Design Strategy of Infrared 4-Hydroxybenzylidene-imidazolinone-Type Chromophores based on Intramolecular Charge Transfer:a Theoretical Perspective

Partial genetically encoded 4-hy-droxybenzylidene-imidazolinone(HBI)-type chromophores are new promising fluorescent probes,which are suitable for imaging and detection of living cells.How-ever,the lack of infrared chro-mophores hinders the develop-ment seriously.Here more than 30 HBI-type chromophores with reg-ular structure modifications were employed and typical spectral redshift change laws and mechanisms were investigated by quantum methods.Results show that both one-photon spectrum(OPS,absorption/emission)and two-photon absorption(TPA)can achieve large redshift via either extending conjugated lengths of frag-3 or enlarging conjugated areas of frag-1 of HBI skeleton.Spectral redshifts of all chromophores are highly related to intramolecular charge transfer(ICT),but neutral ones are closely related to the total ICT or electron-accept-ing-numbers of frag-3,and the high correlative factor of anions is the aromaticity of frag-2 bridge.The frag-2 bridge with high aromaticity can open a reverse charge transfer channel in anion relative to neutral,obtaining significant redshift.Based on analysis,a new 6-hydroxyl-naphthalene-imidazolinone(HNI)series,which have larger conjugated area in frag-1,are pre-dicted.The OPS and TPA of anionic HNI ones acquire about 76−96 nm and 119−146 nm red-shift relative to traditional HBI series respectively as a whole.The longest emission of anionic HNI-4 realizes more 244 nm redshift relative to HBI-1.Our work clarifies worthy spectral reg-ularities and redshift mechanisms of HBI-type chromophores and provides valuable design strategy for infrared chromophores synthesis in experiment.

Impacts of Water-Sediment Regulation Scheme on Chromophoric Dissolved Organic Matter in the Lower Yellow River

As a river with more than 3000 reservoirs in its watershed,the Yellow River has been affected by dams not only on the sediment load,but also on the water quality.Water-sediment regulation scheme(WSRS),which has been carried out annually in the Yellow River since 2002,is a typical human activity affecting river water quality.Chromophoric dissolved organic matter(CDOM)in river is susceptible to changes in ecological and environmental conditions as well as human activities.Here,we report variations in dissolved organic carbon concentrations,compositions and sources of CDOM in time series samples in the lower Yellow River during WSRS.In addition,a parallel factor fluorescence analysis(PARAFAC)method is applied to identify different fluorescent components in water samples during WRSR,showing four major components including tryptophan-like component(C1),microbial humic-like component(C2),terrestrial humic-like component(C3)and tyrosine-like component(C4).In general,C1 increased after water regulation,while C2 and C3 increased after sediment regulation,indicating that the water and sediment released by the dam have different effects on CDOM compositions.Under the impacts of the dam,source of CDOM in the lower Yellow River is mainly autochthonous related to microbial activities,and is regulated by the terrestrial input during WSRS period.Sediment resuspension inhibits microbial activities and reduces the production of autochthonous CDOM.Overall,human activities especially WSRS,as exemplified here,significantly alter the quality and quantity of CDOM in the lower Yellow River,affecting CDOM dynamics and biogeochemical processes in the estuarine environment.

Synthesis and Non-linear Optical(NLO) Properties of a Series of Alkoxysilane Derivative Chromophores

1 Introduction Nonlinear optical materials（NLO） have drawn a great intrest of some scholars and scientists in the last dacades because of their tremendous potential application in optoelectronic. The fabrication of efficient optoelectron devices is a challenging task because such systems need to meet the stringentable requirements for high optical quality and large and sustainable electro-optical（EO） response. In pursuit of NLO materials with excellent optoelectronic property,

