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Covalent edge-functionalization of graphene oxide with porphyrins for highly efficient photoinduced electron/energy transfer and enhanced nonlinear optical performance

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Nano Research 2023年第1期16卷 25-32页

作者： lulu fu Mark G.Humphrey Chi Zhang China-Australia Joint Research Center for functional Molecular Materials School of Chemical Science and EngineeringTongji UniversityShanghai 200092China School of Chemical and Material Engineering Jiangnan UniversityWuxi 214122China Research School of Chemistry Australian National UniversityCanberraACT 2601Australia

Covalent modification of graphene oxide(GO)with functional chromophores plays an important role in constructing various kinds of advanced optoelectronic materials for applications in molecular diagnosis,light-harvesting,photodynamic therapy,and optical ***,a new approach to functionalizing GO with meso-substituted formylporphyrins at GO’s edge sites via imidazole condensation is developed,which affords a novel GO-imi-Por nanohybrid covalently-linked by imidazole rings between two *** structure of the GO-imi-Por nanohybrid was thoroughly characterized by scanning electron microscopy(SEM),attenuated total reflectance-Fourier transform infrared(ATR-FTIR),Raman,and X-ray photoelectron spectroscopy(XPS).The red-shifted steady-state absorption,95%quenched fluorescence,and largely enhanced nonlinear optical(NLO)properties through Z-scan studies at lower input energies demonstrate that this GO-imi-Por nanohybrid exhibits a more effective photoinduced energy/electron transfer between the intrahybrid two components and can be flexibly applied as an optical limiter *** covalent edge-functionalization approach provides a new paradigm for constructing various edge-expanding GO nanohybrids with an efficient energy/electron transfer process and improved nonlinear optical effects,which would draw inspiration for engineering more adaptable optoelectronic devices.

关键词： covalent edge-functionalization nonlinear optics graphene oxide porphyrin nanohybrid

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Study on multi-size seed-metering device for vertical plate soybean precision planter

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International Journal of Agricultural and Biological Engineering 2015年第1期8卷 1-8页

作者： Liu Hongxin Guo Lifeng fu lulu Tang Shifa College of Engineering Northeast Agricultural UniversityHarbin 150030China

Aiming to solve the problem of small range of the appropriately sowing seeds existing in a vertical disc seed-metering device,the planter plate series with four sizes were developed according to the variety and size distribution of all soybeans in *** structure and working principle of the vertical disc soybean seed-metering device were detailed,and the influence of the diameter of soybean on the working performance of the seed-metering device was analyzed through the software EDEM virtual simulation,so as to achieve the goal of covering the soybean seeds with all sizes by the minimum planter plate series as well as to obtain the most appropriate operating speed of each planter plate by *** the planter plates with the hole diameter of 7,9,12,16 mm,the appropriate size ranges of sowing seeds are 4.5-6.0,6.0-8.0,8.0-10.5,10.5-13.0 mm,respectively,and the appropriate operating speeds are 9,8,7,6 km/h,*** results show that this planter plate series can meet the requirements of seeding with all sizes of soybeans at the range of the most appropriate operating *** study method can provide a reference for design and optimization of precision planters.

关键词： precision planter seed-metering device soybean seed hole size EDEM simulation planter plate series optimization

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Strong near-infrared and ultrafast femtosecond nonlinearities of a covalently-linked triply-fused porphyrin dimer-SWCNT nanohybrid

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Nano Research 2022年第2期15卷 1355-1365页

