Chlorosilanes are versatile reagents in organic synthesis and material science.Amild pathway is nowreported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Ya s ah ydrogen-atom-transfer photocatalyst and dichloromethane as ac hlorinating agent. Stepwise chlorination of di-and trihydrosilanes was achieved in ah ighly selective fashion assisted by continuous-flowm icro-tubing reactors.T he ability to access silyl radicals using photocatalytic SiÀHa ctivation promoted by eosin Yoffers new perspectives for the synthesis of valuable silicon reagents in aconvenient and green manner.

Gold nanoparticle modifications for TiO2 (Au/TiO2) can extend the absorption wavelength from UV to visible (Vis) and enhance the photocatalytic performance, thus fueling increasing attention as an emerging photocatalysis strategy. To explore the plasmon-enhanced photocatalytic mechanism and directly unveil the intrinsic properties of Au/TiO2, the decay kinetics of photoelectrons upon UV (355 nm) or Vis (532 nm) excitation are monitored by means of nanosecond time-resolved infrared spectroscopy, which is a unique tool offering observations without interference of the holes. Under UV irradiation, the longer lifetime of photoelectrons observed in Au/TiO2 compared to that in bare TiO2 provides unambiguous evidence for the enhanced charge separation by AuNPs. Under Vis irradiation, the long-lived (hundreds of microseconds) electrons produced by injection from AuNPs into TiO2 upon plasmon excitation are here detected for the first time. Moreover, the effects of TiO2 phase composition and the amount of AuNPs loading on the decay kinetics of long-lived photoelectrons are examined.

The triplet metal to ligand charge transfer (3MLCT) luminescence of ruthenium (II) polypyridyl complexes offers attractive imaging properties, specifically towards the development of sensitive and structure-specific DNA probes. However, rapidly-deactivating dark state formation may compete with 3MLCT luminescence depending on different DNA structures. In this work, by combining femtosecond and nanosecond pump-probe spectroscopy, the 3MLCT relaxation dynamics of [Ru(phen)2(dppz)]2+ (phen = 1,10-phenanthroline, dppz = dipyridophenazine) in two iconic G-quadruplexes has been scrutinized. The binding modes of stacking of dppz ligand on the terminal G-quartet fully and partially are clearly identified based on the biexponential decay dynamics of the 3MLCT luminescence at 620 nm. Interestingly, the inhibited dark state channel in ds-DNA is open in G-quadruplex, featuring an ultrafast picosecond depopulation process from 3MLCT to a dark state. The dark state formation rates are found to be sensitive to the content of water molecules in local G-quadruplex structures, indicating different patterns of bound water. The unique excited state dynamics of [Ru(phen)2(dppz)]2+ in G-quadruplex is deciphered, providing mechanistic basis for the rational design of photoactive ruthenium metal complexes in biological applications.

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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible‐light irradiation using neutral eosin Y as a hydrogen‐atom‐transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di‐ and trihydrosilanes was achieved in a highly selective fashion assisted by continuous‐flow micro‐tubing reactors. The ability to access silyl radicals using photocatalytic Si−H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.

Phosphorothioate (PS) modified oligonucleotides (S-DNA) naturally exist in bacteria and archaea genome and are widely used as an antisense strategy in gene therapy. However, the introduction of PS as a redox active site may trigger distinct UV photoreactions. Herein, by time-resolved spectroscopy, we observe that 266 nm excitation of S-DNA d(A ps ) 20 and d(A ps A) 10 leads to direct photoionization on the PS moiety to form hemi-bonded -P-S∴S-P-radicals, in addition to A base ionization to produce A +• /A(-H) • . Fluorescence spectroscopy and global analysis indicate that an unusual charge transfer state (CT) between the A and PS moiety might populate in competition with the common CT state among bases as key intermediate states responsible for S-DNA photoionization. Significantly, the photoionization bifurcating to PS and A moieties of S-DNA is discovered, suggesting that the PS moiety could capture the oxidized site and protect the remaining base against ionization lesion, shedding light on the understanding of its existence in living organisms.

Triplex DNA structure has potential therapeutic application in inhibiting the expression of genes involved in cancer and other diseases. As a DNA-targeting antitumor and antibiotic drug, coralyne shows a remarkable binding propensity to triplex than canonical duplex and thus can modulate the stability of triplex structure, providing a prospective gene targeting strategy. Much less is known, however, about coralyne binding interactions with triplex. By combining multiple steady-state spectroscopy with ultrafast fluorescence spectroscopy, we have investigated the binding behaviors of coralyne with typical triplexes. Upon binding with G-containing triplex, the fluorescence of coralyne is markedly quenched owing to photoinduced electron transfer (PET) of coralyne with G base. Systematic studies show that the PET rates are sensitive to the binding configuration and local microenvironment, from which coexisting binding modes of monomeric (full and partial) intercalation and aggregate stacking along sugar-phosphate backbone are distinguished and their respective contributions are determined. It shows that coralyne has preferences for monomeric intercalation within CGG triplex and pure TAT triplex, whereas CGC+ triplex adopts mainly backbone binding of coralyne aggregates due to charge repulsion, revealing the sequence-specific binding selectivity. The triplex-DNA-induced aggregation of coralyne could be used as a probe for recognizing the water content in local DNA structures. The strong π-π stacking of intercalated coralyne monomer with base-triplets plays important roles in stabilizing the triplex structure. These results provide mechanistic insights for understanding the remarkable propensity of coralyne in selective binding to triplex DNA and shed light on the prospective applications of coralyne-triplex targeted anti-gene therapeutics.

Cyclobutane pyrimidine dimer (CPD) is the most abundant DNA photolesion, and it can be repaired by photolyases based on electron-transfer mechanisms. However, photolyase is absent in the human body and lacks stability for applications. Can one develop natural enzyme mimetics utilizing nanoparticles (termed nanozymes) to mimic photolyase in repairing DNA damage? Herein, we observe the successful reversal of thymine dimer T<>T to normal T base by TiO2 under UVA irradiation. Time-resolved spectroscopy provides direct evidence that the photogenerated electron of TiO2 transfers to T<>T, causing structural instability and initiating the repair process. T–T – would then undergo bond cleavage to form T and T – , and T – returns an electron to TiO2, finishing the photocatalytic cycle. For the first time, TiO2 is discovered to exhibit photocatalytic properties similar to those of natural enzymes, pointing to its extraordinary application potential as a nanozyme to mimic photolyase in repairing DNA damage.