Dual responsive chemosensors for anions : the combination of fluorescent PET (Photoinduced Electron Transfer) and colorimetric chemosensors in a single molecule

The design and synthesis of two novel fluorescent PET anion sensors is described, based on the principle of ‘fluorophore-spacer-(anion)receptor’. The sensors 1 and 2 employ simple diaromatic thioureas as anion receptors, and the fluorophore is a naphthalimide moiety that absorbs in the visible part of the spectrum and emits in the green. Upon recognition of anions such as F⁻ and AcO⁻ in DMSO, the fluorescence emission of 1 and 2 was ‘switched off’, with no significant changes in the UV–vis spectra. This recognition shows a 1:1 binding between the receptor and the anions. In the case of F⁻, further additions of the anion, gave rise to large changes in the UV–vis spectra, where the λ_max at 455 nm was shifted to 550 nm. These changes are thought to be due to the deprotonation of the 4-amino moiety of the naphthalimide fluorophore. This was in fact found to be the case, using simple naphthalimide derivatives such as 6. Sensors 1 and 2 can thus display dual sensing action; where at low concentrations, the fluorescence emission is quenched, and at higher concentrations the absorption spectra are modulated.

Photoinduced shape conversion and reconstruction of silver nanoprisms

A series of shapes of silver nanoplates were achieved by adjusting the concentration of citrate in the colloid in the photoinduced process. The local surface plasmon resonance (LSPR) of the silver nanoplates could be tuned gradually in a range from 740 to 440 nm. In contrast, the LSPR band can be photomediated again to the long wavelength region within 620-690 nm only by adding more citrate to the colloidal system. The initial silver nanoprisms converted to the discal shape under the light effect. In this conversion, the coupling effect of the plasmon resonance and the light source speeds up the photothermal reaction. Subsequently, the reconstruction of silver nanoprisms from the nanodisks took place in the presence of more citrate through the photoconversion.

Acceleration effect of reduced graphene oxide on photoinduced synthesis of silver nanoparticles

The photoinduced growth reaction of silver nanoparticles was accelerated by reduced graphene oxide (RGO) produced from graphene oxide (GO) during the light irradiation process in aqueous solution. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy demonstrated that RGO was generated in the photoinduced process. The acceleration effect of RGO was investigated through monitoring the extinction spectra of silver nanoparticles during the synthesis process. Moreover, transmission electron microscopy (TEM) was employed to characterize the evolution of morphologies of silver nanoparticles at different irradiation times to demonstrate the effect of RGO. The results indicate that RGO accelerates the photoinduced synthesis of silver nanoparticles. It is proposed that the acceleration effect of RGO on the photoinduced reaction is attributed to the particular property of high electronic conductivity

Photoinduced reversible shape conversion of silver nanoparticles assisted by TiO₂.

Silver nanoprisms were transformed into nanodecahedra through photoinduction of ultraviolet (UV) light in the presence of titanium dioxide (TiO2) quantum dots (QDs). Subsequently, the silver nanodecahedra were reconverted to silver nanoprisms under sodium lamp if there was sufficient citrate in the reaction system. The localized surface plasmon resonance (LSPR) optical properties of silver nanoparticles were tuned during photoinduced shape conversion. The photocatalytic activity of TiO2 QDs assisted the conversion of prisms to decahedra upon UV light irradiation. Nevertheless, the presence of TiO2 did not inhibit the photoinduced reconversion from decahedra to prisms by sodium light. It was demonstrated that citrate was indispensable in the photoinduction process. In addition, oxygen in solution played a vital role in the reversible shape conversion of silver nanoparticles. Moreover, simulated sunlight can convert silver nanoprisms to nanodecahedra instead of UV light with assistance of TiO2 QDs, which would promote the photoinduced reaction of silver nanoparticles based on a natural light source.

