of 0.89A/W under 637 nm illumination.Such finding not only enriches the quantities of DJ hybrid perovskites,but also provides useful assistance for constructing high-performance optoelectronic device in the future.展开更多
Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalterna...Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit.Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic.The extensive conjugated aryl substituents on the acene’s side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups,thereby narrowing the HOMO-LUMO energy gap and enhancing absorptions in the low-energy regions.Furthermore,these fused acenes readily react with base rather than acid,resulting in reversible base/acid stimuli responsiveness.展开更多
文摘Density functional theoretical calculations have been made on the electronic structure of （CH）n（BCO）6-n（n = 0-6） at B3LYP/6- 311 ＋ G（d） level. The nuclear-independent chemical shifts （NICS） values calculated using the gauge-including atomic orbitals （GIAO） method were used to assess on the aromaticities of these molecules. The results shows that （CH）n（BCO）6n（n = 0-6） species are aromatic.
文摘Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory （B3LYP） and two post- Hartree-Fock approaches （MP2, CCSD（T））, several stable isomers for new three pnictogen dianionic Sb4^2-, Bi4^2-, and （SbBi）2^2- species were determined. For two homoatomic Sb4^2- and Bi4^2- species, there are three stable isomers： square （D4h）, roof-shaped （C2v-1）, and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian- ionic （SbBi）2^2- species, there are also three stable isomers： rhombus （D2h）, roof-shaped （C1）, and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts （NICS） values of roof-shaped isomers for Sb4^2-, Bi4^2-, and （SbBi）2^2- species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.
基金the Department of Science and Technology(DST),Govt.of India for providing funds under the FIST program and PURSE grant vide No.SR/PURSE/2020/31 to the department of Chemistry,University of Kashmir.
文摘This study presents a thorough investigation into the use of single and twin-tailed cationic and anionic surfactant-modified chitosan(SMCS)hydrogel beads as effective adsorbents for the elimination of hazardous polycyclic aromatic hydrocarbons(PAHs)from aqueous solutions.The Chitosan(CS)hydrogel beads were modified with single/twin-tailed anionic surfactants,sodium dodecyl sulfate(SDS)and sodium bis(2-ethylhexyl)sulfosuccinate(AOT),and cationic surfactants,dodecyltrimethylammonium bromide(DTAB)and didodecyldimethylammonium bromide(DDAB),to enhance their adsorption capacity of PAHs.The CS and SMCS beads were evaluated for their structural,mechanical,and adsorption properties using a range of techniques,including infrared spectroscopy(IR),energy-dispersive X-ray spectroscopy(EDX),rheometry,and field emission scanning electron microscopy(FESEM).Adsorption experiments of naphthalene(Nap),acenaphthene(Ace),and phenanthrene(Phe)on SMCS beads demonstrate that they have significantly higher adsorption capacities than CS beads,due to increase in hydrophobic interactions.Adsorption capacity followed the trend,Phen>Ace>Nap for all the beads revealing that twin-tailed SMCS bead possess much higher adsorption capacities(Qmax)compared to single-tailed SMCS beads.For twin tailed surfactants,the maximum adsorption capacities for Nap,Ace and Phe varied as CS-AOT(CS-DDAB):430.0(323.8)611.60(538.18)633.39(536.99)mg/g respectively,outperforming other reported hydrogel beads.The study highlights the simplicity,eco-friendliness,and enhanced performance of surfactant modification for developing high-efficiency adsorbents,paving the way for cost-effective solutions in water re-mediation.
基金supported by the National Natural Science Foundation of China(Nos.22361162668 and 42021004)the National Key Research and Development Program of China(No.2023YFC3706203).
