Multi-branched carbazole derivatives for two-photon absorption and two-photon excited fluorescence

Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl） -[ 1, 3, 4 ] oxadiazol-2-yl ] -phenyl }-vinyl ） -carbazole （ 2 ） are synthesized through Wittig reaction and characterized by nuclear magnetic resonance（NMR）and infrared（IR）. The two- photon absorption properties of chromophores are investigated. These chromophores exhibit large two-photon absorption crosssections and strong blue two-photon excited fluorescence. The cooperative enhancement of two-photon absorption（TPA） in the multi-branched structures is observed. This enhancement is partly attributed to the electronic coupling between the branches. The electronic push-pull structures in the arm and their cooperative effects help the extended charge transfer for TPA.

Two-photon Excited Fluorescence of Bithiophene Derivatives

Two new bithiophene derivatives named as 5, 5-bis(p-N,N-dimethylaminostyryl)-2, 2 -bithiophene (BMSBT), and 5, 5-bis(p-N,N-diethylaminostyryl)-2, 2-bithiophene (BESBT) have been synthesized. Both compounds can emit strong single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (TPEF) with the emission peaks around ~560 nm and with the lifetime of ~1ns.

New Thiophene Derivatives with Two-photon Excited Fluorescence

Two new compounds involving a thiophene moiety named as 2,5-bis[4-(N,N- diphenyl- amino)styryl]thiophene (BPST) and 2,5-bis[4-(N,N-diethylamino)styryl]thiophene (BEST) have been synthesized. The two-photon absorption cross section of BPST was measured as large as 256 × 10-50 cm4·s/photon, when it was excited by 800 nm femtosecond laser.

Single & Two-photon Excited Fluorescence of Two New Compounds with 2-Benzothiazolyl as Electron Acceptor

Two new D--A type compounds, where electron-donor D is tertiary amino group, electron-acceptor A is 2-benzothiazolyl and ?is two conjugated styryl units, have been synthesized. They are named as trans, trans-2-{4-[4-(N, N-diethylamino)styryl]styryl}-1, 3-benzothiazole and trans, trans-2-{4-[4-(N, N-diphenylamino)styryl]styryl}-1, 3-benzothiazole. Both compounds show strong two-photon excited fluorescence in yellow-orange region when excited by a femtosecond laser at 800 nm.

Optical second-harmonic generation imaging for identifying gastrointestinal stromal tumors

Gastrointestinal stromal tumors(GISTs)are the most common mesenchymal tumors arising in the digest tract.It brings a challenge to diagnosis because it is asymptomatic clinically.It is well known that tumor development is often accompanied by the changes in the morphology of collagen fibers.Nowadays,an emerging optical imaging technique,second-harmonic generation(SHG),can directly identify collagen fibers without staining due to its noncentrosymmetric properties.Therefore,in this study,we attempt to assess the feasibility of SHG imaging for detecting GISTs by monitoring the morphological changes of collagen fibers in tumor microenvironment.We found that collagen alterations occurred obviously in the GISTs by comparing with normal tissues,and furthermore,two morphological features from SHG images were extracted to quantitatively assess the morphological difference of collagen fibers between normal muscular layer and GISTs by means of automated image analysis.Quantitative analyses show a significant difference in the two collagen features.This study demonstrates the potential of SHG imaging as an adjunctive diagnostic tool for label-free identification of GISTs.

ULTRASHORT PULSE MULTISPECTRAL NON-LINEAR OPTICAL MICROSCOPY

Ultrashort pulse,multispectral non-linear optical microscopy(NLOM)is developed and used to image,simultaneously,a mixed population of cells expressing different fluorescent protein mutants in a 3D tissue model of angiogenesis.Broadband,sub-10-fs pulses are used to excite multiple fluorescent proteins and generate second harmonic in collagen.A 16-channel multispectral detector is used to delineate the multiple non-linear optical signals,pixel by pixel,in NLOM.The ability to image multiple fluorescent protein mutants and collagen,enables serial measurements of cell-cell and cell-matrix interactions in our 3D tissue model and characterization of fundamental processes in angiogenic morphogenesis.

Synthesis and Two-photon Absorption Properties of s-Triazine Derivatives

Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The two-photon absorption cross-section σ, and the two-photon excited fluorescence (TPEF) intensities are increased significantly from dipolar compound to octupolar compound.