Generalized characteristics of photo-elastic birefringence in polymer strip waveguides

This work investigates the material birefringence in a polymer strip waveguide which originates from thermal stress during the fabrication process. The stress is estimated through a comprehensive numerical study based on a realistic finite element model. The characteristics of birefringence are obtained in a generalized form and expressed by an empirical formula, which is applicable to various polymer materials. The developed formula can be employed to specify the photo-elastic birefringence of a polymer strip channel only by knowing the birefringence in its planar film. This will eliminate the necessity of extensive numerical analysis of thermal stress in such polymer waveguides, and accordingly help the management of stress-induced effects efficiently.

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Relationship between DNA damage and sperm head birefringence

Birefringence or double refraction is the decomposition of a ray of light into two rays when it passes through an anisotropic material such as quartz. Sperm cells have been demonstrated to be optically anisotropic. The objective of this study was to evaluate the relationship between the pattern of human sperm head birefringence (SHBF) and DNA damage. A total of 26 patients with normal semen were included. DNA damage (fragmentation and denaturation) was evaluated in the sperm head in the context of birefringence, both total (SHBF-T) and partial (SHBF-P), by terminal deoxyribonucleotidyl transferase (TdT)-mediated dUDP nick-end labelling assay and acridine orange fluorescence, respectively. Positive DNA fragmentation in spermatozoa with SHBF-T (205/1053; 19.5%) was significantly higher (P < 0.0001) than in spermatozoa that presented SHBF-P (60/820; 7.3%). However, the percentage of denatured DNA in spermatozoa with SHBF-T (824/1256; 65.6%) was not significantly different from the ones with SHBF-P (666/1009; 66.0%). In conclusion, the data support a positive relationship between spermatozoa with total SHBF in their head and increased DNA fragmentation. (C) 2011, Reproductive Healthcare Ltd. Published by Elsevier Ltd. All rights reserved.

Evaluation of zona pellucida birefringence intensity during in vitro maturation of oocytes from stimulated cycles

Background: This study evaluated whether there is a relationship between the zona pellucida birefringence (ZP-BF) intensity and the nuclear (NM) and cytoplasmic (CM) in vitro maturation of human oocytes from stimulated cycles.Results: The ZP-BF was evaluated under an inverted microscope with a polarizing optical system and was scored as high/positive (when the ZP image presented a uniform and intense birefringence) or low/negative (when the image presented moderate and heterogeneous birefringence). CM was analyzed by evaluating the distribution of cortical granules (CGs) throughout the ooplasm by immunofluorescence staining. CM was classified as: complete, when CG was localized in the periphery; incomplete, when oocytes presented a cluster of CGs in the center; or in transition, when oocytes had both in clusters throughout cytoplasm and distributed in a layer in the cytoplasm periphery Nuclear maturation: From a total of 83 germinal vesicle (GV) stage oocytes, 58 of oocytes (69.9%) reached NM at the metaphase II stage. From these 58 oocytes matured in vitro, the high/positively scoring ZP-BF was presented in 82.7% of oocytes at the GV stage, in 75.8% of oocytes when at the metaphase I, and in 82.7% when oocytes reached MII. No relationship was observed between NM and ZP-BF positive/negative scores (P = 0.55). These variables had a low Pearson's correlation coefficient (r = 0.081). Cytoplasmic maturation: A total of 85 in vitro-matured MII oocytes were fixed for CM evaluation. Forty-nine oocytes of them (57.6%) showed the complete CM, 30 (61.2%) presented a high/positively scoring ZP-BF and 19 (38.8%) had a low/negatively scoring ZP-BF. From 36 oocytes (42.3%) with incomplete CM, 18 (50%) presented a high/positively scoring ZPBF and 18 (50%) had a low/negatively scoring ZP-BF. No relationship was observed between CM and ZP-BF positive/negative scores (P = 0.42). These variables had a low Pearson's correlation coefficient (r = 0.11).Conclusions: The current study demonstrated an absence of relationship between ZP-BF high/positive or low/negative score and nuclear and cytoplasmic in vitro maturation of oocytes from stimulation cycles.