Chromophore Content Research Articles

Photoresponsive behaviour of “T-type” azopolyimides. The unexpected high efficiency of diffraction gratings, modulations and stability of the SRG in azopoly(ether imide)

In this paper, we compare the light-induced properties of three “T-type“ polyimide containing azobenzene chromophores with the properties of their structural counterparts containing azopyridine moieties. The processes of photoinduced birefringence generation and surface relief grating (SRG) formation are efficient in azobenzene polyimides, while in the azopyridine analogues the processes are non-detectable. Density functional theory calculations performed to reveal a possible structural reason for the lack of optical response in the azopyridine materials showed a formation of intramolecular H-bonds. Azopoly(ether imide) with 2,2′-diphenylopropane structure despite relatively low chromophore content exhibited one of the highest diffraction efficiency (ca. 20%) and the largest modulation of the SRG (260 nm) as have ever been observed for azopolyimides. Two years after inscription, modulation of the SRG was still observed without a decrease in the relief depth, which is important in applications requiring long-term stability of SRGs.

Nonlinear Optical Stability of Polyphenylsulfone (PPSU)‐Containing Anthraquinones with High Transmittance

AbstractIn a previous study, three kinds of polymers are synthesized by the covalent bonding of three anthraquinone chromophores to polyphenylene sulfone. Herein, the nonlinear optical (NLO) properties of solutions and thin films of anthraquinone‐containing polyphenylsulfone, which can function as effective optical limiting materials are discussed in detail. The reasons for the improved NLO properties of the thin films are explained from the perspective of chromophore content, polarization orientation, and energy level transition. In addition, the NLO properties thermal stability and chemical stability of the three polymers are tested. The results show that the three types of polyphenylsulfone materials have excellent optical limiting properties. Further, since the nonlinear optical coefficient decreases by less than 8% after treatment by heat and acid or basic solutions, they exhibit excellent nonlinear optical stability.

Direct mapping from diffuse reflectance to chromophore concentrations in multi-fx spatial frequency domain imaging (SFDI) with a deep residual network (DRN).

Spatial frequency domain imaging (SFDI) is an emerging technology that enables label-free, non-contact, and wide-field mapping of tissue chromophore contents, such as oxy- and deoxy-hemoglobin concentrations. It has been shown that the use of more than two spatial frequencies (multi-fx ) can vastly improve measurement accuracy and reduce chromophore estimation uncertainties, but real-time multi-fx SFDI for chromophore monitoring has been limited in practice due to the slow speed of available chromophore inversion algorithms. Existing inversion algorithms have to first convert the multi-fx diffuse reflectance to optical absorptions, and then solve a set of linear equations to estimate chromophore concentrations. In this work, we present a deep learning framework, noted as a deep residual network (DRN), that is able to directly map from diffuse reflectance to chromophore concentrations. The proposed DRN is over 10x faster than the state-of-the-art method for chromophore inversion and enables 25x improvement on the frame rate for in vivo real-time oxygenation mapping. The proposed deep learning model will help enable real-time and highly accurate chromophore monitoring with multi-fx SFDI.

Single probe diffuse reflectance spectroscopy to assess the effect of sarcopoterium spinosum treatment on the cerebral tissue properties of ApoE knockout mouse.

