Synthesis,spectroscopic properties and applications of novel N-heterocycle-containing benzotriazoles as UV absorbers

Two novel N-heterocycle-containing benzotriazole compounds, 5-（5-chloro-2-benzotriazolyl）-6-hydroxy-l,4-dimethyl-3-car- bonitrile-2-pyddone （2） and 4-（5-chloro-2-benzotdazolyl）-5-methyl-2-phenyl-3-pyrazolone （4）, were synthesized from reactant 4- chloro-2-nitroaniline via diazotization, azo coupling, reductive cyclization and acidification. Their structures were confirmed by Fr-IR, 1H NMR, mass spectroscopy and elemental analysis. Their spectral properties were investigated and compared with that of a common commercial benzotriazole UV absorber Tinuvin 326. It is found that the novel N-heterocycle-containing benzotriazole compounds exhibit sharp single peak in the range of 280-400 nm and have much higher molar extinction coefficients than that of Tinuvin 326. Their anti-UV protection properties on polyester fabric were also evaluated and compound 4 was much superior to compound 2 due to its higher exhaustion.

Functionalization of Silica Surface with UV-Active Molecules by Multivalent Organosilicon Spacer

Immobilization of active molecules by attachment onto solid surfaces is a well-established practice in many processes and applications. Silica micro- and nano-particles are attractive candidates as support for active molecules as a result of a combination of desirable properties. The present study deals with grafting of a functional UV active molecule onto silica surfaces via hydrosilylation reactions using multivalent organosilicon spacers. Different types of organosilicon precursors based on dimethylsiloxysilanes containing multiple SiH groups were used as spacers between vinyl-modified silica surface and the benzotriazole UV-absorber (UVA). Firstly, the surface of silica was modified with vinyltrimetoxsisilane coupling agent. The UVA molecules were attached to the silica-vinyl by a two-step procedure involving hydrosilylation reaction. The successful grafting was confirmed by FTIR, TGA and UV-Vis characterization. More than fivefold increase in UVA loading was found for the MH30 multifunctional spacer, which contains approximately 75 SiH groups per molecule, when compared to a four-functional spacer. Furthermore a branched, bulky six-functional spacer is preferred over a linear spacer of the same functionality. UV activity of functionalized silica was studied by UV-Vis spectroscopy, indicating that the immobilization of UVA onto silica surface has not altered its UV absorbance properties.

Characterization of dissolved organic matter fractions from Lake Hongfeng, Southwestern China Plateau

With XAD-series and ion exchange resins, dissolved organic matter （DOM） from Lake Hongfeng in Southwestern China Plateau was isolated into 6 fractions, i.e., humic acid （HA）, fulvic acid （FA）, hydrophobic neutrals （HON）, hydrophilic acids （HIA）, hydrophilic bases （HIB） and hydrophilic neutrals （HIN）. Those fractions were characterized by high performance size exclusion chromatography, fluorescence spectroscopy and UV absorbance. Among the 6 fractions, FA was predominant and accounted for 51% of the total DOM. The weight-average （Mw） and number-averaged （Mn） molecular weight of these fractions ranged from 1688 to 2355 Da and from 1338 to 1928 Da, respectively. A strong correlation was observed between specific UV absorbance at 280 nm, E2/E3 （absorbance at 250 nm to 365 nm）, and the molecular weight for DOM fractions. UV-Vis fulvic-like fluorescence peaks were found in all fractions. Proteinlike fluorescence peaks existed in HON may indicate that microbial activity was severely in Lake Hongfeng. There was a significant relationship between fluorescence intensities and specific UV absorbance at 254 nm for those DOM fractions, suggesting their similar luminescence characteristics. The values of fluorescence index （f450/500） indicated that hydrophobic fractions may derive from terrestrial sources, and the hydrophilic fractions from microbial and terrestrial origins. Those results suggest that there were inter-relationships between molecular weight, fluorescence and absorbance characteristics, and also subtle consistencies between the hydrophilic and hydrophobic properties and the sources for these 6 fractions from Lake Hongfeng.