文摘Along with decrease of fine particulate matter(PM_(2.5))concentration in recent years in China,secondary species become increasingly important.This work focuses on characterizing secondary components,and a few important groups of organics including organic nitrogen(ON),organonitrates(OrgN),organosulfates(OS)and polycyclic aromatic hydrocarbons(PAHs),via online measurement of submicron aerosols(PM_(1))in Nanjing,China,during 2022 summer.The average PM_(1) concentration was 15.39μg/m^(3),dominated by secondary components(69.1%),which were even more important at higher PM_(1) levels.The primary organic aerosols(POA)were from traffic,industry and cooking;the two secondary OA factors were both closely linked with photochemistry,with one(OOA1)being relatively fresh and important in early afternoon and another(OOA2)being aged and important in late afternoon.Sulfate formation was also governed by photochemistry but resembled that of OOA2 not OOA1;nitrate formation was associated strongly with heterogeneous hydrolysis and thermodynamic equilibrium.Results also reveal a possible photochemical reaction channel from POA to OOA1,then to OOA2.Case studies show that formations of secondary components responded differently to different weather conditions and governed summer PM_(1) pollution.The average ON,OrgN,OS and PAHs concentrations were determined to be 122.8,84.4,45.6 and 3.3 ng/m^(3),respectively.ON was dominated by primary sources(53.8%).OrgN varied similarly to nitrate.OS formation was linked with aqueous-phase reactions,which were insignificant therefore its level was low.PAHs was mainly from traffic,and photochemical oxidation might be its important sink during afternoon.
基金supported by the National Key R&D Program of China(Nos.2018YFC1004300 and 2018YFC1004302)the Science&Technology Program of Guizhou Province(Nos.QKHHBZ[2020]3002,QKHPTRC-GCC[2022]039-1 and QKHPTRCCXTD[2022]014)the Scientific Research Program of Guizhou Provincial Department of Education(No.QJJ[2023]019).
文摘Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure from the living environment.This study included 1311 women in late pregnancy from the Zunyi birth cohort and measured the urinary concentrations of 10 hydroxylated PAH metabolites(OH-PAHs).Risk assessment was conducted based on the estimated daily intake to calculate the hazard quotient and hazard index(HI).A linear regression model was used to analyze the relationship between creatinine-adjusted OH-PAHs concentrations and living environment and lifestyle factors,while principal component analysis was applied to trace the sources of PAHs exposure.1-OHPYR was detected in all participants’urine,with naphthalene metabolites having the highest concentrations among creatinine-adjusted PAHs.OH-PAHs concentrations were associated with housing type,room number,cooking frequency,household size,exercise frequency,fuel type,distance from main road,and drinking water source.Pregnant women using traditional fuels and living in bungalows had higher health risks than those using clean energy and living in buildings.Those living within 100 m of a main road had higher HI than those farther away.Coal combustion was identified as the primary source of PAHs exposure.The study emphasizes the importance of reducing PAHs exposure,especially for pregnant women living in polluted environments.It recommends public health interventions such as improving indoor ventilation and providing clean energy to reduce related health risks.
基金supported by the Research Project of the Shanghai Health Commission,No.2020YJZX0111(to CZ)the National Natural Science Foundation of China,Nos.82021002(to CZ),82272039(to CZ),82171252(to FL)+1 种基金a grant from the National Health Commission of People’s Republic of China(PRC),No.Pro20211231084249000238(to JW)Medical Innovation Research Project of Shanghai Science and Technology Commission,No.21Y11903300(to JG).
文摘Nowadays,presynaptic dopaminergic positron emission tomography,which assesses deficiencies in dopamine synthesis,storage,and transport,is widely utilized for early diagnosis and differential diagnosis of parkinsonism.This review provides a comprehensive summary of the latest developments in the application of presynaptic dopaminergic positron emission tomography imaging in disorders that manifest parkinsonism.We conducted a thorough literature search using reputable databases such as PubMed and Web of Science.Selection criteria involved identifying peer-reviewed articles published within the last 5 years,with emphasis on their relevance to clinical applications.The findings from these studies highlight that presynaptic dopaminergic positron emission tomography has demonstrated potential not only in diagnosing and differentiating various Parkinsonian conditions but also in assessing disease severity and predicting prognosis.Moreover,when employed in conjunction with other imaging modalities and advanced analytical methods,presynaptic dopaminergic positron emission tomography has been validated as a reliable in vivo biomarker.This validation extends to screening and exploring potential neuropathological mechanisms associated with dopaminergic depletion.In summary,the insights gained from interpreting these studies are crucial for enhancing the effectiveness of preclinical investigations and clinical trials,ultimately advancing toward the goals of neuroregeneration in parkinsonian disorders.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804202)the National Natural Science Foundation of China(Nos.22020102004 and 22125603)+1 种基金Tianjin Municipal Science and Technology Bureau(No.21JCZDJC00280)the Fundamental Research Funds for the Central Universities,and the Ministry of Education of China(No.T2017002).