In this work, diffuse near-infrared light reflectance spectroscopy based on a single optical probe, contains central single collection fiber surrounded by a circular array of illumination fibers, was used to quantify cerebral tissue properties in ApoE knockout mice following Sarcopoterium spinosum treatment. Sarcopoterium spinosum, also known as Thorny burnet, is a Mediterranean plant widely used as a traditional therapy for the treatment of a variety of pathologies, primarily type 2 diabetes mellitus (T2D). While it's efficacy in the treatment of T2D, and of other components of metabolic syndrome, have already been validated by us, the aim of this study was to investigate the effects of Sarcopoterium spinosum extract (SSE) on dyslipidemia and vascular functions. We utilized ApoE deficient mice (ApoE-/- , Atherosclerosis-prone apolipoprotein E-deficient), who have a severe impairment in plasma lipoprotein clearance and thus develop alterations in blood lipid profile and are highly susceptible to atherogenic plaque formation. A total of 34 male mice were divided into five groups representing various genetic, dietary, and treatment configurations. Optical measurements were used to assess changes in diffused reflectance spectra, optical properties (absorption and scattering), and cerebral tissue chromophore contents. Specifically, significant improvement in cerebral hemoglobin level was observed in ApoE KO mice, fed an artherogenic diet (ATD), upon SSE treatment. Biochemical and histological analyses of ApoE-/- ATD mice showed elevated body weight and a high level of blood triglycerides, free fatty acids and cholesterol. In contrast, in SSE treated mice improvement was observed, suggesting beneficial effects of SSE. In ApoE-/- ATD mice group a higher levels of deoxyhemoglobin was monitored indicating that the rate of oxygen release to the tissue is low. This was supported by decrease in oxygen saturation. It was also shown a reduction in water content in the brain of ApoE KO. Mice fed with the atherogenic diet demonstrated increased water content as compared to STD-fed ApoE KO mice, while SSE administration reversed the effect of the diet. To our knowledge, no such study has been reported before.

On nitrogen fixation and “residual nitrogen content” in cellulosic pulps

Cellulosic material is capable of permanently retaining nitrogen compounds (mostly having amino functions), which is reflected in a residual nitrogen content (in the low per mille range to the low percent range) of some pulps and certain lab samples. Merely adsorptively bound compounds can be removed by mild acidic washing, but part of the nitrogen seems to be resistant and very tightly bound, and thus not accessible for removal by washing. Tertiary and aromatic amines are not retained in this way, but only primary and secondary amines. There is only a weak correlation between the “firmly bound nitrogen” and the carbonyl content in cellulosics (because of oxidative damage), so that possible aminal, Schiff base and enamine structures can hardly be relevant as major nitrogen sources. However, there is a very good linear correlation between the ISO brightness (chromophore content) in aged pulps and the residual nitrogen content. In particular the concentration of the cellulosic key chromophore 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ) determines the permanent N-binding capacity of the pulp. DHBQ reacts very readily with primary and secondary amines under ambient conditions to 2,5-diamino-substituted [1,4]-benzoquinones, which have very low solubility (because of zwitterionic resonance contributions) and thus remain on/in the pulp. Examples of nitrogen fixation in pulps are the binding of piperidine (a common amine catalyst in derivatization reactions), amine degradation products of the cellulose solvent NMMO, dimethylamine in materials processed from the cellulose solvent DMAc/LiCl, imidazole (a degradation product of 1-alkyl-3-methylimidazolium ionic liquids), and of amino groups in proteins after enzymatic treatment. The nature of the respective DHBQ-amine addition compound has been verified by complete structure determination.

D-π-A chromophores with a quinoxaline core in the π-bridge and bulky aryl groups in the acceptor: Synthesis, properties, and femtosecond nonlinear optical activity of the chromophore/PMMA guest-host materials

Novel D-π-A chromophores with quinoxaline/quinoxalinone core in the π-conjugated bridge and various bulky groups in the acceptor moiety have been synthesized and systematically investigated at molecular level by UV–Vis spectroscopy, DFT calculations, electrochemical and TGA-DSC methods as well as at materials level by the example of PMMA-based composite polymer materials doped with different chromophore contents using molecular modeling and SHG technique. Chromophores exhibit positive dioxane/chloroform solvatochromic shift of ca. 50 nm, high values of first hyperpolarizability and dipole moment, small energy gap and good thermal stability. Tolyl and cyclohexylphenyl substituents unlike phenyl can be treated as most effective isolating groups, preventing chromophore pronounced aggregation even at 30 wt% content. Femtosecond nonlinear optical (NLO) activity was studied for poled thin guest-host polymer films with various chromophore weight content. Film DBA-VQPhV-TCFPhCy(25 wt%)/PMMA with bulky cyclohexylphenyl groups in chromophore acceptor shows maximal NLO coefficient, d33, values among the studied materials (37 pm/V) as well as good long-term stability of NLO response together with excellent chromophore thermal stability (Td = 256 °C). Composite materials doped with quinoxaline chromophores are photostable with respect to laser pulses with peak intensities up to 11 GW/cm2.