Preparation of nano-sized cerium and titanium pyrophosphates via solid-state reaction at room temperature

Nano-sized cerium-titanium pyrophosphates Ce1-xTixP2O7 （with x = 0, 0.2, 0.5, 0.7, 0.9, and 1.0） were obtained by grinding a mixture of Ce（SO4）2·4H2O, Ti（SO4）2, and Na4P2O7·10H2O in the presence of surfactant PEG-400 at room temperature, washing the mixture with water to remove soluble inorganic salts, and drying at 100℃. The products and their calcined samples were characterized using ultraviolet-visible spectroscopy （UV-vis）, thermogravimetry and differential thermal analyses （TG/DTA）, X-ray powder diffraction （XRD）, and transmission electron microscopy （TEM）. The results show that nano-sized Ce1-xTixP2O7 behave as an excellent UV-shielding material. Thereinto, the CeP2O7 has the most excellent UV-shielding effect, and the amorphous state of Ce0.8Ti0.2P2O7 can keep at a higher temperature than CeP2O7. Therefore, the stabilization of the amorphous state of the cerium pyrophosphates was carded out by doping titanium. This stabilization is a significant improvement, which enables to apply these amorphous pyrophosphates not only to cosmetics and paints, but also plastics and films.

Preparation and Characterization of CeO_2-TiO_2/SnO_2:Sb Films Deposited on Glass Substrates by R.F.Sputtering

CeO2-TiO2 films and CeO2-TiO/SnO2：Sb （6 mol%） double films were deposited on glass substrates by radio-frequency magnetron sputtering （R.F. Sputtering）, using SnO2：Sb（6 mol%） target, and CeO2- TiO2 targets with different molar ratio of CeO2 to TiO2 （CeO2：TiO2-0：1.0; 0.1：0.9; 0.2：0.8; 0.3：0.7; 0.4：0.6; 0.5：0.5; 0.6：0.4; 0.7：0.3; 0.8：0.2; 0.9：0.1; 1.0：0）. The films are characterized by UV-visible transmission and infrared reflection spectra, scanning electron microscopy （SEM）, Raman spectroscopy, X-ray photoelectron spectroscopy （XPS） and X-ray diffraction （XRD）, respectively. The obtained results show that the amorphous phases composed of CeO2-TiO2 play an important role in absorbing UV, there are Ce^3-, Ce^4- and Ti^4- on the surface of the films; the glass substrates coated with CeO2-TiO2 （Ce/Ti=0.5：0.5; 0.6：0.4）/SnO2：Sb（6 mol%） double films show high absorbing UV（〉99）, high visible light transmission （75%） and good infrared reflection （〉70%）. The sheet resistance of the films is 30-50 Ω/□. The glass substrates coated with the double functional films can be used as window glass of buildings, automobile and so on.

Preparation of new sunscreen materials Ce_(1-x)Zn_xO_(2-x) via solid-state reaction at room temperature and study on their properties

Superfine cerium-zinc oxides Ce1-xZnxO2-x with x = 0, 0.1, 0.3, 0.5, and 1.0 were obtained by grinding Ce（SO4）2·4H2O, ZnSO4·7H2O and NH4HCO3 under the condition of surfactant PEG-400 being present at room temperature, washing the mixture with water to remove soluble inorganic salts, drying at 80°C, and calcining.The precursor and its calcined samples were characterized using thermogravimetry and differential thermal analyses（TG/DTA）, UV-vis absorption spectroscopy, X-ray powder diffraction（XRD）, and scanning electron microscopy（SEM）.The results showed that superfine Ce1-xZnxO2-x behaved as an excellent UV-shielding material.The ZnO-doped CeO2 can facilitate the formation of crystalline state CeO2.The catalytic ability of products used in air oxidation of castor oil was investigated.The results showed that the catalytic abilities of products decreased with increasing zinc amount.