作者： lulu fu Jun Ye Hui Li Zhipeng Huang Mark GHumphrey Chi Zhang China-Australia Joint Research Center for functional Molecular Materials School of Chemical and Material EngineeringJiangnan UniversityWuxi 214122China China-Australia Joint Research Center for functional Molecular Materials School of Chemical Science and Engineerinz Ton^ii UniversityShanghai 200092China Research School of Chemistry Australian National UniversityCanberraACT 2601Australia

functional materials displaying large ultrafast third-order optical nonlinearities across a wide spectral region and broad temporal domain are required for all-optical signal *** desirable is nonlinear optical(NLO)activity at near-infrared(NIR)wavelengths with femtosecond *** the first triply-fused porphyrin dimer(TFP)-functionalized single-walled carbon nanotube(SWCNT)nanohybrid was successfully constructed by covalently grafting TFPs onto *** results of Z-scan techniques demonstrate that the newly obtained TFP-SWCNT nanohybrid was found with a strong NLO performance under both nanosecond and femtosecond *** the nanosecond regime,an enhancement in optical limiting(OL)of the TFP-SWCNT nanohybrid is seen at 532 nm when compared with the performance of porphyrin monomer-functionalized SWCNT nanohybrid *** femtosecond irradiation,the TFP-SWCNT nanohybrid exhibits a particularly strong OL effect with a giant two-photon absorption(TPA)cross section value(ca.15,500 GM)at 800 nm pulses that mainly stems from intense TPA of TFP,in sharp contrast to the Por-SWCNT nanohybrid which exhibits only saturable absorption under identical *** results demonstrate that the newly-developed TFP-SWCNT nanohybrid is a very promising OL candidate for practical applications across wide spectral and temporal domains,and that covalently functionalizing carbon-based materials with triply-fused chromophores may be a useful approach to engineering adaptable photonic devices with broad-ranging NLO activity.

关键词： triply-fused porphyrin dimer carbon nanotube near-infrared femtosecond nonlinear optical materials

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Machine learning assisted prediction of charge transfer properties in organic solar cells by using morphology-related descriptors

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Nano Research 2023年第2期16卷 3588-3596页

作者： lulu fu Haixia Hu Qiang Zhu Lifeng Zheng Yuming Gu Yaping Wen Haibo Ma Hang Yin Jing Ma Key Laboratory of Mesoscopic Chemistry of Ministry of Education School of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210023China School of Physics Shandong UniversityJinan 250100China Jiangsu Key Laboratory of Advanced Organic Materials School of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210023China

Charge transfer and transport properties are crucial in the photophysical process of exciton dissociation and recombination at the donor/acceptor(D/A)***,machine learning(ML)is applied to predict the charge transfer state energy(ECT)and identify the relationship between ECT and intermolecular packing structures sampled from molecular dynamics(MD)simulations on fullerene-and non-fullerene-based systems with different D/A ratios(RDA),oligomer sizes,and D/A *** gradient boosting regression(GBR)exhibits satisfactory performance(r=0.96)in predicting ECT withπ-packing related features,aggregation extent,backbone of donor,and energy levels of frontier molecular *** charge transport property affected byπ-packing with different RDA has also been investigated by space-charge-limited current(SCLC)measurement and MD *** SCLC results indicate an improved hole transport of non-fullerene system PM6/Y6 with RDA of 1.2:1 in comparison with the 1:1 counterpart,which is mainly attributed to the bridge role of donor unit in *** reduced energetic disorder is correlated with the improved miscibility of polymer with RDA increased from 1:1 to 1.2:*** morphology-related features are also applicable to other complicated systems,such as perovskite solar cells,to bridge the gap between device performance and microscopic packing structures.

关键词： charge transfer charge transport packing modes machine learning organic solar cells

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Synergistic regulation of intermolecular interactions to control chiral structures for chiral recognition

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Chinese Chemical Letters 2023年第3期34卷 332-336页

作者： Weilin Chen lulu fu Zhiqiang Zhu Jingyan Liu Linxiu Cheng Zhou Xu Hao Dong Jing Ma Yibao Li Xiaolin Fan Key Laboratory of Organo-pharmaceutical Chemistry Gannan Normal UniversityGanzhou 341000China Key Laboratory of Mesoscopic Chemistry of Ministry of Education School of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210023China Kuang Yaming Honors School and Institute for Brain Sciences Nanjing UniversityNanjing 210023China

Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.

