Fluorophores emitting in the second near-infrared window (NIR-II, 900–1700nm) allow for high-resolution deep-tissue bioimaging owing to minimal tissue scattering. Although J-aggregation offers a promising approach to...Fluorophores emitting in the second near-infrared window (NIR-II, 900–1700nm) allow for high-resolution deep-tissue bioimaging owing to minimal tissue scattering. Although J-aggregation offers a promising approach to developing long-wavelength emitters, the scarcity of J-type backbones and reliable design principles limits their application in biological imaging. Here, we introduce a strategy for engineering high-brightness NIR-II J-aggregated fluorophores by incorporating electron-withdrawing substituents into a fused-ring backbone. These substituents modulate the electrostatic potential (ESP) distribution across the conjugated backbone, reducing both electrostatic repulsion and intermolecular distance, which promotes ordered J-aggregation. As a result, Y8 aggregate (Y8 nanoparticles) exhibits an outstanding fluorescence quantum yield of up to 12.9% and strong near-infrared absorption in aqueous solution for high-performance NIR-II fluorescence imaging in vivo. This work not only presents a novel J-type backbone but also advances the understanding of the structure–property relationship critical to designing NIR-II J-aggregates.展开更多
Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer.Herein,we designed 1,7-diphenyl-substituted meso–CF_(3)-BDP monomer confirmed by X-...Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer.Herein,we designed 1,7-diphenyl-substituted meso–CF_(3)-BDP monomer confirmed by X-ray crystallographic analysis.The low-barrier rotation of the–CF_(3)group in meso–CF_(3)-BDP1 significantly enhances the non-radiative efficiency,and the photothermal conversion efficiency(PCE)of the self-assembled nanoparticles(1-NPs:λ_(abs)=746 nm)by J-aggregates was 82%.1-NPs could effectively block cell cycle progression,inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation(0.2 W/cm^(2)).This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.展开更多
Protonated tetraphenylporphine（H2TPP） J-aggregates were prepared by aggregation on the liquid-air interface. Using FTIR spectroscopy, the authors observed the infrared absorption spectra of H2TPP and its J-aggregate...Protonated tetraphenylporphine（H2TPP） J-aggregates were prepared by aggregation on the liquid-air interface. Using FTIR spectroscopy, the authors observed the infrared absorption spectra of H2TPP and its J-aggregates. The IR spectra of H2TPP J-aggregates show significant changes compared with that of HETPP monomer. Intensity changes（e.g., strong enhancement of the in-plane vibronic mode and weakening of the out-of-plane vibronic mode of phenyl and porphyrin skeletal） were interpreted on the basis of stacking effects. Observation of the same type of bands collapse into single band was explained by the increase in the symmetry of H2TPP molecules. And the new bands at 1635 and 3407 cm^-1 indicate the aggregates containing a large amount of bound water.展开更多
J-aggregates of dye molecules are a unique supramolecular structure, which shows great promise in photoelectric devices due to its remarkable optical and transport properties. In this paper, we report the templated fo...J-aggregates of dye molecules are a unique supramolecular structure, which shows great promise in photoelectric devices due to its remarkable optical and transport properties. In this paper, we report the templated formation of J-aggregate nanotubes by the adsorption of 3,3’-diethylthiacarbocyanine iodide on the self-assembled nanotubes of lithocholic acid. The optical and electronic properties of the templated J-aggregate nanotubes are studied. A sensor platform is fabricated by depositing the J-aggregate nanotubes on interdigitated gold electrodes for the detection of dopamine (DA). We find that the current change of the J-aggregate nanotube-based sensor platform in response to DA is linear in the concentration range from 10 nM to 70 nM, giving the detection limit of 0.27 nM.展开更多
Photodynamic therapy(PDT)and photothermal therapy(PTT)synergistic treatment for hypoxic tumors,always requires highintensity light irradiation.This study introduces an intramolecular modulation approach for achieving ...Photodynamic therapy(PDT)and photothermal therapy(PTT)synergistic treatment for hypoxic tumors,always requires highintensity light irradiation.This study introduces an intramolecular modulation approach for achieving PDT and PTT synergy under gentle light irradiation via the formation of tightly packed J-aggregated nanorings.Specifically,cyanine dyes,designated as TYA and TYB,were synthesized and compared to investigate the influence of intramolecular and intermolecular forces on the formation of compact J-aggregates.Compared to TYA(14.22°,8.58Å),the planar quinoline moieties in TYB exhibit a more pronounced rotation around the methylene linker(50.21°),which facilitates intermolecular slippage and reduces the stacking distance to 4.91Åin J-aggregated nanorings(TYB J-NPs).The smaller monomer separations facilitate the generation of photothermal effects under mild light irradiation.These TYB J-NPs generate reactive oxygen species(ROS)levels comparable to those produced by TYA J-aggregates,while simultaneously producing a thermal effect under near-infrared(NIR)light irradiation(35 mW/cm^(2),10 min,ΔT>20℃).This dual functionality synergistically enables in vivo fluorescence and photothermal imaging,and effectively inhibits the growth and invasion of 4T1 tumors in mice.Moreover,TYB J-NPs demonstrate substantial antibacterial efficacy against both Gram-positive and Gram-negative bacteria,thereby offering effective antibacterial protection during tumor phototherapy.In summary,the intramolecular twisting of TYB effectively resolves the bottleneck associated with intermolecular repulsions at large molecular separations,thereby facilitating the formation of densely packed J-aggregates.This represents the first instance where J-aggregated nanorings enable concurrent PDT and PTT with antibacterial effectiveness under low-density NIR light irradiation.This work may significantly enhance the therapeutic potential of cyanine dyes in cancer treatment,pathogenic bacterial infections,and other diseases.展开更多