Fabrication of Zn-Ti layered double hydroxide by varying cationic ratio of Ti^(4+) and its application as UV absorbent

ZnTi-layered double hydroxides（LDHs） with varying Zn/Ti ratio have been synthesized by coprecipitation of zinc and titanium salts from homogeneous solution.The obtained ZnTi-LDHs possess high crystallinity and hierarchical structure with improved UV-absorbance property.The UV-vis spectra show that the UV absorbing properties of ZnTi-LDHs is stronger and broader than both MgAl-LDH and ZnAl-LDH due to the existence of Ti.Moreover,the UV absorption property increased with the content of Ti,which can be ascribed to the decrease in the band gap energy,as clearly confirmed by density functional theory calculations.When irradiated by UV rays,the property of the samples with generated free radicals（OH^·and O2^·） was evaluated by means of electron spin resonance（EPR）.ZnTi-LDHs generated a relatively lower active radicals in contrast with TiO2 and ZnO,which implied an increased safety used as sunscreens.Therefore,this work provides a detailed understanding of UV shielding properties of ZnTiLDHs which was unrevealed previously,and demonstrates the expansive application prospects of ZnTiLDHs in the field of sunscreens.

Physiological Defense Mechanism of Ligularia intermedia Against UV-B Radiation on Dongling Mountain

Ligularia intermedia growing at different altitudes were used to investigate the mechanism of ultraviolet (UV) resistance on physiological aspects in the field. The tests compared the absorbance of the UV absorbing compound, the content of chlorophyll a, chlorophyll b, and carotenoids, and the activities of peroxidase (POX) and superoxide dismutase (SOD) in Ligularia intermedia growing at three different altitudes on Dongling Mountain in northern China. There were no significant differences between the plants growing at 1160 m and 1820 m. However, all of these factors increased dramatically at 2190 m. The results indicate that the UV resistance of the plants mainly depends on the mechanism of filtering the radiation and preventing the reactive oxygen species (ROS) damage produced by UV B

Fabrication of intercalated p-aminobenzoic acid into Zn-Ti layered double hydroxide and its application as UV absorbent

An organic ultraviolet （UV） ray absorbent, p-aminobenzoic acid （PABA） was intercalated into a Zn-Ti layered double hydroxide （LDH） precursor by an anion-exchange reaction to obtain ZnTi-PABA-LDH, a new organic-inorganic nanocomposite. The structure and the thermal stability of ZnTi-PABA-LDH were characterized by XRD, FT-IR and TG-DTA. The results indicate ZnTi-PABA-LDH, synthesized by this method, exhibit relatively high crystallinity, and markedly enhanced thermal stability of PABA after intercalation into ZnTi-LDH. The UV-vis-NIR spectrophotometric and ESR data show excellent UV ray resistance and greatly decreased photocatalytic activity when PABA is intercalated into the interlayers of the ZnTi-LDH. The studies suggest that ZnTi-PABA-LDH may have potential applications as safe sunscreen materials.

Contrasting altitudinal patterns of leaf UV reflectance and absorbance in four herbaceous species on the Qinghai-Tibetan Plateau

