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.

Subunit composition and chromophore content of R－phycocyanin and allophycocyanin from Porphyra haitanensis

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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, 1H NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (b) are calculated and compared with those of the analogues containing either benzene or thiophene as the conjugation bridge.

Synthesis and characterization of multifunctional copolyimide incorporating triarylamine and NLO chromophore in backbone

Presents the synthesis of Copolyimide containing triarylamine and NLO chromophore in backbone by azo coupling of 4 nitrobenzenediazonium tetrafloroborate to copoly(amic acid) in organic solvent and characterized by IR and UV Vis spectra, which had high glass transition temperatrue and big second order nonlinear optical coefficient  x (2) .

Triphenylamine-based highly active two-photon absorbing chromophores with push-pull systems

Two triphenylamine-based star-type push-pull chromophores(T1, T2) were designed and synthesized.Triphenylamine serves as the central core and acts as an electron-donating group surrounded by electronwithdrawing pentafluorobenzene or N,N-dimethyl substituted tetrafluorobenzene, which are connected by ethylene bridges. Single-crystal X-ray diffraction confirmed the structures and molecular arrangement of two chromophores. The systematic photophysical research of T1 and T2 absorption characteristics was carried out to gain a better understanding of how structure-property relationships affect the observed nonlinear optical absorption phenomenon. Complementary calculations based on density functional theory(DFT) further confirmed the experimental results. Both chromophores exhibited excellent two-photon absorption(TPA) properties in CH_(2)Cl_(2). Notably, T2 has more remarkable nonlinear optical absorption effects with the TPA cross-section up to 4.24 × 10~7GM. By adjusting the electronic structures of the chromophores through introducing pentafluorobenzene or N,N-dimethyl as functional groups with different electron-donating or withdrawing behaviors, the TPA performance of the small organic molecule could be greatly enhanced. These molecular structures with push-pull systems were excellent candidates for different two-photon applications.

Synthesis,structure and nonlinear optical properties of two novel two-photon absorption chromophores

Two triphenylamine-based derivatives that can be used as two-photon absorption chromophore,tris{4-[4-(3-trifluoromethyl-3-oxopanoyl)]phenyl}amine (1) and tris{4-[4-(3-phenyl-3-oxopanoyl)] phenyl} amine (2) were successfully synthesized and fully characterized by elemental analysis,IR,1H NMR and MS. The single crystal X-ray diffraction analysis showed that the molecules possess D-(π-A)3 structures. One-and two-photon absorption and fluorescence in various solvents were experimentally investigated. A data recording experiment proved the potential application of these chromophores.

Theoretical studies of vibrationally resolved absorption and emission spectra: From a single chromophore to multichromophoric oligomers/aggregates

Absorption and photoluminescence spectroscopies are useful tools to study the photo-physical properties of materials. The theoretical methods for calculation of the spectra of molecules/supermolecules and aggregates, whose structures can differ significantly, are reviewed from the viewpoint of computational efficiency. Several model compounds/multimers are taken as examples for the spectral calculations. The numerical results achieve a satisfactory agreement between the theory and experiment.

DFT study on second-order nonlinear optical properties of Pt (Ⅱ) complexes with different chromophores

DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.

Dendronized Polymers with High FTC-chromophore Loading Density:Large Second-order Nonlinear Optical Effects, Good Temporal and Thermal Stability

In this study,two new dendronized nonlinear optical(NLO)polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains.Due to their suitable molecular weights,both of them possessed good solubility in common solvents.They also inherited the advantages of dendrimers(large NLO coefficient),especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V^–1.Also,PG2 had a good temporal stability with 80%of its maximum value being retained at the temperature as high as 129℃.

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.

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.