Characterization of bony anatomic regions in pediatric and adult healthy volunteers using diffuse optical spectroscopic imaging.

.Significance: Diffuse optical spectroscopic imaging (DOSI) measures quantitative functional and molecular information in thick tissue in a noninvasive manner using near-infrared light. DOSI may be useful for diagnosis and prognosis of bone pathologies including osteosarcoma and Ewing’s sarcoma, but little is currently known about DOSI-derived parameters in bony anatomic locations where this disease occurs.Aim: Our goal is to quantify the optical characteristics and chromophore content of bony anatomic locations of healthy volunteers and assess differences due to anatomic region, age, sex, ethnicity, race, and body fat.Approach: Fifty-five healthy volunteers aged 4 to 72 were enrolled in the study. The optical properties and quantitative tissue concentrations of oxyhemoglobin, deoxyhemoglobin, water, and lipids were assessed at the distal humerus, distal femur, and proximal tibia. Body fat was assessed using skinfold calipers. One volunteer underwent a more comprehensive body scan from neck to foot to explore chromophore distributions within an individual. Regression analysis was used to identify the most important sources of variation in the measured data set.Results: Statistical differences between bony locations were found for scattering, water, and lipids, but not for hemoglobin. All chromophores had statistical differences with sex, but there were no significant age-related correlations. Regression analysis revealed that body fat measured with skinfold calipers was the most important predictor of oxy-, deoxy-, total hemoglobin, and lipids. Hemoglobin and lipid levels were highly correlated () over the subject population and within the single-subject body scan.Conclusions: DOSI can successfully measure bony anatomic sites where osteosarcomas and Ewing’s sarcomas commonly occur. Future studies of bone pathology using DOSI should account for the variation caused by anatomic region, sex, race and ethnicity, and body fat as these cause substantial variations in DOSI-derived metrics.

The effect of various substituents in donor moiety on the aggregation of nonlinear-optical quinoxaline-based chromophores in composite polymer materials

A series of substituents of various types in chromophore donor moiety in ortho- and meta-positions relative to divinylquinoxaline π-electron bridge was examined for isolating ability, preventing the dipole chromophores antiparallel detrimental aggregation in polymer matrix. The study was performed by molecular modeling of PMMA-based composite polymer materials with different content of pristine chromophore with dibutylaniline donor, divinylquinoxaline π-electron bridge and tricyanofuran acceptor (I) in the range from 10 wt% to 30 wt%, and of composite polymer materials with 30 wt% load of chromophores with various isolating groups of aryl, alkyl and mixed nature in donor moiety. The effect of the substituents in donor groups on the molecular nonlinear-optical (NLO) characteristics of chromophores – first hyperpolarizability – was estimated by quantum-chemical calculations at DFT level with M06-2X density functional. Introduction of isolating group in meta-position of donor is shown to lead to a strong decrease of the first hyperpolarizability of a chromophore compared to that of pristine chromophore. Joint consideration of results of molecular modeling and quantum-chemical calculations allows one to nominate o-ethyl, o-benzyloxyhexyloxy and m-methoxy-o-phenyl groups to be the best isolating ones.

Dissolved organic matter dynamics in the pristine Krka River estuary (Croatia)