Characteristics of extracellular fluorescent substances of aerobic granular sludge in pilot-scale sequencing batch reactor

The aerobic granular sludge was cultivated in a pilot-scale sequencing batch reactor （SBR）, and some of the granules were stored at 8 ℃ for 150 d. Extracellular polymeric substances （EPS） of sludge samples were extracted and analyzed during the granulation and storage process. The results show that the contents of protein and EPS increase along with the granulation process, while polysaccharides remain almost unchanged. The content of protein in EPS is almost two-fold larger than that of polysaccharides in granular sludge cultivated with municipal wastewater. Moreover, some of the granules disintegrate during storage, corresponding to the decrease of protein contents in EPS. Three peaks are identified in three-dimensional excitation emission matrix （EEM） fluorescence spectra of the EPS in the aerobic granules. Two peaks （A and B） are attributed to the protein-like fluorophores, and the third （peak C） is related to visible fulvic-like substances. Peak A gradually disappears during storage, while a new peak related to ultraviolet fulvic acid （peak D） is formed. The formation and the stability of aerobic granules are closely dependent on the quantity and composition of EPS proteins. Peak C has no obvious changes during granulation, while the fulvic-like substances present an increase in fluorescence intensities during storage, accompanied with an increase in structural complexity. The fulvie-like substances are also associated with the disintegration of the aerobic granules.

Two-photon excitation fuorescence lifetime imaging microscopy:A promising diagnostic tool for digestive tract tumors

Digestive tract tumors acount for 15%and 19.3%of the cancer incidence and deaths,respec-tively.Early detection of digestive tract tumors is crucial to the reduction of global cancer burden.Two-photon excitation fuorescence lifetime imaging microscopy(TP-FLIM)allows non-invasive,label free,three-dimensional,high-resolution imaging of living tisues with not only histological but also biochemical characterization ability in both qualitative and quantitative way.Benefiting from these advantages,this technology is protmising for clinical diagnosis of digestive tract tumors.In recent years,many efforts have'been made in this field and some remarkable progress has been achieved.In this paper,we overview the recent progress of TP-FLIM-based researches on digestive tract tumor detection.Among them,our latest results on the gastric cancer and esophageal cancer are elaborately depicted.Finally,we outlook and discuss the potential advantages and challenges of TP-FLIM in future clinical applications.

Studies on NaLn(WO_4)_2 Single Crystals(Ln=La,Pr,Nd)

The crystals of NaLn(WO4)_2(Ln=La,Pr,Nd)are grown from a melt of LiCl-Na_2WO_4 flux by slow cooling method.The chemical analysis data show that the crystals are NaLa(WO_4)_2,NaPr(WO4)_2 and NaNd(WO_4)_2 respectively.The structures of the crystals are ascertained that they belong to scheelite structure of the tetragonal system with a space group of 14_1/a.The lattice parameters of the crystals have been calculated.It is found that the cell volume of NaLn(WO_4)_2 crystals decrease with a decrease of Ln^(3+)radius. The bond distances and their angles in NaLa(WO_4)_2 and NaNd(WO_4)_2 are given.It is found that in accordance with the decrease of ionic radii of Ln^(3+)due to increase of atomic number,the bond distances between Ln-O,Ln-Ln and W-O decrease regularly.The infrared spectra of NaLn(WO_4)_2 are measured.The tetrahedra characteristic absorptions of WO_4^(2-)are shown.The sensitization of host lattice is observed from the excitation and fluorescent spectra of NaLa(WO_4)_2 and NaPr(WO_4)_2.

Luminescence Properties of Ca(NbO_3)_2∶Dy^(3+)

On the base of the luminescence properties of the Dy (3+) activated Ⅱ-Ⅴ group complex oxide,the luminescence properties of Ca(NbO_3)_2∶Dy (3+) and compensation effect by Na + for the Ca(NbO_3)_2∶Dy (3+) were introducted. The Dy (3+) concentrations in the phosphor powder of Ca(NbO_3)_2∶Dy (3+) and Ca(NbO_3)_2Na +∶Dy (3+) are different. The excitation spectrum,the emission spectrum and the blue-yellow ratios are obtained,and the spectrum law and the luminescence mechanism are also discussed.