Aims Alpine plants have to cope with intense ultraviolet(UV)radiation and its altitudinal changes.It has been argued that leaf UV reflec-tance and absorbance should play a central role in acclimation and adaptation to changes in UV radiation,but evidence is lim-ited from high altitudinal ecosystems.In this study,we assessed whether leaf UV reflectance and leaf pigments jointly vary with altitude in alpine broadleaved herbaceous species.The primary hypothesis is that leaves with higher UV reflectance should have lower UV absorbance and/or lower contents of photosynthetic pigments.Methods Leaf UV reflectance,leaf UV absorbance and photosynthetic pig-ments(chlorophyll a and b,carotenoids)were examined in four broadleaved herbaceous species in relation to their habitat alti-tudes.The leaf surface reflectance and leaf extract absorbance at wavelengths of 305 and 360 nm were measured to examine the leaf optical and photochemical characteristics in the UV-B and UV-A bands,respectively.The species included Saussurea katochaete Maxim.,Saussurea pulchra Lipsch.,Anaphalis lactea Maxim.and Rheum pumilum Maxim.,which are distributed along the same slope from 3200 to 4200 m in the Qilian Mountains,Qinghai-Tibetan Plateau.Important Findings The leaf UV absorbance was approximately twice as high at 305 nm(UV-B)than at 360 nm(UV-A)for all species except R.pumilum.Among the four species,the leaf UV absorbance was the highest and almost all values were within 2-6 Abs cm^(−2)(absorbance cm^(−2))in S.pulchra,but the lowest(frequently<1 Abs cm^(−2))were observed in R.pumilum.Only R.pumilum showed significantly higher values at higher elevations.Leaf UV reflectance was generally higher at higher elevations for all species except for A.lactea,and exhibited much larger altitudinal variations compared to leaf UV absorbance.Anaphalis lactea showed a very high UV reflectance even at low altitudes.Among the four species,photosynthetic pigments tended to decrease with an increase in leaf UV reflectance but increased with leaf UV absorbance.The study suggests that leaf UV reflec-tance,rather than leaf UV absorbance,plays a more active role in acclimation to altitudinal changes in UV radiation,and a high investment in leaf UV reflectance may limit the accumulation of photosynthetic pigments in alpine plants.

Enhancing photostability and power conversion efficiency of organic solar cells by a “sunscreen” ternary strategy

The field has witnessed the rapid growth in the power conversion efficiency(PCE)of organic solar cells(OSCs)over the past decade,reaching the threshold for practical commercialization.However,a major issue remains that OSC lifetimes are seriously limited by the ultraviolet(UV)-induced photodegradation.Here,inspired by the superior photostability of car paint under sunlight and ambient air,a“sunscreen”molecule,2-(2-hydroxy-5-tert-octylphenyl)benzotriazole(UV329),is used to construct the PM6:Y6 ternary device.The addition of UV329 mainly enhances the ordered stacking of PM6 and increases the light utilization of blend films with the improved crystallization and appropriate phase separation.Accordingly,the ternary device exhibits stronger light response and obviously higher and more balanced carrier mobilities,contributing to higher short-circuit current density,fill factor and PCE.Similar PCE boost is also verified in PM6:BTP-e C9 and PM6:L8-BO systems.The photodegradation of PM6 dominates the photo-degradation process of PM6:Y6 systems,while the UV329 can effectively suppress such degradation,and thus the ternary device can retain nearly 90%of the initial PCE under continuous illumination for 120 min.Moreover,ternary devices also preserve better thermal stability and shelf-life with the enhanced PCE.This work provides a simple yet effective strategy for simultaneously improving PCE and photostability of OSCs.

4D biofabrication via instantly generated graded hydrogel scaffolds

Formation of graded biomaterials to render shape-morphing scaffolds for 4D biofabrication holds great promise in fabrication of complex structures and the recapitulation of critical dynamics for tissue/organ regeneration.Here we describe a facile generation of an adjustable and robust gradient using a single-or multi-material one-step fabrication strategy for 4D biofabrication.By simply photocrosslinking a mixed solution of a photocrosslinkable polymer macromer,photoinitiator(PI),UV absorber and live cells,a cell-laden gradient hydrogel with pre-programmable deformation can be generated.Gradient formation was demonstrated in various polymers including poly(ethylene glycol)(PEG),alginate,and gelatin derivatives using various UV absorbers that present overlap in UV spectrum with that of the PI UV absorbance spectrum.Moreover,this simple and effective method was used as a universal platform to integrate with other hydrogel-engineering techniques such as photomask-aided microfabrication,photo-patterning,ion-transfer printing,and 3D bioprinting to fabricate more advanced cell-laden scaffold structures.Lastly,proof-of-concept 4D tissue engineering was demonstrated in a study of 4D bone-like tissue formation.The strategy’s simplicity along with its versatility paves a new way in solving the hurdle of achieving temporal shape changes in cell-laden single-component hydrogel scaffolds and may expedite the development of 4D biofabricated constructs for biological applications.

