Electrospinning preparation,characterization, and enhanced photocatalytic activity of an Silicotungstic acid (H4SiW12O40)/poly(vinyl alcohol)/poly(methyl methacrylate) composite nanofiber membrane

Silicotungstic acid (H₄SiW₁₂O₄₀)/poly(vinyl alcohol) (PVA)/poly(methyl methacrylate) (PMMA) composite nanofiber membranes were prepared by an electrospinning technique. A PMMA emulsion was mixed with PVA and H₄SiW₁₂O₄₀ evenly in water (electrospinning solvent). The configuration and elemental composition of the membranes were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The results indicate that H₄SiW₁₂O₄₀ with an intact Keggin structure existed in the composite membrane. The as‐prepared H₄SiW₁₂O₄₀/PVA/PMMA membranes exhibited enhanced photocatalytic efficiency (>84%) in the degradation of methyl orange (MO); it outperformed H₄SiW₁₂O₄₀ powder (4.6%) and the H₄SiW₁₂O₄₀/PVA nanofiber membrane (75.2%) under UV irradiation. More importantly, the H₄SiW₁₂O₄₀/PVA/PMMA membranes could be easily separated from the aqueous MO solution, and the photocatalytic efficiency of the membranes decreased inappreciably after three photocatalytic cycles. This may have been due to the enhanced water tolerance of the membranes and the stability of H₄SiW₁₂O₄₀ in the membranes. The photocatalytic process was driven by the reductive pathway with a much faster degradation rate because of the presence of PVA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43193.     

Native Chemical Ligation Directed by Photocleavable Peptide Nucleic Acid (PNA) Templates

A novel peptide–peptide ligation strategy is introduced that has the potential to provide peptide libraries of linearly or branched coupled fragments and will be suited to introduce simultaneous protein modifications at different ligation sites. Ligation is assisted by templating peptide nucleic acid (PNA) strands, and therefore, ligation specificity is solely encoded by the PNA sequence. PNA templating, in general, allows for various kinds of covalent ligation reactions. As a proof of principle, a native chemical ligation strategy was elaborated. This PNA‐templated ligation includes easy on‐resin procedures to couple linkers and PNA to the respective peptides, and a traceless photocleavage of the linker/PNA oligomer after the ligation step. A 4,5‐dimethoxy‐2‐nitrobenzaldehyde‐based linker that allowed the photocleavable linkage of two bio‐oligomers was developed.     

Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

Study of the photochemical behaviour of sunscreens – benzylidene camphor and derivatives

Benzylidene camphor derivatives have been currently used as ultraviolet filters in sunscreen compositions. When solutions of these compounds are exposed to the light from a solar simulator, a photoinduced cis-trans isomerization is observed. The initial quantum yields of this photochemical isomerization of studied molecules have been determined in several solvents. Their photochemical behaviour depends neither on the concentration nor on the presence or absence of oxygen or other inhibitors such as isopropanol or biacetyl. It means that the lifetime of the precursor states of isomerization is about 10⁻¹²s, that is to say, too short for them to react with neighbouring molecules.
For each compound, the ratio     of the respective concentrations of 'E' and 'Z' forms was also determined by photostationary state. A good agreement between theoretical and experimental values of this ratio shows that the studied compounds are only very slightly photodegradable. This was confirmed by the low values of photodegradation quantum yields.
In case of the studied compounds, the isomerization process observed is totally reversible. During irradiation a photostationary state is quickly reached, each isomer may change into the other form after absorption of a photon which leads to a mixture of isomers. In practice, it is this mixture of E and Z forms which acts as UV filters.
It may be said that a very short lifetime of the excited states, a good light stability and a reaction inertia under light irradiation make these compounds excellent sunscreen agents.
Comportement photochimique des antisolaires. Benzylidène camphre et certans de ses dérivés     

Multiphoton molecular photorelease in click-chemistry-functionalized gold nanoparticles

Yellow-green controlled photorelease: probes click-linked to peptide-coated gold nanospheres by a triazole ring can be released in living cells under a focused 561 nm laser at low power. Photocleaving follows a three-photon event stimulated by the excitation of the localized surface plasmon resonance.     

Photochemical modulation of DNA conformation by organic dications

A group of azobenzene derivatives containing two quaternary ammonium groups with various intercharge distances between them was synthesised and used to control photochemically the conformation of genomic DNA by switching the distance between cationic ammonium groups in the dications. It was found that isomerisation of either dication from the trans form to cis resulted in an increase in the dication's efficiency for DNA compaction; this is associated with a decrease in intercharge distance between ammonium groups and leads to a better match of the binder's cationic groups to adjacent phosphate groups of DNA. Ammonium dications have several important advantages over the photosensitive surfactant type of diazobenzene reported earlier: they can be used at significantly lower (>100-fold) concentrations than photosensitive surfactants, and DNA conformation control can be performed over a broader concentration range of dications. The influence of intercharge distance in photosensitive dications on photo-induced DNA binding discrimination is discussed, and the molecular mechanism is proposed.     

UV radiation induces genome-mediated, site-specific cleavage in viral proteins

Much research has been dedicated to understanding the molecular basis of UV damage to biomolecules, yet many questions remain regarding the specific pathways involved. Here we describe a genome-mediated mechanism that causes site-specific virus protein cleavage upon UV irradiation. Bacteriophage MS2 was disinfected with 254 nm UV, and protein damage was characterized with ESI- and MALDI-based FT-ICR, Orbitrap, and TOF mass spectroscopy. Top-down mass spectrometry of the products identified the backbone cleavage site as Cys46-Ser47 in the virus capsid protein, a location of viral genome-protein interaction. The presence of viral RNA was essential to inducing backbone cleavage. The similar bacteriophage GA did not exhibit site-specific protein cleavage. Based on the major protein fragments identified by accurate mass analysis, a cleavage mechanism is proposed by radical formation. The mechanism involves initial oxidation of the Cys46 side chain followed by hydrogen atom abstraction from Ser47 C(α). Computational protein QM/MM studies confirmed the initial steps of the radical mechanism. Collectively, this study describes a rare incidence of genome-induced protein cleavage without the addition of sensitizers.     

唑烷酮类化合物的光合成研究

通过光化学方法取代传统的金属催化等法合成重要的药物中间体唑烷酮,反应条件温和、操作简便、产率较高且污染少.同时研究了丙酮、甲醇、乙腈3种溶剂与水的不同配比对反应产物的影响.随着溶剂极性增加,立体选择性有一定提高.     

Xanthene dyes/amine as photoinitiators of radical polymerization: A comparative and photochemical study in aqueous medium

The efficiency of several xanthene dyes as photoinitiators of the free radical polymerization in aqueous medium was evaluated. These results show that dyes with triplet quantum yield higher than 0.1 present similar efficiencies, independently of their different chemical structure. A detailed study of the photophysics of the dyes under the polymerization conditions was carried out using laser time-resolved spectroscopies. These studies show that the active radicals are those which formed in the interaction of excited triplet state of the dye with the amine through an electron transfer process. In spite of this, the photoinitiation efficiency is not correlated with the triplet quantum yield. Also, the photophysics studies show that the quantum yield of the different pathways of the decomposition of the charge transfer intermediate is an important parameter to predict the efficiency of these photoinitiator systems. The experimentally measured active radical formation is well correlated with that calculated from the polymerization rate. The presence of heavy atoms in the xanthene ring increases the triplet quantum yield, but decreases the active radical yield, and then the polymerization rate.