The karstic Krka River is characterized by having lower dissolved organic carbon (DOC) concentrations (~30 μM) than coastal seawater (~60 μM). This peculiarity, together with the pristine nature of this area, makes the Krka River estuary a natural laboratory where it is possible to discriminate among the different dissolved organic matter (DOM) sources (riverine, marine and produced in-situ) and to study the main processes of DOM production and removal. The hypothesis behind this work is that in winter, due to the high discharge of the river, most of the DOM has a terrestrial signature, whereas in summer autochthonous DOM compose the main fraction of the DOM pool because of the reduced discharge, the high temperature and primary production. Our data shows that DOM in the river mainly consists of terrestrial molecules, as suggested by the high chromophoric content and low spectral slope (S275–295) values, as well by the predominance of humic-like substances. DOM in the seawater features the concentration and optical properties of the “typical” marine DOM from open sea waters. In summer, low riverine discharge and high temperature promote the intense biological activity, with an increase in DOC concentrations of up to 148 μM, resulting in a non-conservative behavior of DOM in the estuary. The high stratification combined with a decoupling between production and removal processes can explain the observed DOM accumulation. In the bottom layer DOM was released and quickly removed when oxygen was available, whereas in hypoxic waters the production of DOC, chromophoric DOM (CDOM) and fluorescent DOM (FDOM) was linearly related to oxygen consumption. Our work highlights the need of further studies combining chemical and biological information in order to gain new insights into the main processes responsible for DOM dynamics in this system.

Poly(amic acid)s vs. polyimides with π-conjugated –N[dbnd]N- units: Cis-trans isomerization reaction and kinetics of thermal imidization

The paper describes the synthesis and characterization of “T-type” polyimides and their precursors – poly(amic acid)s. Investigated polymers contained azobenzene derivatives with no substituent or with fluorine atom in para position to the NN linkage. The influence of the main chain architecture (open or close imide rings), location and content of azo chromophores in polymers chains on physicochemical properties were studied. To the best of our knowledge, for the first time, the cis-trans isomerization reaction was studied for azo poly(amic acid)s, that was 1–18% after 3-minutes of 405 nm-light irradiation. Poly(amic acid)s characterized higher stability of isomerization than their polyimide counterparts. The studied azo polyimides showed high glass transition temperatures (174–206 °C) and high thermal stability with the beginning of the decomposition at 246–345 °C. The imidization kinetic of the studied poly (amic acid)s were investigated by differential scanning calorimetry (DSC) using Kissinger and Ozawa models. It was found that the studied azo polymers characterized high activation energies (275.4–357.1 kJ mol−1) and frequency factors (6.5 × 1029–1.3 × 1037 s−1).

Trap-Controlled White Electroluminescence From a Single Red-Emitting Thermally Activated Delayed Fluorescence Polymer.

Single white-emitting polymers have been reported by incorporating the second-generation carbazole dendron into the side chain of a red-emitting thermally activated delayed fluorescence (TADF) polymer. Due to the prevented hole trap effect, in this case, excitons can be generated simultaneously on the polymeric host and the red TADF dopant to give a dual emission. Consequently, a bright white electroluminescence is achieved even at a dopant loading as high as 5 mol.%, revealing a maximum luminous efficiency of 16.1 cd/A (12.0 lm/W, 8.2%) and Commission Internationale de l'Eclairage (CIE) coordinates of (0.42, 0.32). The results clearly indicate that the delicate tuning of charge trap is a promising strategy to develop efficient single white-emitting polymers, whose low-band-gap chromophore content can be up to a centesimal level.

Occurrence and sources of chromophoric organic carbon in fine particulate matter over Xi'an, China

Understanding the characteristics and sources of atmospheric chromophores is essential to assess their impact on climate change and the quality of atmospheric environment. In this work, the fine particulate matter (PM2.5) samples of Xi'an, China in 2017 were analyzed by excitation-emission matrices and parallel factor analysis (EEM-PARAFAC) method to obtain the species, content, sources and seasonal variation characteristics of atmospheric chromophores. The results showed that humic-like (HULIS) chromophores and polycyclic aromatic hydrocarbons-like (PAHs-like) chromophores were the most abundant chromophores in the samples, accounting for 42% and 33%, respectively. With the aggravation of air pollution, the relative content of low-polarity chromophores increased markedly, while the relative content of polar chromophores decreased. The concentrations of atmospheric chromophores exhibited obvious seasonal variation characteristics: high in winter and low in summer. Similarly, the relative contributions of atmospheric chromophores from each source varied with the season. In addition, special weather and human activities had a significant influence on the source of atmospheric chromophores. Dust source was an important source of atmospheric chromophores, which was susceptible to long-range incoming air masses from northwestern regions in spring. However, the chromophores from the dust source were easily removed by wet precipitation, which was the same as the chromophores from the combustion source. The chromophores from the combustion source were susceptible to human activities. The contribution of combustion source to atmospheric chromophores was reduced due to the implementation of air pollution control policies during the Chinese Spring Festival. In summer, the formation of photochemical secondary chromophores was more significant than in other seasons, and the photochemical secondary chromophores increased due to the formation of liquid phase reactions under high relative humidity conditions.