The development of photothermal agents with high photothermal conversion efficiency(PCE)and long ab-sorption wavelengths is crucial for safe and effective anti-cancer treatment.However,achieving these advantages often...The development of photothermal agents with high photothermal conversion efficiency(PCE)and long ab-sorption wavelengths is crucial for safe and effective anti-cancer treatment.However,achieving these advantages often requires precise molecular design and complex synthetic procedures.In this study,we present a simple,precise,and effective method for fabricating photothermal agents with high PCE using long wavelength exci-tation.This approach involves linking two electron-donating components,diphenylamine(DPA),and an electron-withdrawing squaraine(SQ),via aπ-bridge thiophene(T).The resulting D-π-A-π-D structure leads to a red-shifted absorption band.Within the DTS structure,DPA functions as a molecular rotor,T serves as a coplanar backbone,and SQ promotes J aggregation.When DTS nanoparticles(NPs)are fabricated using an amphiphilic nano-carrier,the maximum absorption wavelength shifts from 701 to 803 nm.This shift is accompanied by reduced fluorescence and an exceptionally high PCE of 86.0%.Both in vitro and in vivo assessments confirm that DTS NPs exhibit strong potential for photothermal antitumor therapy.Overall,this strategy offers a valuable framework for designing photothermal agents with clinical applications in mind,offering a simpler and more efficient approach to achieving high PCE and long absorption wavelengths.展开更多
Optical cavity polaritons,originated from strong coupling between the excitons in materials and photons in the confined cavities field,have recently emerged as their applications in the high-speed lowpower polaritons ...Optical cavity polaritons,originated from strong coupling between the excitons in materials and photons in the confined cavities field,have recently emerged as their applications in the high-speed lowpower polaritons devices,low-threshold lasing and so on.However,the traditional exciton polaritons based on metal plasmonic structures or Fabry-Perot cavities suffer from the disadvantages of large intrinsic losses or hard to integrate and nanofabricate.This greatly limits the applications of exciton poalritons.Thus,here we implement a compact low-loss dielectric photonic–organic nanostructure by placing a 2-nm-thick PVA doped with TDBC film on top of a planar Si asymmetric nanogratings to reveal the exciton polaritons modes.We find a distinct anti-crossing dispersion behavior appears with a 117.16 meV Rabi splitting when varying the period of Si nanogratings.Polaritons dispersion and mode anti-crossing behaviors are also observed when considering the independence of the height of Si,width of Si nanowire B,and distance between the two Si nanowires in one period.This work offers an opportunity to realize low-loss novel polaritons applications.展开更多
Bioimaging and biosensing in the second nearinfrared(NIR-II)window have attracted great attention due to their unprecedented high temporal–spatial resolution,sensitivity,and penetration depth.Although some organic fl...Bioimaging and biosensing in the second nearinfrared(NIR-II)window have attracted great attention due to their unprecedented high temporal–spatial resolution,sensitivity,and penetration depth.Although some organic fluorescence dyes have been developed in this window,it is still a great challenge to synthesize hydrophilic organic contrast agents with both absorbance and emission wavelengths beyond 1300 nm.J-aggregation is a facile pathway to achieve the wavelength red-shift of organic dyes to the NIR-II window and simultaneously improve their hydrophilicity.Here,we report FD-1080 J-aggregates(FD-J)with absorbance of 1360 nm and emission of 1370 nm through heating H-aggregated FD-1080 cyanine dyes in an aqueous solution.With FD-J administration,real-time imaging of mice brain and hindlimb vasculatures can be performed beyond 1500 nm.Meanwhile,arterial and venous vessels can be clearly distinguished through dynamic imaging after injection of FD-J.In addition,reactive oxygen species-responsive NIR-II ratiometric fluorescence sensors were available based on FD-J and lanthanide nanoparticles to enable the detection of inflammation in living mice.展开更多
Recently we have reported our study on the J-aggregate formation of an anionic cyanine promoted by the counterions of added salts under environmental conditions. The result showed that the counterions are bound to the...Recently we have reported our study on the J-aggregate formation of an anionic cyanine promoted by the counterions of added salts under environmental conditions. The result showed that the counterions are bound to the dye ion J-stacks in 'stoichiometric' relation. Concerning the fact that polyeletrolytes could promote the formation of J-aggregate of cyanine dye ions, the authors suggested that the J-aggregates of an ionic cyanine might more easily induce the J-aggregation of other cyanine ions with opposite charges. The two展开更多
Drug loading capacity is very important in the construction of targeted drug delivery systems(TDDSs)for the improvement of drug delivery efficiency.However,the drug-loading capacity of most nanomaterials is non-ideali...Drug loading capacity is very important in the construction of targeted drug delivery systems(TDDSs)for the improvement of drug delivery efficiency.However,the drug-loading capacity of most nanomaterials is non-idealistic,and developing the high drug-loading TDDSs is still a critical challenge.In this work,an ultrahigh loading system(denoted as HMPB_(2))was prepared via J-aggregation of an aza-boron dipyrromethene derivative(Bod)by using hollow MnO_(2)modified with glucosamine pillar[5]arene as a carrier,which was demonstrated to have typical J-aggregate absorption of Bod,specific cancer cells targeting ability,negligible dark cytotoxicity,and potent phototoxicity.This work provides a successful example to construct an ultrahigh drug-loading system via J-aggregation for targeted delivery.展开更多
As H-and J-aggregation receive more and more attention in the research of organic solar cells(OSCs),especially in small molecular systems,deep understanding of aggregation behavior is needed to guide the design of con...As H-and J-aggregation receive more and more attention in the research of organic solar cells(OSCs),especially in small molecular systems,deep understanding of aggregation behavior is needed to guide the design of conjugated small molecular structure and the fabrication process of OSC device.For this end,this review is written.Here,the review firstly introduced the basic information about H-and J-aggregation of conjugated small molecules in OSCs.Then,the characteristics of H-and J-aggregation and the methods to identify them were summarized.Next,it reviewed the research progress of H-and J-aggregation of conjugated small molecules in OSCs,including the factors influencing H-and J-aggregation in thin film and the effects of H-and J-aggregation on OPV performance.展开更多