Chemical properties of colored dissolved organic matter in the sea-surface microlayer and subsurface water of Jiaozhou Bay, China in autumn and winter

The distribution and chemical properties of chromophoric dissolved organic matter （CDOM） in the Jiaozhou Bay, China were examined during four cruises in 2010-2011. The influence of freshwater and industrial and municipal sewage along the eastern coast of the bay was clearly evident as CDOM level- s （defined as a30s）, and dissolved organic carbon （DOC） concentrations were well correlated with salinity during all the cruises. Moreover, DOC concentrations were significantly correlated with chlorophyll a con- centrations in the surface microlayer as well as in the subsurface water. The concentrations of DOC and CDOM displayed a gradually decreasing trend from the northwestern and eastern coast to the central hay, and the values and gradients of their concentrations on the eastern coast were generally higher than those on the western coast. In addition, CDOM and DOC levels were generally higher in the surface microlayer than in the subsurface water. In comparison with DOC, CDOM exhibited a greater extent of enrichment in the microlayer in each cruise, with average enrichment factor （EF） values of 1.38 and 1.84, respectively. Four fluorescent components were identified from the surface microlayer and subsurface water samples and could be distinguished as peak A, peak T, peak B and peak M. For all the cruises, peak A levels were higher in the surface microlayer than in the subsurface water. This pattern of variation might be attributed to the terrestrial input.

Non-invasive imaging of pathological scars using a portable handheld two-photon microscope

Background:Pathological scars are a disorder that can lead to various cosmetic,psychological,and functional problems,and no effective assessment methods are currently available.Assessment and treatment of pathological scars are based on cutaneous manifestations.A two-photon microscope(TPM)with the potential for real-time non-invasive assessment may help determine the under-surface pathophysiological conditions in vivo.This study used a portable handheld TPM to image epidermal cells and dermal collagen structures in pathological scars and normal skin in vivo to evaluate the effectiveness of treatment in scar patients.Methods:Fifteen patients with pathological scars and three healthy controls were recruited.Imaging was performed using a portable handheld TPM.Five indexes were extracted from two dimensional(2D)and three dimensional(3D)perspectives,including collagen depth,dermo-epidermal junction(DEJ)contour ratio,thickness,orientation,and occupation(proportion of collagen fibers in the field of view)of collagen.Two depth-dependent indexes were computed through the 3D second harmonic generation image and three morphology-related indexes from the 2D images.We assessed index differences between scar and normal skin and changes before and after treatment.Results:Pathological scars and normal skin differed markedly regarding the epidermal morphological structure and the spectral characteristics of collagen fibers.Five indexes were employed to distinguish between normal skin and scar tissue.Statistically significant differences were found in average depth(t=9.917,P<0.001),thickness(t=4.037,P<0.001),occupation(t=2.169,P<0.050),orientation of collagen(t=3.669,P<0.001),and the DEJ contour ratio(t=5.105,P<0.001).Conclusions:Use of portable handheld TPM can distinguish collagen from skin tissues;thus,it is more suitable for scar imaging than reflectance confocal microscopy.Thus,a TPM may be an auxiliary tool for scar treatment selection and assessing treatment efficacy.

Characterization of chromophoric dissolved organic matter(CDOM) in the East China Sea in autumn using excitationemission matrix(EEM) fluorescence and parallel factor analysis(PARAFAC)

Samples of chromophoric dissolved organic matter （CDOM） in the East China Sea in autumn （October in 2011） were analyzed by excitation emission matrix （EEM） fluorescence spectroscopy combined with parallel factor analysis （PARAFAC）. Three terrestrial humic-like components （C1, C2 and C3） and one protein-like component （C4） were identified. Based on spatial dis- tributions, as well as relationships with salinity, the following assignments were made. The three humic-like components （CI, C2 and C3） showed conservative mixing behavior and came mainly from riverine input. The protein-like component （C4） was considered a combination of autochthonous production and terrestrial inputs and a biologically labile component. Path analysis of samples from the middle and bottom layers revealed that the causal effects on C1 were -78.46% for salinity, and -21.54% for apparent oxygen utilization （AOU）; those on C2 were -76.43% for salinity, and -23.57% for AOU; those on C3 were -70.49% for salinity, 7.01% for Chl-a, and -22.50% for AOU; those on C4 were -55.54% for salinity, 14.6% for Chl-a, and -29.86% for AOU in middle layer; and those on C4 were -57.37% for salinity, 29.02% for Chl-a, and -13.61% for AOU in bottom layer. Results indicated that CDOM in tile East China Sea was mainly affected by terrestrial inputs, and microbial ac- tivities also played a key role in biogeochemical processes of CDOM. The application of the EEM-PARAFAC model present- ed a unique opportunity to observe compositional changes in CDOM in the East China Sea. In addition, the humification index （HIX） suggested that CDOM from the East China Sea was less stable and stayed shorter in the environment.