Polymer Matrix Effect on Nonlinear Optical Response of Composite Materials Doped with a Chromophore Containing a Divinylqunoxaline π-Electron Bridge

The effect of polymer matrices on the nonlinear-optical properties of composite materials with guest chromophores containing a divinylquinoxaline π-electronic bridge has been investigated. Poly(methyl methacrylate) and different methacrylic copolymers as well as epoxy-amine oligomers with azo chromophores in the backbone or as side groups have been used as polymer matrices. The use of a polymer matrix containing carboxylic groups has resulted in significant decrease in the nonlinear-optical coefficient d33 as compared to the case of poly(methyl methacrylate) matrix with a guest chromophore content of 20 wt%. For materials with binary chromophores, d33 values of the studied materials have been higher than for conventional composites.

Predictive model for the quantitative analysis of human skin using photothermal radiometry and diffuse reflectance spectroscopy.

We have recently introduced a novel methodology for the noninvasive analysis of the structure and composition of human skin in vivo. The approach combines pulsed photothermal radiometry (PPTR), involving time-resolved measurements of mid-infrared emission after irradiation with a millisecond light pulse, and diffuse reflectance spectroscopy (DRS) in the visible part of the spectrum. Simultaneous fitting of both data sets with respective predictions from a numerical model of light transport in human skin enables the assessment of the contents of skin chromophores (melanin, oxy-, and deoxy-hemoglobin), as well as scattering properties and thicknesses of the epidermis and dermis. However, the involved iterative optimization of 14 skin model parameters using a numerical forward model (i.e., inverse Monte Carlo - IMC) is computationally very expensive. In order to overcome this drawback, we have constructed a very fast predictive model (PM) based on machine learning. The PM involves random forests, trained on ∼9,000 examples computed using our forward MC model. We show that the performance of such a PM is very satisfying, both in objective testing using cross-validation and in direct comparisons with the IMC procedure. We also present a hybrid approach (HA), which combines the speed of the PM with versatility of the IMC procedure. Compared with the latter, the HA improves both the accuracy and robustness of the inverse analysis, while significantly reducing the computation times.

Characterizing the molecular weight distribution of dissolved organic matter by measuring the contents of electron-donating moieties, UV absorbance, and fluorescence intensity

Electron-donating moieties (EDM) have recently been used to characterize the redox properties and treatability of dissolved organic matter during water and wastewater treatment. In this study, size exclusion chromatography followed by a derivatization-spectrometric method was developed to determine the molecular weight (MW) distribution of EDM in dissolved organic matter. The relationships between EDM concentration and chromophore content (indicated by UVA254), fluorophore content (indicated by fluorescence), and dissolved organic carbon (DOC) concentration were analyzed for different MW fractions. In general, natural organic matter (NOM) showed higher total EDM concentration and higher EDM average MW than effluent organic matter (EfOM). For NOM, fractions with MW between 1.8 k and 6.9 k Da accounted for most of the EDM (45.4%–48.6%), followed by the fractions with MW < 1.8 k Da (25.6%–42.4%). By contrast, the EDM in EfOM occurred predominantly in fractions with MW < 1 k Da (51.8%–58.6%), with lower concentrations in fractions with MW > 1.8 k Da (<20.2%). The heterogeneous MW distribution of EDM was strongly correlated to the presence of chromophores, but not DOC or fluorophores. The EDM difference between MW fractions suggested that the fraction with MW 1.8–6.9 k Da (40.7%–47.1%) and the fractions with MW < 1 k Da (50.2%–58.8%) should be the dominant oxidant consumers in NOM and EfOM, respectively. When the EDM was normalized by the DOC for each MW fraction (EDMMW/DOCMW), the EDMMW/DOCMW of relatively high-MW fractions (>1.8 k Da) is 1.2–1.9 times of relatively low-MW (<1 k Da) fractions for both NOM and EfOM, which indicates that higher-MW fractions are more susceptible to chemical oxidations. The relationship between EDM change and UVA254 change varied for different MW fractions during advanced ozonation treatment, because of the different oxidation mechanisms in operation for MW fractions. The ozonation of EfOM fractions with higher MW (>1.8 k Da) and lower MW (<1 k Da) preferentially resulted in benzoquinone formation and ring-cleavage, respectively.