NONLINEAR OPTICAL PROPERTIES OF X-TYPE CHROMOPHORES AND THEIR DOPED FILMS

Two X-type chromophores, 2-[4-(4,5-di(4-nitrophenyl) imidazolyl) phenyl]-4,5-di(4-methoxyphenyl)-imidazole (DNPIPDMOPI), 2-[4-(4,5-di(4-nitrophenyl)-imidazolyl) phenyl]-4,5-di(4-aminophenyl)-imidazole (DNPIPDAPI), were synthesized and characterized. The results show that they possess good nonlinearity, considerable blue-shifted absorption (385 nm and 379 nm in THF) and high decomposition temperature (377 'C and 405 'C). These mean that the X-type chromophores possess a rather good nonlinearity-transparency-thermal stability trade-off. The multi-step corona-poling technique at elevated temperature and in-situ SHG measurements were used to obtain and evaluate the poled films of these chromophores doped in PMMA. The largest SHG signals appeared at 110-120°C, which are 12.5 pm/V and 16.7 pm/V respectively. The dependence of poling induced orientation stability on temperature was measured by depoling experiments and the results indicate that the poling-induced orientation of the films is stable at about 100°C. Theoretic analyses imply that better orientation stability arises from the X-type structure of chromophore. The X-type chromophore has two crossed intramolecular CT, both β xxx and β xyy can contribute to the second-order susceptibility, and the ratio of the tensorial components (γ= β xyy /β xxx ) is about 1/3, so the orientation decay of the films induced by rising temperature will provide a certain compensation for the contribution of β xyy of chromophores.

Synthesis and Nonlinear Optical Property of a Series of New Chromophores Containing Furan Ring as the Only Conjugation Bridge

This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, H-1 NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (beta) are calculated and compared with those or the analogues containing either benzene or thiophene as file conjugation bridge.

Theoretical Studies on the First Hyperpolarizabilities of One-dimensional Donor-bridge-acceptor Chromophores

The ground-state dipole moments and second-order nonlinear optical （NLO） properties of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures have been investigated by using the second-order MФller-Plesset （MP2） and density functional theory （DFT） methods with the basis set of 6-31＋G（d）. According to the calculated results, the relationship between the molecular static first hyperpolarizability （βμ） and the directions of electron transition has been summarized. In terms of the sign of βμ, these 1D organic chromophores were classified into two categories： type Ⅰ with negative βμ and type Ⅱ bearing positive βμ. The analyses show that the remarkable difference of the first hyperpolarizabilities between Ⅰ and Ⅱ chromophores is associated mainly with the electrostatic interaction between terminal groups and the transport electrons in excited states. Moreover, different from the popular viewpoint, the obtained results also show that most of this series of 1D D-B-A molecules are more charge-separated in the ground states than in the excited states. As a whole, this theoretical investigation, to some extent, can be considered as a useful reference in designing the NLO chromophores with large first hyperpolarizabilities.

Nonlinear optical properties of novel H-shaped chromophores

Novel and effective H-shaped chromophores were doped into polymethyl methacrylate （PMMA） to form guest-host polymer thin films. The measurement results of Maker fringe method show that the polymer thin films containing the H-shaped chromophores as a guest exhibit high second harmonic coefficients （d33） compared with other two-dimensional chromophores.

Theoretical Studies on the First Hyperpolarizabilities of One-dimensional Donor-bridge-acceptor Chromophores and New Applications of BLA in Determining Molecular First Hyperpolarizabilities

We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.

Synthesis,Characterization,and Linear and Nonlinear Optical Properties of Phenylene-vinylene Based Chromophores for Singlet Oxygen Generation

A series of symmetrical and unsymmetrical phenylene-vinylene （PV） based chro- mophores with the molecular configuration of donor-π-donor （D-g-D） were prepared and characterized. Iodine was first introduced into the Jr-conjugation backbone of the PV based chromophores in order to study the heavy atom effect on their linear absorption, two-photon absorption （TPA） properties, as well as singlet oxygen generation properties. TPA cross-sections of these chromophores were investigated by using the two-photon excited fluorescence method. The unsymmetrical chromophores were found to have larger TPA cross-section values compared to their symmetrical counterparts. For one of the unsymmetrical chromophores with the iodine incorporation, a large TPA cross section value with quenched emission was found. The decreased fluorescence quantum yield of a molecule can be ascribed to the increased intersystem crossing, which is favorable for enhancing the singlet oxygen generation. Therefore, the unsymmetrical PV based chromophores with heavy atom incorporation are promising singlet oxygen sensitizers for the photodynamic therapy application.