Recently, the highly ordered J-aggregates of organic dyes with intriguing optical properties have received considerable attention in biomedical applications. Herein, binary metal ions Mn(Ⅱ)/Fe(Ⅲ) are used to induce ...Recently, the highly ordered J-aggregates of organic dyes with intriguing optical properties have received considerable attention in biomedical applications. Herein, binary metal ions Mn(Ⅱ)/Fe(Ⅲ) are used to induce the formation of indocyanine green(ICG) J-aggregates.Further, the sheet-like J-aggregates are able to act as "carriers" for loading hydrophobic chemotherapeutic gambogic acid(GA), realizing the effect of "killing two birds with one stone" for both treatment and delivery. The as-designed nanoassembly is formed spontaneously in aqueous environment via π-π stacking, electrostatic interaction, and hydrophobic force, exhibiting enhanced photostability of ICG and outstanding reactive oxygen species(ROS) generation ability. Moreover, significant inhibition of tumor growth by the synergetic effect of phototherapy and chemotherapy is verified in a subcutaneous4T1 tumors model. In conclusion, this work not only presents a facile and green approach to manufacture carrier-free nanodrugs, but also establishes a universal platform that has potential application in the co-delivery of near-infrared dye and hydrophobic molecules.展开更多
An activatable photosensitizer that could induce phototoxicity only in target sites is highly demanded to overcome the potential off-target toxicity in photodynamic therapy.It is of great significance to design tailor...An activatable photosensitizer that could induce phototoxicity only in target sites is highly demanded to overcome the potential off-target toxicity in photodynamic therapy.It is of great significance to design tailored photosensitizers with a new caging mechanism that can be activated by molecular signatures of pathogenic tissues.Herein,we report a novel supramolecularly activatable photosensitizer that employs cucurbit[7]uril(CB[7])to regulate the J-aggregate and monomer state of a thio-pentamethine cyanine dye withα-naphthyl group on side arms(Naph-α-TCy5),switching its photosensitizing property between off-on states.The host–vip complex Naph-α-TCy5-CB[7]is a caged photosensitizer with a superior luminescence property in an aqueous solution.It could be effectively activated by polyamines in cancer cells through competitive host–vip complexation;then the restored J-aggregates of Naph-α-TCy5 could efficiently generate singlet oxygen.Eventually,the supramolecularly activatable Naph-α-TCy5-CB[7]demonstrated appreciable antitumor bioactivity in vivo with excellent biosafety.It is anticipated that this design strategy of supramolecularly activatable photosensitizers opens new horizons for efficient photodynamic therapy with specificity and safety.展开更多
The characteristics of the LB films of Schiff base aluminium(Ⅲ), tris(2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium(Ⅲ)[Al(TA12)_3], were studied. The surface pressure-area(π-A) isotherm of Al(TA12)_3 in...The characteristics of the LB films of Schiff base aluminium(Ⅲ), tris(2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium(Ⅲ)[Al(TA12)_3], were studied. The surface pressure-area(π-A) isotherm of Al(TA12)_3 in the pure water subphase was investigated. The molecular area, 0.48 nm^2, is one-third of the expected value that indicates the formation of an aggregate. The Langmuir-Blodgett(LB) films of Al(TA12)_3 were transferred and characterized. The UV-Vis spectra and the AFM image both confirmed that the J-aggregates formed. The polarized UV-Vis spectra indicated that the complex plane had to be oriented with an angle of about 30° to the substrate surface. The IR spectra suggested that the complexation took place between aluminium ions and the oxygen atoms of the ligand rather than the nitrogen atom.展开更多
Atomic force microscopy (AFM) was used for the morphological characterization and precise height meas-urements of two-dimensional molecular layers of carbocyanine dye 3,3’-di(r-sulfopropyl)-4,4’,5,5’-dibenzo-9-ethy...Atomic force microscopy (AFM) was used for the morphological characterization and precise height meas-urements of two-dimensional molecular layers of carbocyanine dye 3,3’-di(r-sulfopropyl)-4,4’,5,5’-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt. The AFM measurements reveal three morphological types of molecular aggregates: leaves, stripes and spots. The leaves are stripes have same monolayer height ~1.4 nm and different crystal shapes: the leaves are monoloyers with the lens shape and the stripes are bilay-ers with the shape of extended rectangles. The monolayer height ~1.4 nm was interpreted as indicating the symmetrical packing arrangement of dye molecules. In the symmetrical monolayer, the sulfopropyl groups of all-trans monomer units are located on both monolayer sides whereas the adjacent stacked dye molecules have a lateral slippage providing the J-aggregate optical properties. The lower height of spots ~1 nm was explained by the model of an asymmetric monolayer with sulfopropyl groups of all-trans monomers occupy-ing the same position with respect to the monolayer plane. The packing arrangement of all-trans monomers in the asymmetric monolayer corresponds to H-aggregate. The alternative models of the packing arrange-ment in monolayers with mono-cis1 monomer configuration are discussed.展开更多