Molecular Modification of Benzophenone Derivatives for Lower Bioenrichment and Toxicity Through the Pharmacophore Model

In this study,we used the improved extreme-difference normalization method to calculate the comprehensive evaluation values of bioenrichment and toxicity of benzophenone UV light absor-bers(BPs).Based on this parameter,a 3D-QSAR(QSAR=quantitative structure activity relationship)pharmacophore model was constructed using Discovery Studio software and applied to the mole-cular modification of BPs.With three commonly used ingredients in sunscreen 2-hydroxy-4-methoxybenzophenone(BP-3),2,2'-dihydroxy-4,4'-dimethoxybenzophenone(BP-6)and 2,2'-dihydroxy-4-methoxybenzophenone(BP-8)as target molecules,we performed BPs substitution reaction based on the binding positions of characteristic elements of the pharmacophore model and designed BP derivatives with reduced bioenrichment and toxicity.Stability and function evaluation showed that while the stability of 6 BP derivatives was enhanced,the light absorption capacity was also significantly enhanced(from 9.16%to 43.16%).Molecular dynamics simulation results showed that the binding ability of BP-609 molecule with serum albumin was reduced by 16.37%compared with BP-6,and the binding with collagen could not occur spontaneously,which could be used as an explanation for the simultaneous reduction of its bioenrichment and toxicity.Besides,through the simulation of human metabolism,it was found that the liver metabolites of BP-609 were less toxic,which reduced the potential risk of human metabolism.It proved that the molecular modification scheme of BPs was environment-friendly.

Selective elimination of chromophoric and fluorescent dissolved organic matter in a full-scale municipal wastewater treatment plant

Effluent organic matter（Ef OM） from municipal wastewater treatment plants potentially has a detrimental effect on both aquatic organisms and humans.This study evaluated the removal and transformation of chromophoric dissolved organic matter（CDOM） and fluorescent dissolved organic matter（FDOM） in a full-scale wastewater treatment plant under different seasons.The results showed that bio-treatment was found to be more efficient in removing bulk DOM（in term of dissolved organic carbon,DOC） than CDOM and FDOM,which was contrary to the disinfection process.CDOM and FDOM were selectively removed at various stages during the treatment.Typically,the low molecular weight fractions of CDOM and protein-like FDOM were more efficiently removed during bio-treatment process,whereas the humic-like FDOM exhibited comparable decreases in both bio-treatment and disinfection processes.Overall,the performance of the WWTP was weak in terms of CDOM and FDOM removal,resulting in enrichment of CDOM and FDOM in effluent.Moreover,the total removal of the bulk DOM（P 〈 0.05） and the protein-like FDOM（P 〈 0.05） displayed a significant seasonal variation,with higher removal efficiencies in summer,whereas removal of CDOM and the humic-like FDOM showed little differences between summer and winter.In all,the results provide useful information for understanding the fate and transformation of DOM,illustrating that sub-fractions of DOM could be selectively removed depending on treatment processes and seasonality.

Thermo-oxidative degradation of Nylon 1010 films:Colorimetric evaluation and its correlation with material properties

The thermo-oxidative aging behaviors of Nylon 1010 films were studied by various analytical methods,such as measuring the chromaticity,relative viscosity,carbonyl index,UV absorbance at 280 nm and elongation at break of the aged films.The thermo-oxidative aging plots of the results obtained via these various methods at different temperatures are subjected to the time-temperature superposition analysis,which are found to be well superposed.The b＊ values are used as X axis and the other results,i.e.,relative viscosity,carbonyl index,UV absorbance at 280 nm and elongation at break,are used as V axis,respectively.The relationship between the b values and the other results is obtained,from which we can derive the changes of physical and chemical properties at different b＊ values.Since the b＊ values can be quickly determined by using a portable spectrophotometer,the on-line evaluation of the thermo-oxidative aging of Nylon 1010 can be realized.