Molecular dynamics simulations investigation of Neocarzinostatin Chromophore releasing pathways from the Holo-NCS protein

The enediyne ring chromophore with strong DNA cleavage activity of neocarzinostatin is labile and therefore stabilization by forming the complex (carrying protein + chromophore:

Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics

This study reports the facile synthesis,characterization and quantitative structure-property relationship analysis of molecular and material properties of tricyanofuran-based(TCF)dipolar heptamethines with different electron donors of indoline(F1),benzo[e]-indoline(F2),benz[cd]indoline(F3),and Michler’s base derivatives(Ml and M2).The linear and nonlinear optical(NLO)properties of these chromophores have been thoroughly investigated,and the relationship between molecular and bulk response has been analyzed and compared with dipolar tetraene AJLZ53 as one of the best chromophores for electro-optic(EO)devices.In particular,we provide responsible data collection and analysis of optical and EO properties for poled thin films using a widelyrecognized and accredited methodology of prism coupling system with the help of rigid oriented gas model.We found that these push-pull heptamethines with synthetic efficacy exhibit high near-infrared absorption,excellent chemical stability and large hyperpolarizabilities(β)varied from 1,023×10^-30 esu for F1,3,047×10^-30 esu for M1,and 3,547×10^-30 esu for F3 at 1,304 nm in poled films,respectively.Theβvalues of these molecules are among the highest ones for TCF-based dipolar chromophores,and also agree well with reported analytical results in the solutions.In poled polymers with a modest chromophoric loading density of1.3×10^20 cm^-3,Ml and M2 give a high poled-induced noncentrosymmetric order and relatively large r33 values around40 pm V^-1 at 1,304 nm,indicative of largeμβvalues and suitable structural modification for high poling efficiency.Furthermore,a binary EO polymer based on the co-loading of Ml and AJLZ53 achieve a large r33 value of 143.3 pm V^-1 at 1,304 nm.Our studies suggest that concise synthesis and molecular design of push-pull polymethines can be well guided by the tabulation of their linear and NLO properties in bulk materials,and streamline future development of high performance organic EO materials for photonic applications.

PREPARATION AND SECOND-ORDER OPTICAL NONLINEARITY OF NOVEL PHENOXYSILICON NETWORKS BY SOL-GEL PROCESS

Four phenoxysilicon networks for nonlinear optical (NLO) applications were designed and prepared by an extended sol-gel process without additional H20 and catalyst. All poled polymer network films possess high second-order nonlinear optical coefficients (d33) of 10-?～10-8 esu. The investigation of NLO temporal stability at room temperature and elevated temperature (120°C) indicated that these films exhibit high d33 stability because the orientation of the chromophores are locked in the phenoxysilicon organic/inorganic networks.

SYNTHESIS AND OPTICAL PROPERTIES OF A NOVEL ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL POLYMER VIA SOL-GEL PROCESS

A new organic/inorganic hybrid nonlinear optical (NLO) material was developed by the sol-gel process of an alkoxysilane dye with tetraethoxysilane. A NLO moiety based on 4-nitro-4′-hydroxy azobenzene was covalently bonded to the triethoxysilane derivative, i.e. γ-isocyanatopropyl triethoxysilane. The preparation process and properties of the sol-gel derived NLO polymer were studied and characterized by SEM, FTIR, 1H-NMR, UV-Vis, DSC and second harmonic generation (SHG) measurement. The results indicated that the chemical bonding of the chromophores to the inorganic SiO2 networks induces Iow dipole alignment relaxation and preferable orientational stability. The SHG measurements also showed that the bonded polymer film containing 75 wt% of the akoxysilane dye has a high electro-optic coefficient (r33) of7. 1 pm/V at 1.1 μm wavelength, and exhibit good SHG stability, the r33 values can maintain about 92.7% of its initial value at room temperature for 90 days, and can maintain about 59.3% at 100℃ for 300 min.

Synthesis and Characterization of (E)-5-[2-(N-hexylcarbazolyl)vinyl] furan Derivatives with Acceptor Groups

A new series of (E)-5-[2-(N-hexylcarbazolyl)vinyl]furan chromophores with various acceptors have been synthesized by the Knoevenagel condensation of (E)-5-[2-(N-hexylcarbazolyl) vinyl]-2-furaldehydes with malononitrile, 1,3-diethyl-2-thiobarbituric acid, or 3-phenyl-5-isoxazol one, respectively. They are characterized by 1H-NMR, FT-IR, UV-VIS, MS and elemental analysis, and have shown strong solvatochromism and high thermal stability.

