A high triplet-energy polymer: synthesis and photo-physical properties of a π-stacked vinyl polymer having a xanthone moiety in the side chain

RSC Advances ◽  
2015 ◽  
Vol 5 (27) ◽  
pp. 21310-21315 ◽  
Author(s):  
Hiroyoshi Sugino ◽  
Yasuhito Koyama ◽  
Tamaki Nakano
Keyword(s):  
Excitation Energy ◽  
Physical Properties ◽  
Polymer Synthesis ◽  
Side Chain ◽  
Triplet Energy ◽  
Vinyl Polymer ◽  
Blue Phosphorescent

Poly(xanthon-3-yl methacrylate) having a π-stacked conformation efficiently harvests photo excitation energy for sky blue phosphorescent emission of iridium bis[(4,6-difluorophenyl)pyridinato-N,C2]picolinate (FIrpic) in solution and in film.

Thymine Dimerization Induced by Oxidative DNA Lesions and Epigenetic Intermediates via Triplet-Triplet Energy Transfer

2020 ◽  
Author(s):  
Mauricio Lineros-Rosa ◽  
Antonio Francés-Monerris ◽  
Antonio Monari ◽  
Miguel Angél Miranda ◽  
Virginie Lhiaubet-Vallet
Keyword(s):  
Energy Transfer ◽  
Excitation Energy ◽  
Transient Absorption ◽  
Theoretical Calculations ◽  
Dna Lesions ◽  
Transient Absorption Spectroscopy ◽  
Triplet Energy ◽  
Pyrimidine Dimers ◽  
Triplet Energy Transfer ◽  
Dna Nucleobases

Interaction of nucleic acids with light is a scientific question of paramount relevance not only in the understanding of life functioning and evolution, but also in the insurgence of diseases such as malignant skin cancer and in the development of biomarkers and novel light-assisted therapeutic tools. This work shows that the UVA portion of sunlight, not absorbed by canonical DNA nucleobases, can be absorbed by 5-formyluracil (ForU) and 5-formylcytosine (ForC), two ubiquitous oxidative lesions and epigenetic intermediates present in living beings in natural conditions. We measure the strong propensity of these molecules to populate triplet excited states able to transfer the excitation energy to thymine-thymine dyads, inducing the formation of the highly toxic and mutagenic cyclobutane pyrimidine dimers (CPDs). By using steady-state and transient absorption spectroscopy, NMR, HPLC, and theoretical calculations, we quantify the differences in the triplet-triplet energy transfer mediated by ForU and ForC, revealing that the former is much more efficient in delivering the excitation energy and producing the CPD photoproduct. Although significantly slower than ForU, ForC is also able to harm DNA nucleobases and therefore this process has to be taken into account as a viable photosensitization mechanism. The present findings evidence a rich photochemistry crucial to understand DNA photodamage and of potential use in the development of biomarkers and non-conventional photodynamic therapy agents.

A study of the relationships of interactions between Asp-201, Na+ or K+, and galactosyl C6 hydroxyl and their effects on binding and reactivity of β-galactosidase

2004 ◽  
Vol 82 (2) ◽  
pp. 275-284 ◽  
Author(s):  
Julia Xu ◽  
Mary A.A McRae ◽  
Scott Harron ◽  
Beatrice Rob ◽  
Reuben E Huber
Keyword(s):  
Physical Properties ◽  
Negative Charge ◽  
Binding Pocket ◽  
Side Chain ◽  
Wild Type ◽  
Sodium Potassium ◽  
The Difference ◽  
Potassium Binding ◽  
Covalent Intermediate ◽  
Catalytic Effects

The interactions between Na+ (and K+) and Asp-201 of β-galactosidase were studied. Analysis of the changes in Km and Vmax showed that the Kd for Na+ of wild type β-galactosidase (0.36 ± 0.09 mM) was about 10× lower than for K+ (3.9 ± 0.6 mM). The difference is probably because of the size and other physical properties of the ions and the binding pocket. Decreases of Km as functions of Na+ and K+ for oNPG and pNPG and decreases of the Ki of both shallow and deep mode inhibitors were similar, whereas the Km and Ki of substrates and inhibitors without C6 hydroxyls remained constant. Thus, Na+ and K+ are important for binding galactosyl moieties via the C6 hydroxyl throughout catalysis. Na+ and K+ had lesser effects on the Vmax. The Vmax of pNPF and pNPA (substrates that lack a C6 hydroxyl) did not change upon addition of Na+ or K+, showing that the catalytic effects are also mediated via the C6 hydroxyl. Arrhenius plots indicated that Na+, but not K+, caused k3 (degalactosylation) to increase. Na+ also caused the k2 (galactosylation) with oNPG, but not with pNPG, to increase. In contrast, K+ caused the k2 values with both oNPG and pNPG to increase. Na+ and K+ mainly altered the entropies of activation of k2 and k3 with only small effects on the enthalpies of activation. This strongly suggests that only the positioning of the substrate, transition states, and covalent intermediate are altered by Na+ and K+. Further evidence that positioning is important was that substitution of Asp-201 with a Glu caused the Km and Ki values to increase significantly. In addition, the Kd values for Na+ or K+ were 5 to 8 fold higher. The negative charge of Asp-201 was shown to be vital for Na+ and K+ binding. Large amounts of Na+ or K+ had no effect on the very large Km and Ki values of D201N-β-galactosidase and the Vmax values changed minimally and in a linear rather than hyperbolic way. D201F-β-galactosidase, with a very bulky hydrophobic side chain in place of Asp, essentially obliterated all binding and catalysis.Key words: β-galactosidase, sodium, potassium, binding, aspartic acid.

A Porous 4d-4f Heterometallic Coordination Polymer: Synthesis, Crystal Structure and Physical Properties

2011 ◽  
Vol 637 (11) ◽  
pp. 1555-1559 ◽  
Author(s):  
Guang-Xiang Liu ◽  
Xin-Long Li ◽  
Xiao-Chun Zha ◽  
Chun-You Zhang ◽  
Yan Wang ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Coordination Polymer ◽  
Physical Properties ◽  
Polymer Synthesis ◽  
Heterometallic Coordination Polymer
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