Photodynamic therapy(PDT)and photothermal therapy(PTT)have emerged promising applications in both fundamental research and clinical trials.However,it remains challenging to develop ideal photosensitizers(PSs)that conc...Photodynamic therapy(PDT)and photothermal therapy(PTT)have emerged promising applications in both fundamental research and clinical trials.However,it remains challenging to develop ideal photosensitizers(PSs)that concurrently integrate high photostability,large near-infrared absorptivity,and efficient therapeutic capabilities.Herein,we reported a sample engineering strategy to afford a benzene-fused Cy5 dimer(Cy-D-5)for synergistically boosting PDT/PTT applications.Intriguingly,Cy-D-5 exhibits a tendency to form both J-aggregates and H-aggregates in phosphate-buffered saline,which show a long-wavelength absorption band bathochromically shifted to 810 nm and a short-wavelength absorption band hypsochromically shifted to 745 nm,respectively,when compared to its behavior in ethanol(778 nm).Density-functional theory calculations combined with time-resolved transient optical spectroscopy analysis reveal that the fused dimer Cy-D-5 exhibits a lowΔEST(0.51 eV)and efficient non-radiative transition rates(12.6 times greater than that of the clinically approved PS-indocyanine green[PS-ICG]).Furthermore,the Cy-D-5 demonstrates a higher photosensitizing ability to produce 1O2,stronger photothermal conversion efficiency(η=64.4%),and higher photostability compared with ICG.These combined properties enable Cy-D-5 to achieve complete tumor ablation upon 808 nm laser irradiation,highlighting its potential as a powerful and dual-function phototherapeutic agent.This work may offer a practical strategy for engineering other existing dyes to a red-shifted spectral range for various phototherapy applications.展开更多
Simultaneous photothermal and photodynamic therapies(PTT and PDT)hold great promise for noninvasive tumor therapy.However,effective regulation of PTT and PDT with optimal synergistic effects remains a challenge.To dat...Simultaneous photothermal and photodynamic therapies(PTT and PDT)hold great promise for noninvasive tumor therapy.However,effective regulation of PTT and PDT with optimal synergistic effects remains a challenge.To date,there are only a few synergistic PTT and PDT methods with suitable collaborative effects due to the rarity of efficient nanoplatforms with good cascading properties.To overcome this limitation,a proof-of-concept of self-cascade PTT and PDT was developed for hypoxia-reversible tumor therapy.With the assembly of dimeric indocyanine green(DICG)with oxygen nanobubbles(O_(2)-NBs),DICG/O_(2)-NBs typically exhibit J-aggregates for significant PTT effects,with a high photothermal conversion efficiency of 51.45% under 880 nm light irradiation.Interestingly,the PTT performance of DICG/O_(2)-NBs can switch J-aggregates of DICG into DICG monomers with efficient O_(2) gas liberation,while producing hydroxyl radicals for type Ⅰ PDT.Additionally,the evolved DICG monomer reacts with the released O_(2) to generate plenty of 1O_(2) for efficient type Ⅱ PDT.With these advantages,the cascaded nanoplatform achieves good tumor targeting and biocompatibility,and thus has high tumor inhibition of 94.26%,with an obvious ability to reverse hypoxia.This work demonstrates the efficiency of self-cascade PTT and PDT nanomedicine for high-performance hypoxia-reversible tumor ablation,thus providing a new approach for the development of cascading phototheranostics in vivo.展开更多
Drug-induced hepatotoxicity is a long-standing concern of modern medicine.The production of peroxynitrite(ONOO^(-))is proposed as an early sign of the progression of drug-induced hepatotoxicity.However,conventional bl...Drug-induced hepatotoxicity is a long-standing concern of modern medicine.The production of peroxynitrite(ONOO^(-))is proposed as an early sign of the progression of drug-induced hepatotoxicity.However,conventional blood tests fail to offer a real-time unambiguous visualization of such hepatotoxicity in vivo.ONOO^(-)probes that are currently reported are mainly located in the visible or the first near-infrared(NIR-I)window,which have limited in vivo biosensing application due to the autofluorescence and photon scattering.Here,we report an ONOO^(-)responsive cyanine dye,IR-1061 J-aggregate(J_(IR-1061)),which exhibits a red shift over 500 nm,with an absorption peak at 1580 nm in the NIR-IIb region.By conjugating J_(IR-1061) with rare earth nanoparticles(RENPs)that have NIR-IIb emission at 1550 nm,a dual-mode imaging probe RENPs-J_(IR-1061) is developed.RENPs-J_(IR-1061) shows a fast and sensitive response to ONOO^(-),with activatable NIR-IIb fluorescence and a change in the photoacoustic signals,which is successfully applied for real-time monitoring of hepatotoxicity in vivo.展开更多
Carbon-oxygen-bridged (CO-bridged) ladder-type units already proved to be promising electron-donating building blocks for making acceptor-donor-acceptor (A-D-A) nonfullerene acceptors [1].Compared with traditional car...Carbon-oxygen-bridged (CO-bridged) ladder-type units already proved to be promising electron-donating building blocks for making acceptor-donor-acceptor (A-D-A) nonfullerene acceptors [1].Compared with traditional carbon-bridged (C-bridged) units, CObridged units present stronger electron-donating capability due to electron-rich oxygen atoms.展开更多
J-aggregates of cyanine have shown great merits in tumor photothermal therapy(PTT)due to their distinct redshift absorption as well as superior photothermal conversion efficiency(PCE).However,due to the complexity of ...J-aggregates of cyanine have shown great merits in tumor photothermal therapy(PTT)due to their distinct redshift absorption as well as superior photothermal conversion efficiency(PCE).However,due to the complexity of intermolecular interactions,especially the impact of steric hindrance on aggregation,exploring effective strategies to regulate the aggregation modes of organic materials remains challenging.Herein,steric hindrance-regulated J-aggregation of near-infrared(NIR)cyanine was reported based on Pt-coordinated cyanine self-assembly with unexpected“butterfly effect”.Two Pt-coordinated cyanine dimers CyR-Pt(R=Me and Et)were synthesized and spontaneously self-assembled into aggregates in aqueous solution.CyEt-Pt aggregates were loose and amorphous stacking.By replacing ethyl with methyl to reduce steric hindrance,a tiny change resulted in the generation of tightly stacked cyanine J-aggregates(thickness less than 3 nm)observed in CyMe-Pt self-assembly.Significantly,this unexpected“butterfly effect”enabled CyMe-Pt J-aggregates to effectively inhibit reactive oxygen species and greatly improve its photostability.Besides,CyMe-Pt J-aggregates with NIR-II absorption exhibited outstanding photothermal stability and higher PCE(η=37%)than CyEt-Pt disordered aggregates(η=20%).Evident tumor suppression performance of CyMe-Pt J-aggregates was validated under 980 nm laser irradiation,demonstrating its great potential in tumor PTT.展开更多
基金support from the National Natural Science Foundation of China (Nos. 62175201 and 52373142)the Natural Science Foundation of Jiangsu Province of China (No. BK20220404)+1 种基金the Fundamental Research Funds for the Central Universitiesthe open research fund of State Key Laboratory of Organic Electronics and Information Displays.