Spectroscopic Properties and Three-photon Absorption Induced Optical Limiting of Series of Novel Nonlinear Chromophores

有对称的 D 的三新奇非线性的色基 -- D 分子的结构和扩大结合的长度被综合。Solvatochromism 分析显示出在在地面和激动的状态之间的偶极子时刻由改进发生在色基的大对称的 intramolecular 充电转移。限制由三光子的吸收(3PA ) 导致了的光力量的性质被表明。大 3PA coeficients 和象 1074 cm6 s2 一样高的相应的分子的生气的节从非线性的传播大小在 1.06 m 为毫微秒激光脉搏被获得。

Theoretical investigation of nonlinear properties of electrooptical chromophores

Organic electrooptical （EO） chromophores are now gaining more attention because the property of organic photorefrative （PR） materials could be controlled by doped EO chromophores. In this paper, nonlinear optical （NLO） properties of a new group of organic electrooptical chromophores, synthesized recently in our laboratory, were elucidated theoretically with the quantum chemical density functional theory （DFT） and the intermediate neglect of differential overlap Hamilton and the configuration interaction （INDO/CI）, as well as semiemperical Austin Model 1 （AM1） methods. The electronic transition intensity, dipole moment and the second-order polarizability were obtained. The results show this group of chromophores possess appropriate optical absorption property and good electrooptical property and optical activity. The second-order polarizabilities β are as large as the order of 10-29 to 10-28 ESU, indicating the promising applications in the future. The physical mechanism of NLO is discussed by means of molecular orbital and electronic charge distribution.

过氧化氢漂白过程中慈竹机械浆发色基团演变及溶出机制

在常规工艺下难以制备高白度(>78%)竹材化学机械浆是制约竹类资源在高附加值纸产品领域规模化应用的关键技术瓶颈。使用乙醇-水二元介质碱性过氧化氢漂白体系可以突破当前慈竹机械浆漂白上限,将纸浆白度提升至80%以上。以慈竹机械浆为原料,对比研究了常规过氧化氢用量(90 kg/t)水相体系两段漂工艺、高过氧化氢用量(180 kg/t)水相四段漂工艺和高过氧化氢用量(180 kg/t)乙醇-水二元介质相四段漂工艺中各段处理所得纸浆的发色基团结构特点,以及3种工艺漂白段溶出物的结构特点,以此探索二元体系漂白过程中发色基团形成和溶出规律。结果表明,在漂白过程中,慈竹机械浆中的苯环类共轭结构含量逐渐降低,但在化学品用量较大的漂白段会生成在水相体系无法被破坏和溶出的呋喃类共轭结构。在漂白体系中引入乙醇,可以显著提高呋喃类共轭结构的溶出效率,同时发现浆料中溶出的部分苯环结构发生了开环反应,推测碱性条件下乙醇电离的微量乙氧根离子对呋喃类共轭结构的脱除具有关键性作用。慈竹机械浆发色基团演变及溶出机制可为开发经济上可行的竹类机械浆漂白工艺提供理论基础。

