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This journal is © The Royal Society of Chemistry 2019.A new concept for difficult-to-replicate security inks for use in advanced anti-counterfeiting applications is presented. Inks fabricated from a mixture of photoactive dyes result in a unique fluorescent color upon irradiation that differs from the starting fluorescence. The dyes are substituted 9,9'-dianthryl sulfoxides that undergo photochemical extrusion of a sulfoxide moiety (SO) to produce emissive red, blue, and green emitters. The resulting emissive feature has specific Commission international de l'éclairage (CIE) coordinates that are used for authentication. Additionally, the temporal evolution of the fluorescence can be monitored, introducing a dynamic nature to these security features. The three compounds show different rates of photoconversion dependent on the irradiation wavelength, allowing selective wavelengths for activation to be used for additional security. CIE coordinates can be extracted from patches containing the three compounds using an inexpensive, commercially available smartphone application (app) and compared against a known value to confirm the validity of the method. This journal is © The Royal Society of Chemistry 2019.Upconversion-based photon-initiated therapeutic modalities, photodynamic therapy (PDT) in particular, have shown significant clinical potential in deep-seated tumor treatment. However, traditional multiphoton upconversion materials involving lanthanide (ion)-doped upconversion nanoparticles (UCNPs) and two-photon absorption (TPA) dyes often suffer from lots of inherent problems such as unknown systematic toxicity, low reproducibility, and extremely high irradiation intensity for realization of multiphoton upconversion excitation. Herein, for the first time, we report a one-photon excitation molecular photosensitizer (FUCP-1) based on a frequency upconversion luminescence (FUCL) mechanism. Under anti-Stokes (808 nm) excitation, FUCP-1 showed excellent photostability and outstanding upconversion luminescence quantum yield (up to 12.6%) for imaging-guided PDT. In vitro cellular toxicity evaluation presented outstanding inhibition of 4T1 cells by FUCP-1 with 808 nm laser irradiation (the half maximal inhibitory concentration was as low as 2.06 μM). After intravenous injection, FUCP-1 could specifically accumulate at tumor sites and obviously suppress the growth of deep-seated tumors during PDT. More importantly, FUCP-1 could be fully metabolized from the body within 24 h, thus dramatically minimizing systemic toxicity. This study might pave a new way for upconversion-based deep-seated cancer PDT. This journal is © The Royal Society of Chemistry 2019.Chemically modified nucleic acids have long served as a very important class of bio-hybrid structures. In particular, the modification with PEG has advanced the scope and performance of oligonucleotides in materials science, catalysis and therapeutics. Most of the applications involving pristine or modified DNA rely on the potential of DNA to form a double-stranded structure. However, a substantial requirement for metal-cations to achieve hybridization has restricted the range of applications. To extend the applicability of DNA in salt-free or low ionic strength aqueous medium, we introduce noncovalent DNA-PEG constructs that allow canonical base-pairing between individually PEGylated complementary strands resulting in a double-stranded structure in salt-free aqueous medium. This method relies on grafting of amino-terminated PEG polymers electrostatically onto the backbone of DNA, which results in the formation of a PEG-envelope. The specific charge interaction of PEG molecules with DNA, absolute absence of metal ions within the PEGylated DNA molecules and formation of a double helix that is significantly more stable than the duplex in an ionic buffer have been unequivocally demonstrated using multiple independent characterization techniques. This journal is © The Royal Society of Chemistry 2019.A versatile Rh(i)-catalyzed C6-selective decarbonylative C-H alkenylation of 2-pyridones with readily available, and inexpensive alkenyl carboxylic acids has been developed. This directed dehydrogenative cross-coupling reaction affords 6-alkenylated 2-pyridones that would otherwise be difficult to access using conventional C-H functionalization protocols. The reaction occurs with high efficiency and is tolerant of a broad range of functional groups. A wide scope of alkenyl carboxylic acids, including challenging conjugated polyene carboxylic acids, are amenable to this transformation and no addition of external oxidant is required. Mechanistic studies revealed that (1) Boc2O acts as the activator for the in situ transformation of the carboxylic acids into anhydrides before oxidative addition by the Rh catalyst, (2) a decarbonylation step is involved in the catalytic cycle, and (3) the C-H bond cleavage is likely the turnover-limiting step. This journal is © The Royal Society of Chemistry 2019.Understanding nonradiative charge recombination mechanisms is a prerequisite for advancing perovskite solar cells. By performing time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics simulations, we show that electron-hole recombination in perovskites strongly depends on the oxidation state of interstitial iodine and oxygen passivation. The simulations demonstrate that electron-hole recombination in CH3NH3PbI3 occurs within several nanoseconds, agreeing well with experiment. [https://www.selleckchem.com/products/SB-216763.html learn more] The negative interstitial iodine delays charge recombination by a factor of 1.3. The deceleration is attributed to the fact that interstitial iodine anion forms a chemical bond with its nearest lead atoms, eliminates the trap state, and decreases the NA electron-phonon coupling. The positive interstitial iodine attracts its neighbouring lattice iodine anions, resulting in the formation of an I-trimer and producing an electron trap. Electron trapping proceeds on a very fast timescale, tens of picoseconds,ovoltaic and optoelectronic devices. This journal is © The Royal Society of Chemistry 2019.A caesium fluoride-mediated hydrocarboxylation of olefins is disclosed that does not rely on precious transition metal catalysts and ligands. The reaction occurs at atmospheric pressures of CO2 in the presence of 9-BBN as a stoichiometric reductant. Stilbenes, β-substituted styrenes and allenes could be carboxylated in good yields. The developed methodology can be used for preparation of commercial drugs as well as for gram scale hydrocarboxylation. Computational studies indicate that the reaction occurs via formation of an organocaesium intermediate. This journal is © The Royal Society of Chemistry 2019.