文摘Fluorophores emitting in the second near-infrared window (NIR-II, 900–1700nm) allow for high-resolution deep-tissue bioimaging owing to minimal tissue scattering. Although J-aggregation offers a promising approach to developing long-wavelength emitters, the scarcity of J-type backbones and reliable design principles limits their application in biological imaging. Here, we introduce a strategy for engineering high-brightness NIR-II J-aggregated fluorophores by incorporating electron-withdrawing substituents into a fused-ring backbone. These substituents modulate the electrostatic potential (ESP) distribution across the conjugated backbone, reducing both electrostatic repulsion and intermolecular distance, which promotes ordered J-aggregation. As a result, Y8 aggregate (Y8 nanoparticles) exhibits an outstanding fluorescence quantum yield of up to 12.9% and strong near-infrared absorption in aqueous solution for high-performance NIR-II fluorescence imaging in vivo. This work not only presents a novel J-type backbone but also advances the understanding of the structure–property relationship critical to designing NIR-II J-aggregates.
基金supported by the National Natural Science Foundation of China(Nos.22078201,U1908202)Natural Science Foundation of Liaoning(No.2021NLTS1206)+2 种基金Serving Local Project of Education Department of Liaoning Province(No.LZ2020005)Liaoning&Shenyang Key Laboratory of Functional Dye and Pigment(Nos.2021JH13/10200018,21-104-0-23)the Distinguished Professor Project Liaoning Province(No.20183532)。
文摘Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer.Herein,we designed 1,7-diphenyl-substituted meso–CF_(3)-BDP monomer confirmed by X-ray crystallographic analysis.The low-barrier rotation of the–CF_(3)group in meso–CF_(3)-BDP1 significantly enhances the non-radiative efficiency,and the photothermal conversion efficiency(PCE)of the self-assembled nanoparticles(1-NPs:λ_(abs)=746 nm)by J-aggregates was 82%.1-NPs could effectively block cell cycle progression,inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation(0.2 W/cm^(2)).This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.
基金Supported by the National Natural Science Foundation of China(No.10774057).
文摘Protonated tetraphenylporphine（H2TPP） J-aggregates were prepared by aggregation on the liquid-air interface. Using FTIR spectroscopy, the authors observed the infrared absorption spectra of H2TPP and its J-aggregates. The IR spectra of H2TPP J-aggregates show significant changes compared with that of HETPP monomer. Intensity changes（e.g., strong enhancement of the in-plane vibronic mode and weakening of the out-of-plane vibronic mode of phenyl and porphyrin skeletal） were interpreted on the basis of stacking effects. Observation of the same type of bands collapse into single band was explained by the increase in the symmetry of H2TPP molecules. And the new bands at 1635 and 3407 cm^-1 indicate the aggregates containing a large amount of bound water.
文摘J-aggregates of dye molecules are a unique supramolecular structure, which shows great promise in photoelectric devices due to its remarkable optical and transport properties. In this paper, we report the templated formation of J-aggregate nanotubes by the adsorption of 3,3’-diethylthiacarbocyanine iodide on the self-assembled nanotubes of lithocholic acid. The optical and electronic properties of the templated J-aggregate nanotubes are studied. A sensor platform is fabricated by depositing the J-aggregate nanotubes on interdigitated gold electrodes for the detection of dopamine (DA). We find that the current change of the J-aggregate nanotube-based sensor platform in response to DA is linear in the concentration range from 10 nM to 70 nM, giving the detection limit of 0.27 nM.
基金supported by the National Natural Science Foundation of China(22108024)the Liaoning Provincial Department of Education University Basic Research Project(LJ212410152028)+1 种基金the Dalian High-level Talent Innovation Support Program of China(2022RQ016)the Fundamental Research Fundamental Funds for the Central Universities(DUT22LAB601).
文摘Photodynamic therapy(PDT)and photothermal therapy(PTT)synergistic treatment for hypoxic tumors,always requires highintensity light irradiation.This study introduces an intramolecular modulation approach for achieving PDT and PTT synergy under gentle light irradiation via the formation of tightly packed J-aggregated nanorings.Specifically,cyanine dyes,designated as TYA and TYB,were synthesized and compared to investigate the influence of intramolecular and intermolecular forces on the formation of compact J-aggregates.Compared to TYA(14.22°,8.58Å),the planar quinoline moieties in TYB exhibit a more pronounced rotation around the methylene linker(50.21°),which facilitates intermolecular slippage and reduces the stacking distance to 4.91Åin J-aggregated nanorings(TYB J-NPs).The smaller monomer separations facilitate the generation of photothermal effects under mild light irradiation.These TYB J-NPs generate reactive oxygen species(ROS)levels comparable to those produced by TYA J-aggregates,while simultaneously producing a thermal effect under near-infrared(NIR)light irradiation(35 mW/cm^(2),10 min,ΔT>20℃).This dual functionality synergistically enables in vivo fluorescence and photothermal imaging,and effectively inhibits the growth and invasion of 4T1 tumors in mice.Moreover,TYB J-NPs demonstrate substantial antibacterial efficacy against both Gram-positive and Gram-negative bacteria,thereby offering effective antibacterial protection during tumor phototherapy.In summary,the intramolecular twisting of TYB effectively resolves the bottleneck associated with intermolecular repulsions at large molecular separations,thereby facilitating the formation of densely packed J-aggregates.This represents the first instance where J-aggregated nanorings enable concurrent PDT and PTT with antibacterial effectiveness under low-density NIR light irradiation.This work may significantly enhance the therapeutic potential of cyanine dyes in cancer treatment,pathogenic bacterial infections,and other diseases.
基金supported by the National Natural Science Foundation of China(32101129,52103230,32101124)Shenzhen Basic Research Special(Natural Science Fund)basic research surface project(No.JCYJ20210324113006017)+1 种基金Guangdong basic and Applied Basic Research Fund Regional Joint Fund Project(key project)(No.2020B1515120091)China Postdoctoral Science Foundation(2021M691440).