文摘Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallowsurface soils,increasing evidence shows that these compounds can leach into the groundwater.Herein,we compare the leachabilities of PBDEs vs.PAHs from contaminated soils collected at an e-waste recycling site in Tianjin,China.Considerable amounts of BDE-209(0.3–2 ng/L)and phenanthrene(42–106 ng/L),the most abundant PBDE and PAH at the site,are detected in the effluents of columns packed with contaminated soils,with the specific concentrations varying with hydrodynamic and solution chemistry conditions.Interestingly,the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles,whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent,but showing essentially no correlation with the concentration of mineral particles.The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive,as PBDEs and PAHs often co-exist at e-waste recycling sites(particularly at the sites wherein incineration is being practiced)and share many similarities in terms of physicochemical properties.One possible explanation is that due to its extremely low solubility,BDE-209 predominantly exists in free-phase(i.e.,as solid(nano)particles),whereas the more soluble phenanthrene is mainly sorbed to soil organic matter.Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.
基金supported by National Natural Science Foundation of China(22361031,22308260).
文摘Volatile aromatic aldehydes,including benzaldehyde(BzH),4-fluorobenzaldehyde(4-F-BzH),4-isobutylbenzaldehyde(4-iBu-BzH),3-trifluoromethylbenzaldehyde(3-CF_(3)-BzH),p-methoxybenzaldehyde(4-MeO-BzH),and o-trifluoromethylbenzaldehyde(2-CF_(3)-BzH),are crucial raw materials for the synthesis of various pesticides and pharmaceuticals[1].
文摘P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process of aromatic hydroxylation and mechanism of regioselectivity catalyzed by cytochrome P450 monooxygenases remained ambiguous.Here,we have resolved these issues.With a stable chiral organofluorine probe,and especially with X-ray data of two isolated arene oxides derivatives,we demonstrate that an arene oxide pathway is definitely involved in P450-catalyzed aromatic hydroxylation.By the capture,isolation,identification and reactivity exploration of the arene 1,2-oxide and arene 2,3-oxide intermediates,together with advanced QM calculations,the mechanism of how two intermediates go to the same product has been elucidated.In addition to the model substrate,we also confirmed that an arene oxide intermediate is involved in the P450-catalyzed hydroxylation pathway of a natural product derivative methyl cinnamate,which indicates that this intermediate appears to be universal in P450-catalyzed aromatic hydroxylation.Our work not only provides the most direct evidence for the arene oxide pathway and new insights into the regioselectivity involved in P450-catalyzed aromatic hydroxylation,but also supplies a new synthetic approach to achieve the dearomatization of aromatic compounds.
基金supported by the Key Program of National Natural Science Foundation of China(No.82241088)the Natural Science Foundation of Hubei Province(No.2022CFB813).