关键词： Supramolecular chemistry Chiral nanostructure Noncovalent interaction forces Molecular dynamics simulations Chiral recognition

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Cascading electron transfer and photophysics in a donor-π-acceptor graphene nanoconjugate

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Nano Research 2023年第4期16卷 5909-5918页

作者： lulu fu Hui Li Yan Fang Zihao Guan Zhiyuan Wei Naying Shan Fang Liu Yang Zhao Mingfei Zhang Zhipeng Huang Mark GHumphrey Chi Zhang China-Australia Joint Research Center for functional Molecular Materials School of Chemical Science and EngineeringTongji UniversityShanghai 200092China Research School of Chemistry Australian National UniversityCanberraACT 2601Australia

Electron-donating porphyrins(Por),electron-accepting phthalocyanines(Pcs),and reduced graphene oxide(RGO)were integrated into a multicomponent nanoconjugate(Por-RGO-Pc).The donor-π-acceptor nanoconjugate Por-RGO-Pc was characterized using Fourier transform infrared spectroscopy(FTIR),transmission electron microscopy(TEM),scanning electron microscopy(SEM),atomic force microscopy(AFM),and ultraviolet-visible(UV-Vis)*** cascading electron/charge transfer from Por to RGO and from RGO to Pc was established from fluorescence,electrochemical,and femtosecond transient absorption(fs-TA)spectroscopy *** increased distance between the electron donors and acceptors of the Por-RGO-Pc nanoconjugate compared to the parent materials and the intermediate RGO-Pc results in longlived charge separation,and an enhancement in nonlinear optical(NLO)absorption(a large NLO coefficient of about 827.44 cm/GW)towards nanosecond laser irradiation at 532 nm.

关键词： graphene nanoconjugate donor-π-acceptor(D-π-A) cascading charge separation nonlinear optics

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Dramatic femtosecond nonlinear absorption at a strongly coupled porphyrin-graphene nanoconjugate

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Nano Research 2023年第4期16卷 5900-5908页

作者： lulu fu Yan Fang Zihao Guan Zhiyuan Wei Rui Yang Naying Shan Fang Liu Yang Zhao Mingfei Zhang Zhipeng Huang Mark GHumphrey Chi Zhang China-Australia Joint Research Center for functional Molecular Materials School of Chemical Science and EngineeringTongji UniversityShanghai 200092China United World College Changshu 215500China Research School of Chemistry Australian National UniversityCanberraACT 2601Australia

Edge-functionalization of graphene is emerging as a powerful chemical method for the construction ofπ-delocalized highlyplanar graphene nanoconjugates that are not accessible through surface-supported ***,a graphene-porphyrin nanoconjugate via a robust pyrazine(pz)linkage has been obtained by condensing 2,3-diamino-5,10,15,20-tetraphenylporphyrin(DA-TPP)with ortho-quinone(o-quinone)moieties at edge sites of graphene oxide(GO).The as-prepared GO-pz-TPP exhibits an intense absorption extending from 375 to 900 nm and a high quenching yield(98%)of fluorescence,indicating a strong electronic coupling effect between GO and TPP ***-pz-TPP displays strong nonlinear optical(NLO)absorption and giant NLO coefficients with 800 and 1,030 nm fs laser,in sharp contrast to traditional graphene-porphyrin nanohybrids only NLO-active towards ns *** a dramatic NLO performance towards femtosecond pulsed laser has not been achieved in any carbonchromophores nanohybridized materials to *** work validates theπ-extended edge-functionalization strategy as a means to tune the NLO properties of graphene,thereby providing a new paradigm for the assembly of versatile optoelectronic materials.