Rapid and simple analysis of amphetamine-type illegal drugs using excitation–emission matrix fluorescence coupled with parallel factor analysis

Nowadays,the abuse of illegal drugs has been an increasingly grim problem in the world.Excitation–emission matrix fluorescence combined with parallel factor analysis was used to make a quantitative analysis of the simulated amphetamine-type illegal drugs.Satisfactory results were achieved for simultaneous determination of methamphetamine(MAM)and 3,4-methylenedioxymethamphetamine(MDMA)in the presence of adulterants.The average recoveries were(99.8±0.6)%and(101.6±5.7)%for MAM and MDMA,respectively.Figures of merit including root-mean-square error of calibration and prediction,sensitivity and selectivity were investigated to evaluate the performance of the proposed method.The limits of detection were 0.054 and 0.0021 g/mL for MAM and MDMA,respectively.

Strong optical nonlinearities of self-assembled polymorphic microstructures of phenylethynyl functionalized fluorenones

Highly efficient nonlinear optical（NLO） materials with well-defined architectures in the wavelength and subwavelength length scales are of particular importance for next generation of integrated photonic circuits. Fluorenone analogues have been demonstrated to be promising candidates as building blocks for assembly of organic NLO materials thanks to their synergistic supramolecular interactions and brilliant optical properties. Here we have studied the polymorphs of a phenylethynyl functionalized fluorenone derivative, and their controlled self-assembly for microstructures with different morphologies. These polymorphic microcrystals exhibit very distinctive NLO properties, highly related to their supramolecular and electronic structures.

Nonlinear optical metal-organic frameworks for ratiometric temperature sensing in physiological range

The precise and real-time sensing of the temperature within the physiological range is of great significance in biology and medicine.Here,a Zn-based metal-organic framework(MOF)named ZnTCOMA is synthesized with good SHG performance due to its unique structure of the ligand and 3 D frameworks.By encapsulating the two-photon fluorescent dye DMASE into the pores of Zn-TCOMA,the composite Zn-TCOMA■DMASE is obtained and simultaneously exhibits SHG response and two-photon fluo rescence.Utilizing the intensity ratio between two-photon fluorescence of DMASE and SHG signal of Zn-TCOMA,Zn-TCOMA■DMASE exhibits ratiometric temperature sensing property at physiological temperature region of 20~60℃with high sensitivity.This MOF thermometer also shows excellent repeatability,good biocompatibility,and high temperature resolution of 0.018℃,opening a new avenue to develop diverse optical thermometric or thermographic applications in biotechnology or other areas.

Assessing the dynamics of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn by EEMs-PARAFAC

In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.

Evidence on the causes of the rising levels of COD_(Mn) along the middle route of the South-to-North Diversion Project in China:The role of algal dissolved organic matter

As the biggest inter-basin water transfer scheme in the world,the South-to-North Water Diversion Project(SNWD) was designed to alleviate the water crisis in North China.The main channel of the middle route of the SNWD is of great concern in terms of the drinking water quality.In this study,we tested the hypothesis that the dissolved organic matter(DOM) derived from the planktonic algae causes the rising levels of COD_(Mn) along the middle route by monitoring data on water quality(2015-2019,monthly resolution).The results showed that algal density in the main channel increased along the channel and was significantly correlated with COD_(Mn)(p <0.01).Five fluorescent components of DOM,including tyrosine-like(14.85%),tryptophan-like(22.48%),microbial byproduct-like(26.34%),fulvic acid-like(11.41%),and humic acid-like(24.92%) components,were detected.The level of tyrosine-like components increased along the channel and was significantly correlated with algal density(p<0.01),indicating that algae significantly changed the level of DOM in the channel.Algal decomposition and metabolism were found to be the main mechanisms that drive the changes in COD_(Mn).Therefore,controlling algal density would be an important measure to prevent further increase in CODMn and for the guarantee of excellent water quality.

Chemical identification and genotoxicity analysis of petrochemical industrial wastewater

The actual harmful effects of industrial waste- water can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical waste- water were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid （HOA）, hydrophobic neutral （HOB）, hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical waste- water （p 〈 0.05）. However, the mixing of aniline waste- water can increase the amount of organic carbon （p 〈 0.05） and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline waste- water can increase the genetic toxicity of the effluent （p〈0.05）, and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan- like substances may play an important role in genetic toxicity.