文摘The associations of polycyclic aromatic hydrocarbon(PAH)exposure with serum uric acid(SUA)or hyperuricemia have been rarely assessed.We aimed to investigate the relationships between urinary PAH metabolites and SUA or hyperuricemia among US adults and to explore the mediating role of systemic inflammation in the associations.A total of 10,307 US adults were conducted to assess the associations of seven urinary hydroxy–PAH with SUA and hyperuricemia and evaluate the role of C-reactive protein(CRP),a biomarker of systemic inflammation,in such associations.Results showed that each 1-unit increase in ln-transformed 2-hydroxynaphthalene(2-OHNa),1-hydroxyphenanthrene(1-OHPh),2&3-hydroxyphenanthrene(2&3-OHPh)and total hydroxyphenanthrene(OHPh)was associated with a 1.68(95%confidence interval(CI):0.19 to 3.17),2.46(0.78 to 4.13),3.34(1.59 to 5.09),and 2.99(1.23 to 4.75)μmol/L increase in SUA,and a 8%(odds ratio(OR):1.08,1.02 to 1.15),9%(OR:1.09,1.02 to 1.18),13%(OR:1.13,1.05 to 1.22),and 12%(OR:1.12,95%CI:1.03,1.21)increase in hyperuricemia,respectively.Co-exposure of seven PAHs was positively associated with SUA and hyperuricemia,with 2&3-OHPh showing the highest weight(components weights:0.83 and 0.78,respectively).The CRP mediated 11.47%and 10.44%of the associations ofΣOHPh and 2&3-OHPh with SUA and mediated 8.60%and 8.62%in associations ofΣOHPh and 2&3-OHPh with hyperuricemia,respectively.In conclusion,internal levels of PAH metabolites were associated with elevated SUA levels and the increased risk of hyperuricemia among US adults,and CRP played a mediating role in the associations.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804501)the National Natural Science Foundation of China(Nos.22036007 and 22122611)+1 种基金the Natural Science Foundation of Shandong Province(No.ZR2020ME228)the Introduction and Cultivation Plan for Young Innovative Talents of Colleges and Universities.
文摘This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high concentrations of 16 EPA PAHs(∑Parent-PAHs)in smelting subarea of studied petroleum refinery facility,total derivatives of PAHs[named as XPAHs,including nitro PAHs(NPAHs),chlorinated PAHs(Cl-PAHs),and brominated PAHs(Br-PAHs)]in gas(mean=1.57×10^(4)ng/m^(3)),total suspended particulate(TSP)(mean=4.33×10^(3) ng/m^(3))and soil(mean=4.37×10^(3) ng/g)in this subarea had 1.76-6.19 times higher levels than those from other subareas of this facility,surrounding residential areas and reference areas,indicating that petroleum refining processes would lead apparent derivation of PAHs.Especially,compared with those in residential and reference areas,gas samples in the petrochemical areas had higher∑NPAH/∑PAHs(mean=2.18),but lower∑Cl-PAH/∑PAHs(mean=1.43×10^(-1))and∑Br-PAH/∑PAHs ratios(mean=7.49×10^(-2)),indicating the richer nitrification of PAHs than chlorination during petrochemical process.The occupational exposure to PAHs and XPAHs in this petroleum refinery facility were 24-343 times higher than non-occupational exposure,and the ILCR(1.04×10^(-4))for petrochemical workers was considered to be potential high risk.Furthermore,one expanded high-resolution screening through GC Orbitrap/MS was performed for soils from petrochemical area,and another 35 PAHs were found,including alkyl-PAHs,phenyl-PAHs and other species,indicat-ing that profiles and risks of PAHs analogs in petrochemical areas deserve further expanded investigation.
文摘Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.
基金supported by the fundamental research funds of Zhejiang Sci-Tech University(No.22212286-Y)the Natural Science Foundation of Zhejiang Province(No.LQ24B040003)。
文摘Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.