文摘The development of photothermal agents with high photothermal conversion efficiency(PCE)and long ab-sorption wavelengths is crucial for safe and effective anti-cancer treatment.However,achieving these advantages often requires precise molecular design and complex synthetic procedures.In this study,we present a simple,precise,and effective method for fabricating photothermal agents with high PCE using long wavelength exci-tation.This approach involves linking two electron-donating components,diphenylamine(DPA),and an electron-withdrawing squaraine(SQ),via aπ-bridge thiophene(T).The resulting D-π-A-π-D structure leads to a red-shifted absorption band.Within the DTS structure,DPA functions as a molecular rotor,T serves as a coplanar backbone,and SQ promotes J aggregation.When DTS nanoparticles(NPs)are fabricated using an amphiphilic nano-carrier,the maximum absorption wavelength shifts from 701 to 803 nm.This shift is accompanied by reduced fluorescence and an exceptionally high PCE of 86.0%.Both in vitro and in vivo assessments confirm that DTS NPs exhibit strong potential for photothermal antitumor therapy.Overall,this strategy offers a valuable framework for designing photothermal agents with clinical applications in mind,offering a simpler and more efficient approach to achieving high PCE and long absorption wavelengths.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFB2200403)the National Natural Science Foundation of China(Grant Nos.61775003,11734001,11527901,and 11804008)+2 种基金the National Postdoctoral Program for Innovative Talents(No.BX201700011)the China Postdoctoral Science Foundation(No.2018M630019)Beijing Municipal Science&Technology Commission(No.Z191100007219001).
文摘Optical cavity polaritons,originated from strong coupling between the excitons in materials and photons in the confined cavities field,have recently emerged as their applications in the high-speed lowpower polaritons devices,low-threshold lasing and so on.However,the traditional exciton polaritons based on metal plasmonic structures or Fabry-Perot cavities suffer from the disadvantages of large intrinsic losses or hard to integrate and nanofabricate.This greatly limits the applications of exciton poalritons.Thus,here we implement a compact low-loss dielectric photonic–organic nanostructure by placing a 2-nm-thick PVA doped with TDBC film on top of a planar Si asymmetric nanogratings to reveal the exciton polaritons modes.We find a distinct anti-crossing dispersion behavior appears with a 117.16 meV Rabi splitting when varying the period of Si nanogratings.Polaritons dispersion and mode anti-crossing behaviors are also observed when considering the independence of the height of Si,width of Si nanowire B,and distance between the two Si nanowires in one period.This work offers an opportunity to realize low-loss novel polaritons applications.
基金supported by the National Key R&D Program of China(no.2017YFA0207303)National Natural Science Foundation of China(NSFC,nos.22088101,21725502,51961145403,and 22004018)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality(nos.20JC1411700,19490713100,20490710600,and 20S3190370)。
文摘Bioimaging and biosensing in the second nearinfrared(NIR-II)window have attracted great attention due to their unprecedented high temporal–spatial resolution,sensitivity,and penetration depth.Although some organic fluorescence dyes have been developed in this window,it is still a great challenge to synthesize hydrophilic organic contrast agents with both absorbance and emission wavelengths beyond 1300 nm.J-aggregation is a facile pathway to achieve the wavelength red-shift of organic dyes to the NIR-II window and simultaneously improve their hydrophilicity.Here,we report FD-1080 J-aggregates(FD-J)with absorbance of 1360 nm and emission of 1370 nm through heating H-aggregated FD-1080 cyanine dyes in an aqueous solution.With FD-J administration,real-time imaging of mice brain and hindlimb vasculatures can be performed beyond 1500 nm.Meanwhile,arterial and venous vessels can be clearly distinguished through dynamic imaging after injection of FD-J.In addition,reactive oxygen species-responsive NIR-II ratiometric fluorescence sensors were available based on FD-J and lanthanide nanoparticles to enable the detection of inflammation in living mice.
文摘Recently we have reported our study on the J-aggregate formation of an anionic cyanine promoted by the counterions of added salts under environmental conditions. The result showed that the counterions are bound to the dye ion J-stacks in 'stoichiometric' relation. Concerning the fact that polyeletrolytes could promote the formation of J-aggregate of cyanine dye ions, the authors suggested that the J-aggregates of an ionic cyanine might more easily induce the J-aggregation of other cyanine ions with opposite charges. The two
基金the National Natural Science Foundation of China(Nos.22171230 and 21877088)the Project of Science and Technology of Social Development in Shaanxi Province(No.2021SF-120)。
文摘Drug loading capacity is very important in the construction of targeted drug delivery systems(TDDSs)for the improvement of drug delivery efficiency.However,the drug-loading capacity of most nanomaterials is non-idealistic,and developing the high drug-loading TDDSs is still a critical challenge.In this work,an ultrahigh loading system(denoted as HMPB_(2))was prepared via J-aggregation of an aza-boron dipyrromethene derivative(Bod)by using hollow MnO_(2)modified with glucosamine pillar[5]arene as a carrier,which was demonstrated to have typical J-aggregate absorption of Bod,specific cancer cells targeting ability,negligible dark cytotoxicity,and potent phototoxicity.This work provides a successful example to construct an ultrahigh drug-loading system via J-aggregation for targeted delivery.
基金financially supported by the National Natural Science Foundation of China(52203024,22225504)the Shandong Provincial Natural Science Foundation(ZR2022QE135)+2 种基金the Youth Innovation Team Project of Shandong Provincial University(2023KJ330)the Qilu University of Technology strong base plan(2023PY001)Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
文摘As H-and J-aggregation receive more and more attention in the research of organic solar cells(OSCs),especially in small molecular systems,deep understanding of aggregation behavior is needed to guide the design of conjugated small molecular structure and the fabrication process of OSC device.For this end,this review is written.Here,the review firstly introduced the basic information about H-and J-aggregation of conjugated small molecules in OSCs.Then,the characteristics of H-and J-aggregation and the methods to identify them were summarized.Next,it reviewed the research progress of H-and J-aggregation of conjugated small molecules in OSCs,including the factors influencing H-and J-aggregation in thin film and the effects of H-and J-aggregation on OPV performance.