鄱阳湖碟形湖和通江水域有色可溶性有机物(CDOM)的吸收与荧光特性对比研究

有色可溶性有机物(CDOM)在水生态系统的生物地球化学循环中起着重要的作用.近年来,在全球气候变暖和人类活动的双重影响下,全球大部分湖泊出现了水文隔离现象.然而,水文隔离如何影响大型湖泊CDOM组成变化仍然知之甚少.本研究于2021年在鄱阳湖碟形湖和通江水域采集水样,运用紫外-可见吸收光谱与三维荧光光谱,结合平行因子分析法(PARAFAC)研究CDOM光学特性,揭示鄱阳湖碟形湖和通江水域CDOM组成和来源的差异.结果表明:①碟形湖溶解性有机碳(DOC)浓度以及CDOM在355 nm处的吸收系数〔a(355)〕的平均值均显著高于通江水域(p<0.001),表明受水文隔离影响的碟形湖水体中存在更丰富的有机物.②基于PARAFAC分析得出的类腐殖质荧光组分(C1、C2)和蛋白质荧光组分(C3)最大荧光强度值(Fmax)的平均值均表现为碟形湖高于通江水域;碟形湖和通江水域的类腐殖质组分(C1+C2)占总荧光强度的比例分别为71.96%和59.93%,且通江水域CDOM中蛋白质荧光组分C3的贡献率高于碟形湖.③通过碟形湖和通江水域CDOM特征参数的对比分析,得出碟形湖CDOM相对分子量和腐殖化程度均高于通江水域.研究显示,水文隔离对鄱阳湖CDOM空间分布及组成变化有显著的影响.

秋季洪泽湖水体有色溶解有机物分布特征及来源解析

利用紫外/可见光谱和三维荧光光谱分析了秋季洪泽湖水体有色溶解有机物(CDOM)的组成和空间分布特征,并探究了其来源。三维荧光光谱共解析出3种类腐殖质和2种类蛋白质组分,其中类腐殖质为主要组分。波长254 nm处的吸收系数(A_(254))及其与溶解有机碳的比(SUVA)和3种类腐殖质组分均表现出入湖河口区高于其他区域的空间分布特征,表明外源河流输入是秋季洪泽湖CDOM的主要来源,自生源指数(BIX)和腐殖化指数(HIX)也佐证了这一结论。人工调蓄对洪泽湖CDOM的组成和来源影响显著。

2022年6月珠江流域洪水对下游溶解有机物浓度和组成的影响

当前极端气候事件频发,引起了人们广泛的关注。然而,气候变化对中国典型河流溶解有机物(DOM)的影响尚且未得到充分的认识。2021年11月至2022年10月,每月于珠江下游广州段采集河水样品,并分析其中溶解有机碳(DOC)、发色溶解有机物(CDOM)和荧光溶解有机物(FDOM)的浓度和组成。采样期间,2022年6月珠江流域遭遇百年一遇的洪水。结果显示,洪水大幅度降低了河水中的DOC和CDOM浓度,并提高了DOM的芳香化程度。尽管洪水对DOM浓度产生了明显的稀释效应,但通过分析FDOM组成,进一步发现FDOM中不同组分对洪水的响应存在较大差异。FDOM短激发波长(230~235nm)处的类蛋白质组分峰值在洪水期间出现高值;与此同时,长激发波长(280~285nm)的类蛋白质组分和激发波长在345nm处的类腐殖质组分峰值在洪水期间出现最低值。此外,与长江下游相比,珠江下游水体中往往具有较高的DOC和CDOM浓度、DOM芳香化程度以及CDOM分子量。研究将有助于进一步了解珠江等世界大河DOM浓度和组成的变化规律和控制机制,以及揭示极端洪水对大河DOM动态变化产生的影响。

秋季长江口及邻近海域有色溶解有机物的分布及河口混合行为

【目的】探究秋季长江口及邻近海域有色溶解有机物(chromophoric dissolved organic matter,CDOM)的分布特征与河口混合行为及影响CDOM分布的因素,以深入了解本研究区域CDOM动态变化机制。【方法】测定研究海域溶解有机碳(dissolved organic carbon,DOC)质量浓度、吸收系数a(350)等参数,分析CDOM含量水平;使用三维荧光光谱-平行因子分析(EEMs-PARAFAC)技术鉴别研究海域CDOM荧光组分。运用物理稀释模型分析CDOM河口混合行为。【结果】研究海域b-a4断面DOC质量浓度的变化范围为0.92~2.36 mg·L^(-1),c-a6断面DOC质量浓度的变化范围为1.00~2.40 mg·L^(-1)。b-a4断面a(350)的变化范围为0.22~1.60 m^(-1),c-a6断面a(350)的变化范围为0.15~1.42 m^(-1)。b-a4断面光谱斜率S275-295的变化范围为0.014~0.022 nm^(-1),c-a6断面S275-295的变化范围为0.016~0.024 nm^(-1)。鉴定出4个荧光组分:类腐殖质组分C1(激发波长265 nm、发射波长445 nm)、类蛋白质组分C2(275、325 nm)、类腐殖质组分C3(245、390 nm)和类蛋白质组分C4(235、340 nm)。【结论】长江口及邻近海域DOC质量浓度和a(350)均呈现出由长江口内向口外逐渐减小的趋势,陆源输入是影响CDOM分布的主要因素;远岸S275-295值高于近岸,主要受浮游生物生产活动的影响,陆源输入影响小;4个荧光组分的高值都出现在河口处,且随离岸距离增加而降低,这是受到陆源输入的影响;两个断面的4个荧光组分均符合理论稀释线,CDOM整体呈现保守混合行为。