文摘Four new coordination polymers,{[Cd(mbtx)(4OHphCOO)]NO_(3)}n(1),{[Zn(mbtx)(1,4-bdc)_(0.5)(H_(2)O)_(2)]·(1,4-bdc)_(0.5)·4H_(2)O}n(2),{[Cd2(mbtx)(5NO_(2)-bdc)_(2)(H_(2)O)_(3)]·4.5H_(2)O}n(3),and{[Zn(H_(2)O)6][Zn_(2)(mbtx)_(2)(btc)_(2)(H_(2)O)_(4)]·2H_(2)O}n(4)(mbtx=1,3-bis(4H-1,2,4-triazole)benzene,4OHphCOO-=p-hydroxybenzoate,1,4-bdc2-=1,4-benzenedicarboxylate,5NO_(2)-bdc2-=5-nitro-isophthalate,btc3-=1,3,5-benzenetricarboxylate),were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction,elemental analyses,and powder X-ray diffraction.Single-crystal X-ray structural analysis shows that complexes 1 and 3 are 2D networks.In 1,the adjacent 2D networks are linked to a 3D network byπ-πstacking interaction.2 and 4 exhibit 1D chains,and the 1D chains are connected into a 3D network byπ-πstacking interaction and intermolecular hydrogen bond.Luminescence and thermogravimetric analysis of the four complexes were discussed.CCDC:2416406,1;2416407,2;2416408,3;2416409,4.
基金partly supported by the National Natural Science Foundation of China(No.22301108)the Project Startup Foundation for Distinguished Scholars of Jiangsu University(Nos.4111310026 and 5501310014).
文摘Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1).The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.
基金supported by National Natural Science Foundation of China(Nos.52373182 and 22175074)Jilin Scientific and Technological Development Program(No.20220101054JC)Department of Education of Jilin Province(No.JJKH20221046KJ)。
文摘Diradicaloid polycyclic hydrocarbons(PHs)own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics.Herein,we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties.We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluoreneπ-skeletons,respectively.The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties,such as diradical and aromatic structures,energy levels and band gaps,as well as magnetic,electrochemical and photophysical properties.Notably,the mode A may decrease the open-shell extent,whereas the mode B can enhance the diradical nature,leading to their well-tuned diradical characters in the range of0.46-0.70.Moreover,the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels,which are remarkably contributed by the B and O atoms,respectively,further giving rise to the decreased band gaps and redshifted absorptions.This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids.These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.
基金supported by the National Key R&D Program of China(2024YFA1211004)the National Natural Science Foundation of China(22402150,22072107)+1 种基金the Natural Science Foundation of Shanghai(23ZR1464800,24ZR1470200)the Foundation of State Key Laboratory of Pollution Control and Resource Reuse(Tongji University)。
文摘Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.
基金financially supported by the National Natural Science Foundation of China(Nos.22005183 and 22275117)the Program of State Key Laboratory of Quantum Optics and Quantum Optics Devices(No.KF202204)。
文摘Dion-Jacobson (DJ) phase hybrid perovskites have been proven to improve the photovoltaic performance of the devices due to its unique structure.At present,some DJ hybrid perovskites have been reported and used for photodetection filed,but most of them are based on lead-bromide systems,which is not conducive to construct broadband photodetection devices due to the limitation of intrinsic absorption.Herein,we constructed a bilayered DJ hybrid perovskite (3AMPY)(EA)Pb_(2)I_(7)(3AMPY^(2+)is 3-(aminomethyl)pyridinium,EA^(+)is ethylammonium) using an aromatic spacer,which exhibit large current on/off ratios of 10~4under 520 and 637 nm illumination.In particular,the single crystal device based on (3AMPY)(EA)Pb_(2)I_(7)shows a distinguished detectivity of 7.4×10^(12)Jones and a high responsivity of 0.89A/W under 637 nm illumination.Such finding not only enriches the quantities of DJ hybrid perovskites,but also provides useful assistance for constructing high-performance optoelectronic device in the future.
基金supported by the National Natural Science Foundation of China(Nos.92156021,22350009,and 22101115)Financial Support for Outstanding Talents Training Fund in Shenzhen,the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+2 种基金high level of special funds(No.G03050K003)Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079)supported by the Center for Computational Science and Engineering at SUSTech.
文摘Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit.Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic.The extensive conjugated aryl substituents on the acene’s side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups,thereby narrowing the HOMO-LUMO energy gap and enhancing absorptions in the low-energy regions.Furthermore,these fused acenes readily react with base rather than acid,resulting in reversible base/acid stimuli responsiveness.