Efficient Calculation of Absorption Spectra in Solution:Approaches for Selecting Representative Solvent Configurations and for Reducing the Number of Explicit Solvent Molecules

Dye-sensitized solar cells(DSSCs) are one of the most promising renewable energy technologies. Charge transfer and charge transport are pivotal processes in DSSCs, which govern solar energy capture and conversion. These processes can be probed using modern electronic structure methods. Because of the heterogeneity and complexity of the local environment of a chromophore in DSSCs(such as solvatochromism and chromophore aggregation), a part of the solvation environment should be treated explicitly during the calculation. However, because of the high computational cost and unfavorable scaling with the number of electrons of high-level quantum mechanical methods, approaches to explicitly treat the local environment need careful consideration. Two problems must be tackled to reduce computational cost. First, the number of configurations representing the solvent distribution should be limited as much as possible. Second, the size of the explicit region should be kept relatively small. The purpose of this study is to develop efficient computational approaches to select representative configurations and to limit the explicit solvent region to reduce the computational cost for later(higher-level) quantum mechanical calculations. For this purpose, an ensemble of solvent configurations around a 1-methyl-8-oxyquinolinium betaine(QB) dye molecule was generated using Monte Carlo simulations and molecular mechanics force fields. Then, a fitness function was developed using data from inexpensive electronic structure calculations to reduce the number of configurations. Specific solvent molecules were also selected for explicit treatment based on a distance criterion, and those not selected were treated as background charges. The configurations and solvent molecules selected proved to be good representatives of the entire ensemble; thus, expensive electronic structure calculations need to be performed only on this subset of the system, which significantly reduces the computational cost.

Collagen crosslinking with photoactivated riboflavin in advanced infectious keratitis with corneal melting: Electrophysiological Study

AIM: To assess the effect of photoactivated chromophore for keratitis crosslinking(PACK-CXL) in case of severe keratitis with melting on the electrophysiological function of the retina and the optic nerve.METHODS: The study included 32 eyes of 32 patients with smear positive severe infectious keratitis with corneal melting. The patients were randomly divided into two groups. Group I(control group) included 16 eyes received systemic and topical antimicrobial drugs guarded by culture and sensitivity test. Group II underwent CXL and then continued their antimicrobial treatment. Full field electroretinogram(ERG) and flash visual evoked potential(VEP) were done for each patient in both groups basically and then 1 wk, 1 and 3 mo post-treatment to assess the changes in the electrophysiological function of the retina and optic nerve.RESULTS: Healing of 10 eyes in group I in comparison to 14 eyes in group II was recorded. The mean duration of healing was 36.56±5.21 d in group I vs 20.2±4.4 d in group II(P<0.005). In group II, ERG showed an insignificant reduction of all parameters of ERG and VEP after CXL. The amplitude of scotopic rod response, oscillatory potential amplitude, flicker amplitude and photopic cone response were insignificantly decreased(P=0.4, 0.8, 0.1, and 0.3 respectively). There were insignificant prolongation of latencies of scotopic rod, oscillatory potential, flicker and photopic cone response(P=0.2, 0.7, 0.5 and 0.1). There was slight delay in latency of VEP without a significant reduction in amplitude.CONCLUSION: CXL is an effective technique in treatment of severe infectious keratitis with melting as it halts the melting process with acceptable safety on the retinal and optic nerve function.

Effect of Skin Pigmentation on Near Infrared Spectroscopy

The purpose of this study was to determine the effects of skin pigmentation regarding Near Infrared Spectroscopy (NIRS) tissue oxygen saturation values (StO2). The study examined NIRS values in individuals with varying skin pigmentation on the anterior compartment of the lower leg and volar forearm to determine if correlation exists among three NIRS devices, the EQUANOX, Casmed, and INVOS. Skin pigmentation was measured on the anterior lower leg (AL) and volar forearm (VF) of participants using a noninvasive colorimeter that employed reflective spectroscopy to produce a quantitative value for erythema (skin “redness”) and melanin (skin pigment). Muscle oxygenation was measured using three oximetry devices with sensors placed in the same areas. The EQUANOX device showed no significant correlation with skin pigmentation, while the Casmed and INVOS devices showed moderate and significant correlation with skin pigmentation, respectively. Different devices have different abilities to remove confounding variables, such as skin pigmentation and erythema, which may affect clinical decision-making, and affect the use of NIRS technology.