Feasible Synthesis of N,O-Bidentate Difluoroboron Chromophores through Direct Functionalization of Quinoxalin-2(1H)-ones with Ketones in One Shot

Organic difluoroboron complexes are a kind of potential platforms for a wide range of applications owing to their excellent photophysical properties.Herein,we have explored a simple and direct synthesis methodology for a library of N,O-bidentate difluoroboron complexes from quinoxalin-2(1H)-ones and ketones in one shot.The photophysical properties of the generated complexes were evaluated and the application potential of these compounds on subcellular imaging was also explored.

基于不同荧光发色基团的Zn^(2+)荧光探针的研究进展

荧光光谱法具有灵敏度高、选择性好、检出限低以及操作简单等特点,设计合成特异性识别和检测Zn^(2+)的荧光探针对化学、生物学、临床医学等研究具有十分重要的意义。以近年来文献报道的Zn^(2+)荧光探针为例,综述了基于不同荧光发色基团的Zn^(2+)荧光探针的作用机制、应用与发展前景,为Zn^(2+)荧光探针研究提供了参考(引用文献44篇)。

Impact of transparent exopolymer particles on the dynamics of dissolved organic carbon in the Amundsen Sea,Antarctica

The Southern Ocean is an important carbon sink pool and plays a critical role in the global carbon cycling.The Amundsen Sea was reported to be highly productive in inshore area in the Southern Ocean.In order to investigate the influence of transparent exopolymer particles(TEP)on the behavior of dissolved organic carbon(DOC)in this region,a comprehensive study was conducted,encompassing both open water areas and highly productive polynyas.It was found that microbial heterotrophic metabolism is the primary process responsible for the production of humic-like fluorescent components in the open ocean.The relationship between apparent oxygen utilization and the two humic-like components can be accurately described by a power-law function,with a conversion rate consistent with that observed globally.The presence of TEP was found to have little impact on this process.Additionally,the study revealed the accumulation of DOC at the sea surface in the Amundsen Sea Polynya,suggesting that TEP may play a critical role in this phenomenon.These findings contribute to a deeper understanding of the dynamics and surface accumulation of DOC in the Amundsen Sea Polynya,and provide valuable insights into the carbon cycle in this region.

羟基-炔点击反应制备具有红移发射的非传统荧光化合物及性能

以丙炔酸甲酯为原料,分别与2-二乙基氨基乙醇、N-甲基二乙醇胺和三乙醇胺经常温羟基-炔点击反应在无催化剂和无溶剂条件下制备得到三组含叔胺和乙烯基醚非传统发色团的有机荧光化合物。利用傅里叶红外光谱仪(FT-IR)和核磁共振波谱仪(NMR)确证所得化合物的分子结构。利用紫外-可见分光光度计(UV-Vis)和荧光分光光度计探究了化合物的荧光性能,结果表明:所得三组化合物均表现出浓度增强发光及激发波长依赖荧光特性。以三乙醇胺、N-甲基二乙醇胺和2-二乙氨基乙醇分别反应所得化合物的发射波长依次红移,且其红移程度依赖于化合物的浓度,表现出结构和浓度依赖红移荧光特性。该方法实现了简单调控化合物的结构和浓度得到长波长的非传统有机荧光化合物,这为设计长波长非传统荧光材料提供了新的方法和思路。