基金supported by the “333 Project Talent Training Fund of Jiangsu Province (BRA2017432)the Project of Double-top Class Innovation Team (CPU2018GY14)+1 种基金the Project Program of State Key Laboratory of Natural Medicines, China Pharmaceutical University (JKGQ201107)the Open Project of Jiangsu Key Laboratory of Druggability of Biopharmaceuticals (JKLDBKF201702)
文摘Recently, the highly ordered J-aggregates of organic dyes with intriguing optical properties have received considerable attention in biomedical applications. Herein, binary metal ions Mn(Ⅱ)/Fe(Ⅲ) are used to induce the formation of indocyanine green(ICG) J-aggregates.Further, the sheet-like J-aggregates are able to act as "carriers" for loading hydrophobic chemotherapeutic gambogic acid(GA), realizing the effect of "killing two birds with one stone" for both treatment and delivery. The as-designed nanoassembly is formed spontaneously in aqueous environment via π-π stacking, electrostatic interaction, and hydrophobic force, exhibiting enhanced photostability of ICG and outstanding reactive oxygen species(ROS) generation ability. Moreover, significant inhibition of tumor growth by the synergetic effect of phototherapy and chemotherapy is verified in a subcutaneous4T1 tumors model. In conclusion, this work not only presents a facile and green approach to manufacture carrier-free nanodrugs, but also establishes a universal platform that has potential application in the co-delivery of near-infrared dye and hydrophobic molecules.
基金supported by the National Natural Science Foundation of China(grant nos.22193020,22193021,and 21821001)the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB36000000).
文摘An activatable photosensitizer that could induce phototoxicity only in target sites is highly demanded to overcome the potential off-target toxicity in photodynamic therapy.It is of great significance to design tailored photosensitizers with a new caging mechanism that can be activated by molecular signatures of pathogenic tissues.Herein,we report a novel supramolecularly activatable photosensitizer that employs cucurbit[7]uril(CB[7])to regulate the J-aggregate and monomer state of a thio-pentamethine cyanine dye withα-naphthyl group on side arms(Naph-α-TCy5),switching its photosensitizing property between off-on states.The host–vip complex Naph-α-TCy5-CB[7]is a caged photosensitizer with a superior luminescence property in an aqueous solution.It could be effectively activated by polyamines in cancer cells through competitive host–vip complexation;then the restored J-aggregates of Naph-α-TCy5 could efficiently generate singlet oxygen.Eventually,the supramolecularly activatable Naph-α-TCy5-CB[7]demonstrated appreciable antitumor bioactivity in vivo with excellent biosafety.It is anticipated that this design strategy of supramolecularly activatable photosensitizers opens new horizons for efficient photodynamic therapy with specificity and safety.
基金Supported by the National Natural Science Foundation of China(No. 29973026, 20073016).
文摘The characteristics of the LB films of Schiff base aluminium(Ⅲ), tris(2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium(Ⅲ)[Al(TA12)_3], were studied. The surface pressure-area(π-A) isotherm of Al(TA12)_3 in the pure water subphase was investigated. The molecular area, 0.48 nm^2, is one-third of the expected value that indicates the formation of an aggregate. The Langmuir-Blodgett(LB) films of Al(TA12)_3 were transferred and characterized. The UV-Vis spectra and the AFM image both confirmed that the J-aggregates formed. The polarized UV-Vis spectra indicated that the complex plane had to be oriented with an angle of about 30° to the substrate surface. The IR spectra suggested that the complexation took place between aluminium ions and the oxygen atoms of the ligand rather than the nitrogen atom.
文摘Atomic force microscopy (AFM) was used for the morphological characterization and precise height meas-urements of two-dimensional molecular layers of carbocyanine dye 3,3’-di(r-sulfopropyl)-4,4’,5,5’-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt. The AFM measurements reveal three morphological types of molecular aggregates: leaves, stripes and spots. The leaves are stripes have same monolayer height ~1.4 nm and different crystal shapes: the leaves are monoloyers with the lens shape and the stripes are bilay-ers with the shape of extended rectangles. The monolayer height ~1.4 nm was interpreted as indicating the symmetrical packing arrangement of dye molecules. In the symmetrical monolayer, the sulfopropyl groups of all-trans monomer units are located on both monolayer sides whereas the adjacent stacked dye molecules have a lateral slippage providing the J-aggregate optical properties. The lower height of spots ~1 nm was explained by the model of an asymmetric monolayer with sulfopropyl groups of all-trans monomers occupy-ing the same position with respect to the monolayer plane. The packing arrangement of all-trans monomers in the asymmetric monolayer corresponds to H-aggregate. The alternative models of the packing arrange-ment in monolayers with mono-cis1 monomer configuration are discussed.
基金supported by the National Natural Science Foundation of China(Nos.22308220 and 22090011)Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120001)+3 种基金Research Team Cultivation Program of Shenzhen University(No.2023QNT005)Shenzhen University 2035 Program for Excellent Research(Nos.00000208,00000225)Shenzhen University Third-Phase Project of Constructing High-Level University(No.000001032104)Marshall Laboratory of Biomedical Engineering,Shenzhen University(No.86122-000001).
文摘Photodynamic therapy(PDT)and photothermal therapy(PTT)have emerged promising applications in both fundamental research and clinical trials.However,it remains challenging to develop ideal photosensitizers(PSs)that concurrently integrate high photostability,large near-infrared absorptivity,and efficient therapeutic capabilities.Herein,we reported a sample engineering strategy to afford a benzene-fused Cy5 dimer(Cy-D-5)for synergistically boosting PDT/PTT applications.Intriguingly,Cy-D-5 exhibits a tendency to form both J-aggregates and H-aggregates in phosphate-buffered saline,which show a long-wavelength absorption band bathochromically shifted to 810 nm and a short-wavelength absorption band hypsochromically shifted to 745 nm,respectively,when compared to its behavior in ethanol(778 nm).Density-functional theory calculations combined with time-resolved transient optical spectroscopy analysis reveal that the fused dimer Cy-D-5 exhibits a lowΔEST(0.51 eV)and efficient non-radiative transition rates(12.6 times greater than that of the clinically approved PS-indocyanine green[PS-ICG]).Furthermore,the Cy-D-5 demonstrates a higher photosensitizing ability to produce 1O2,stronger photothermal conversion efficiency(η=64.4%),and higher photostability compared with ICG.These combined properties enable Cy-D-5 to achieve complete tumor ablation upon 808 nm laser irradiation,highlighting its potential as a powerful and dual-function phototherapeutic agent.This work may offer a practical strategy for engineering other existing dyes to a red-shifted spectral range for various phototherapy applications.