The Effects of Skin Aging Associated with the Use of BioCell Collagen: A Randomized, Double-blind, Placebo-controlled Clinical Trial (P06-122-19)

ObjectivesThe aim of the study intended to correlate the effects of the dietary supplement, BioCell Collagen, with any changes associated with skin aging, since dietary supplements claim cutaneous anti-aging properties for their products; however, research supporting these claims remains sparse. MethodsA 12-week, randomized, double-blind, placebo-controlled trial of 128 female subjects, aged 39–59 (50.57 ± 5.55) randomly assigned to treatment or placebo. Intervention: Twice daily oral administration of a supplement containing 500 mg of a naturally occurring matrix of collagen type-II peptides, hyaluronic acid, and chondroitin sulfate, derived from chicken sternal cartilage, or placebo. Primary outcome measures: trans-epidermal water loss, viscoelasticity, hydration, collagen content, chromophore (melanin) content and hemoglobin level, and photographic analysis. Expert visual grading for facial lines/wrinkles, crow’s feet lines/wrinkles, skin texture/smoothness, and skin tone. Secondary outcomes: Tolerance and incidence of adverse events. Presence of erythema and/or dryness determined tolerance. Participant’s perception of the product’s value. ResultsDietary supplementation significantly reduced facial lines and wrinkles (p = 0.019), crow’s feet lines/wrinkles (p = 0.05), increased skin elasticity (p = 0.05), cutaneous collagen content (p = 0.001), and improved indicators of youthful skin appearance and wrinkle width (p = 0.046), and decreased skin dryness and erythema, compared to placebo. There was no difference between supplement and placebo for skin surface water content or retention. Supplement was well tolerated with no reported adverse reactions. ConclusionsDietary supplementation of this chicken sternal cartilage extract supports the accumulation of types-I/III collagen in skin to promote increased elasticity and reduced skin wrinkling in women 39 to 59 years of age. Funding SourcesBioCell Technology, LLC.

Photochemical production of hydroxyl radical from algal organic matter

Photochemical production of hydroxyl radical (·OH) from algal organic matter (AOM) collected from Lake Torrens in South Australia was examined using a sunlight simulator. The two AOM isolates featured lower molecular weight, lower chromophoric content, and lower SUVA254 (0.7 and 0.9, L mgC−1 m−1) than the reference Suwannee River hydrophobic acid (SR-HPO), they had considerably higher apparent quantum yields (ϕNOMOH, 3.03 × 10−5 and 2.18 × 10−5) than SR-HPO (0.84 × 10−5). Fluorescence excitation-emission matrix (FEEM) showed that the major components in the AOM were aromatic protein-like and soluble microbial substances. Unique formulas of the two AOM isolates as compared to SR-HPO were revealed using FTICR-MS and classified into four areas, namely protein-like molecules with low O/C (H/C > 1.5, O/C: 0.2–0.4), lignin-derived moieties with low O/C (H/C:1.0–1.5, O/C: 0.1–0.3), protein-like molecules with high O/C (H/C > 1.5, O/C: 0.5–0.7), and carbohydrate derivatives (H/C > 1.5, O/C > 0.7). These unique AOM moieties characterised utilizing FEEM and FTICR-MS were tentatively postulated to contribute to the high ϕNOMOH. To the best of our knowledge, this is the first study performed to both evaluate natural AOM as an efficient photosensitiser of ·OH and propose AOM moieties responsible for the high ϕNOMOH.