关键词： graphene oxide porphyrin nanoconjugate femtosecond nonlinear optics

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Middle Triassic post-orogenic extension on Hainan Island: Chronology and geochemistry constraints of bimodal intrusive rocks

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Science China Earth Sciences 2013年第3期56卷 783-793页

作者： TANG LiMei CHEN HanLin DONG ChuanWan YANG ShuFeng SHEN ZhongYue CHENG XiaoGan fu lulu Department of Earth Science Zhejiang University Key Laboratory of Submarine Geosciences Second Institute of Oceanography State Oceanic Administration

This work studies new petrological and geochemical data and zircon U-Pb ages for bimodal intrusive rocks from Xinglong re- gion, Hainan Island. Zircon U-Pb dating yields mean 238U/26pb ages of 238 ± 2 Ma and 234±2 Ma for diabasic and granitic phases, respectively, representing the Middle Triassic emplacement. The diabase and granite bodies were formed from discrete mafic and acidic magma sources that experienced local mechanical mixing at their mutual contacts. Although SiO2 content of intrusions is bimodal, trace element ratios indicate that both were formed in a post-orogenic extensional setting. Sr-Nd isotopic composition reflects a shared EMII type enriched mantle source component, possibly influenced by subduction-fluid metaso- matism.

关键词： bimodal intrusive rocks middle Triassic post-orogenic Hainan Island

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Three Novel Porphyrin-Covalently functionalized Single-Walled Carbon Nanotubes:Synthesis and Enhanced Nonlinear Optical Properties

Three Novel Porphyrin-Covalently Functionalized Single-Walle...

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中国化学会第30届学术年会

作者： Mingfei Zhang lulu fu Huan Liu Jun Ye China-Australia Joint Research Center for functional Molecular Materials School of Chemical and Material EngineeringJiangnan University

As a powerful means to form new functional materials,carbon nanotubes decorated with specific organic molecules have attracted broad attention in the scientific *** here prepare three novel functionalized Single-Walled Carbon Nanotubes（CNTs）,which have porphyrins covalently grafting onto the carbon surface via a stepwise approach involved "click chemistry".The third-order nonlinear optical properties of the resultant composite materials were studied by using the Z-scan technique at 532 nm with both nanosecond and picosecond laser *** results show that the composite materials exhibit significant optical limiting performance as well as improvement in the picosecond regime nonlinear *** can be ascribed to the excellent properties of SWNTs and the effectively decoration with tuned metal-porphyrins.

关键词： Nonlinear optical Single-walled carbon nanotubes Tuned metal-porphyrins Click chemistry

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Synthesis of a novel amine-functionalized fused porphyrin dimer and its near-infrared optical properties

Synthesis of a novel amine-functionalized fused porphyrin di...

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中国化学会第五届卟啉与酞菁学术研讨会

作者： lulu fu Jiaqi Zhou Chi Zhang Jun Ye School of Chemical and Material Engineering Jiangnan University School of Chemical Science and Engineering Tongji University

Porphyrin is one kind of heterocyclic organic compound,which is widely distributed in nature and plays an important role in human beings,animals and *** and its derivatives have high chemical stability and good *** absorption spectra of porphyrins with large conjugation,such as fused porphyrins can easily reach in red or near infrared regions of the solar ***,porphyrins can be used as an antenna in the hybrid structures,which can effectively capture light energy and release ***,porphyrins are often taken as ideal materials for lots of optoelectronic *** this day,porphyrins have been applied to various fields,such as dye-sensitized solar cells,chemical catalytic reactions,electroluminescent materials,biomolecular sensors,molecular targeting drugs and so *** to their large conjugation,fused porphyrins have been found to have good photoelectric properties in earlier ***,due to specific synthesis procedure,the fused porphyrin dimers are often difficult to be modified at the periphery positions for further *** this paper,single porphyrin with two meso-positions exposed was synthesized in advance,and active functional group which has been protected was introduced to one of the meso *** the addition of strong oxidizing agent and following de-protective progress,a novel fused porphyrin dimer with a universal active functional group-amino group was prepared,and its near infrared optical properties were preliminarily studied.

关键词： fused porphyrins near infrared active functional group

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