基金supported by the National Key R&D Program of China(No.2023YFF0713600)the National Natural Science Foundation of China(Nos.62375138,and 52173135)+3 种基金the National Natural Science Innovative Research Group Project(No.61821002)the Frontier Fundamental Research Program of Jiangsu Province for Leading Technology(No.BK 20222002)the Natural Science Foundation of Jiangsu Province(No.BK 20231523)Jiangsu Specially Appointed Professorship.
文摘Simultaneous photothermal and photodynamic therapies(PTT and PDT)hold great promise for noninvasive tumor therapy.However,effective regulation of PTT and PDT with optimal synergistic effects remains a challenge.To date,there are only a few synergistic PTT and PDT methods with suitable collaborative effects due to the rarity of efficient nanoplatforms with good cascading properties.To overcome this limitation,a proof-of-concept of self-cascade PTT and PDT was developed for hypoxia-reversible tumor therapy.With the assembly of dimeric indocyanine green(DICG)with oxygen nanobubbles(O_(2)-NBs),DICG/O_(2)-NBs typically exhibit J-aggregates for significant PTT effects,with a high photothermal conversion efficiency of 51.45% under 880 nm light irradiation.Interestingly,the PTT performance of DICG/O_(2)-NBs can switch J-aggregates of DICG into DICG monomers with efficient O_(2) gas liberation,while producing hydroxyl radicals for type Ⅰ PDT.Additionally,the evolved DICG monomer reacts with the released O_(2) to generate plenty of 1O_(2) for efficient type Ⅱ PDT.With these advantages,the cascaded nanoplatform achieves good tumor targeting and biocompatibility,and thus has high tumor inhibition of 94.26%,with an obvious ability to reverse hypoxia.This work demonstrates the efficiency of self-cascade PTT and PDT nanomedicine for high-performance hypoxia-reversible tumor ablation,thus providing a new approach for the development of cascading phototheranostics in vivo.
基金the National Natural Science Foundation of China,grant number 22374073.
文摘Drug-induced hepatotoxicity is a long-standing concern of modern medicine.The production of peroxynitrite(ONOO^(-))is proposed as an early sign of the progression of drug-induced hepatotoxicity.However,conventional blood tests fail to offer a real-time unambiguous visualization of such hepatotoxicity in vivo.ONOO^(-)probes that are currently reported are mainly located in the visible or the first near-infrared(NIR-I)window,which have limited in vivo biosensing application due to the autofluorescence and photon scattering.Here,we report an ONOO^(-)responsive cyanine dye,IR-1061 J-aggregate(J_(IR-1061)),which exhibits a red shift over 500 nm,with an absorption peak at 1580 nm in the NIR-IIb region.By conjugating J_(IR-1061) with rare earth nanoparticles(RENPs)that have NIR-IIb emission at 1550 nm,a dual-mode imaging probe RENPs-J_(IR-1061) is developed.RENPs-J_(IR-1061) shows a fast and sensitive response to ONOO^(-),with activatable NIR-IIb fluorescence and a change in the photoacoustic signals,which is successfully applied for real-time monitoring of hepatotoxicity in vivo.
基金supported by the National Key Research and Development Program of China(2017YFA0206600)the National Natural Science Foundation of China(51773045,21572041 and21772030)the Youth Association for Promoting Innovation(CAS)
文摘Carbon-oxygen-bridged (CO-bridged) ladder-type units already proved to be promising electron-donating building blocks for making acceptor-donor-acceptor (A-D-A) nonfullerene acceptors [1].Compared with traditional carbon-bridged (C-bridged) units, CObridged units present stronger electron-donating capability due to electron-rich oxygen atoms.
基金supported financially by Guangdong Basic and Applied Basic Research Foundation(2019A1515110441)the Natural Science Foundation of Shandong Province(ZR2020QB001)+1 种基金the National Key Research and Development Program of China(2023YFC3403000)the National Natural Science Foundation of China(22378231 and 22001148)。
文摘J-aggregates of cyanine have shown great merits in tumor photothermal therapy(PTT)due to their distinct redshift absorption as well as superior photothermal conversion efficiency(PCE).However,due to the complexity of intermolecular interactions,especially the impact of steric hindrance on aggregation,exploring effective strategies to regulate the aggregation modes of organic materials remains challenging.Herein,steric hindrance-regulated J-aggregation of near-infrared(NIR)cyanine was reported based on Pt-coordinated cyanine self-assembly with unexpected“butterfly effect”.Two Pt-coordinated cyanine dimers CyR-Pt(R=Me and Et)were synthesized and spontaneously self-assembled into aggregates in aqueous solution.CyEt-Pt aggregates were loose and amorphous stacking.By replacing ethyl with methyl to reduce steric hindrance,a tiny change resulted in the generation of tightly stacked cyanine J-aggregates(thickness less than 3 nm)observed in CyMe-Pt self-assembly.Significantly,this unexpected“butterfly effect”enabled CyMe-Pt J-aggregates to effectively inhibit reactive oxygen species and greatly improve its photostability.Besides,CyMe-Pt J-aggregates with NIR-II absorption exhibited outstanding photothermal stability and higher PCE(η=37%)than CyEt-Pt disordered aggregates(η=20%).Evident tumor suppression performance of CyMe-Pt J-aggregates was validated under 980 nm laser irradiation,demonstrating its great potential in tumor PTT.