Onsite quantifying electron donating capacity of dissolved organic matter

Electron donating capacity (EDC) of dissolved organic matter (DOM) impacts the redox behaviors of DOM in surface waters, groundwaters, wetlands, sediments and soils but lacks applicable onsite quantification methods. To address these disadvantages, a simple and portable device with pre-injected [2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonicacid), ABTS·+] was developed that can be used for EDC onsite measurements of DOM in this work. The proposed device and method had better limits of quantification of Trolox (0.2 nmol) and more flexible DOC concentration requirement of 0.5–20 mg L−1 than that of flow injection analysis (FIA) (5–10 mg L−1) or mediated electrochemical oxidation (MEO) (>20 mg L−1). The proposed device and method greatly reduced the preparation and measurement time for sample tests compared to MEO or FIA method, enabling time-efficient EDC determination for large amount of samples. Meanwhile, the proposed device presented comparable accuracy with established MEO method when quantifying the EDCs of 7 standard humic and fulvic acids. Humic acids with higher molecular weight (MW) (<15,000 Da) had higher EDC than that with low MW (<5000 Da). EDCs of DOM in natural and reclaim water samples were both presented significantly positive correlations with their corresponding chemical oxygen demand, chromophoric DOM content, molecular weight and humification of the DOM in water samples. These results suggested that our device could accurately quantify the EDCs of DOM onsite and had promising applications on the fast quality assessment of natural and reclaimed waters.

Synthesis and nonlinear optical properties of donor-acceptor dyes based on triphenylpyrazolines as a donor block and dicyanoisophorone as acceptor

A series of donor-acceptor dyes based on polyfluoro-substituted triarylpyrazolines (as a donor block) and a dicyanoisophorone group (as an acceptor) were synthesized using the Knoevenagel condensation. The dyes have an absorption in the region of 509–514 nm and intense luminescence at 648–663 nm in chloroform with a large Stokes shift (up to 4410 cm–1). Based on the synthesized dyes, chromophore–polymer (guest–host) films were obtained in a polycarbonate matrix with a chromophore content up to 27 wt.%. Poling of chromophore–polymer films was carried out in an electric field of a corona discharge and the coefficient of nonlinear optical response d33 was measured by the second-harmonic generation method of the fundamental frequency of a Nd-YAG laser (1064 nm). The obtained films have a high initial thermal stability and a nonlinear optical response up to 80 pm V–1, which persists up to 115 °С.

Large nonlinear optical activity of chromophores with divinylquinoxaline conjugated π-bridge

Two chromophores with π-deficient quinoxaline (Q) core in the π-electron bridge together with dibutylaniline (DBA) donor moiety and tricyanofuranyl (TCF) or dicyanovinyl (DCV) acceptor moieties have been synthesized to investigate their macroscopic nonlinear optical (NLO) activity in guest-host materials. A distinctive feature of the 7-DBA-VQPhV-TCF chromophore is predominance of negative solvatochromism over the positive one, which is quite rarely met for the chromophores manifesting inverse solvatochromic behavior as well as the blue shift of the absorption maximum compared to the chromophore FTC with divinylthiophene π-bridge. Introduction of quinoxaline moiety in the conjugated bridge promotes the increase of thermal stability: Td of both compounds is higher than 225 °C. Density functional theory was used to calculate the chromophores first hyperpolarizability (β). Quadratic NLO response characterized by d33 coefficient was measured by SHG technique for thin guest-host polymer films. The influence of chromophore content on the NLO coefficient of 7-DBA-VQPhV-TCF/PMMA film has been investigated and the d33 value of this film reaches 108 pm/V at 25 wt% load. The poled film 7-DBA-VQPh-DCV/PMMA shows twice smaller d33 values (30 pm/V) at the same chromophore load (20 wt%).