The review covers the knowledge on photoremovable protecting
groups and includes all relevant chromophores studied in the
time period of 2000–2012; the most relevant earlier works are
also discussed.

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Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

2.3. [4 + 4] Cycloadditions 1058 2.4. Photocycloadditions of Aromatic Compounds 1058 2.4.1. Benzene Derivatives 1058 2.4.2. Condensed Aromatic Compounds 1060 3. Photochemical Rearrangements 1061 4. Cyclizations 1064 4.1. Pericyclizations 1064 4.2. Norrish−Yang Reaction 1066 5. Photochemical Extrusion of Small Molecules 1067 6. Photochemical Electron Transfer 1068 6.1. Photochemical Electron-Transfer Reactions with a Catalytic Sensitizer 1068

Photochemical Reactions as Key Steps in Organic Synthesis

ZnO nanorod arrays were fabricated using a hydrothermal method. The nanorods were studied by scanning electron microscopy, photoluminescence (PL), time-resolved PL, X-ray photoelectron spectroscopy, and positron annihilation spectroscopy before and after annealing in different environments and at different temperatures. Annealing atmosphere and temperature had significant effects on the PL spectrum, while in all cases the positron diffusion length and PL decay times were increased. We found that, while the defect emission can be significantly reduced by annealing at 200 °C, the rods still have large defect concentrations as confirmed by their low positron diffusion length and short PL decay time constants.

Defects in ZnO nanorods prepared by a hydrothermal method

Defects in three different types of ZnO nanostructures before and after annealing under different conditions were studied. The annealing atmosphere and temperature were found to strongly affect the yellow and orange-red defect emissions, while green emission was not significantly affected by annealing. The defect emissions exhibited a strong dependence on the temperature and excitation wavelength, with some defect emissions observable only at low temperatures and for certain excitation wavelengths. The yellow emission in samples prepared by a hydrothermal method is likely due to the presence of OH groups, instead of the commonly assumed interstitial oxygen defect. The green and orange-red emissions are likely due to donor acceptor transitions involving defect complexes, which likely include zinc vacancy complexes in the case of orange-red emissions.

http://iopscience.iop.org/article/10.1088/0957-4484/18/9/095702/pdf

Defect emissions in ZnO nanostructures

Although researchers have made great progress in the development of responsive polymeric materials for controlled drug release or diagnostics over the last 10 years, therapeutic results still lag behind expectations. The development of special materials that respond to physiological relevant concentrations, typically within the micromolar or nanomolar concentration regime, remains challenging. Therefore, researchers continue to pursue new biomaterials with unique properties and that respond to mild biochemical signals or biomarkers.Selenium is an essential element in human body with potential antioxidant properties. Because of selenium’s electronegativity and atomic radius, selenium-containing compounds exhibit unique bond energy (C–Se bond 244 kJ mol–1; Se–Se bond 172 kJ mol–1). These values give the C–Se or Se–Se covalent bonds dynamic character and make them responsive to mild stimuli. Therefore, selenium-containing polymers can disassemble in response to changes under physiological relevant conditions...

Selenium-containing polymers: promising biomaterials for controlled release and enzyme mimics.

A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR3) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR3 was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two...

Ultrafast time-resolved study of photophysical processes involved in the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds.

The kinetics and mechanism of the photodeprotection and rearrangement reactions for the pHP phototrigger compounds p-hydroxyphenacyl diethyl phosphate (HPDP) and diphenyl phosphate (HPPP) were studied using transient absorption (TA) and picosecond time-resolved resonance Raman (ps-TR 3 ) spectroscopy. TA spectroscopy was employed to detect the dynamics of the triplet precursor decay as well as to investigate the influence of the solvent and leaving group on the triplet quenching process. Ps-TR 3 spectroscopy was used to directly monitor the formation dynamics for the photosolvolytic rearrangement product and its solvent and leaving group dependence. The TA and TR 3 spectroscopy experiments were also used to characterize the structural and electronic properties of the triplet precursor to the HPDP and HPPP deprotection reactions. The solvent effect observed in conjunction with the leaving group dependence of the triplet decay dynamics are consistent with a concerted solvent assisted triplet cleavage through a heterolytic mechanism for the HPDP and HPPP photodeprotection process. Correlation of the dynamics between the deprotection and rearrangement processes reveals there is a consecutive mechanism and the involvement of an intermediate between the two reaction steps. The reaction rate of the deprotection and rearrangement steps and the influence of the solvent and leaving group were determined and evaluated based on kinetic modeling of the dynamical data obtained experimentally for HPDP and HPPP in H 2 O/ MeCN mixed solvents with varying water concentration in the solvent system. A solvation complex with a contact ion pair character was proposed to be the intermediate involved in the deprotection and rearrangement pathway. The results here combined with our previous study on the photophysical events occurring on the early picosecond time scale (Ma; et al. J. Am. Chem. Soc. 2005, 127, 1463-1472) provide a real time overall mechanistic description for the photodeprotection and rearrangement reactions of pHP caged phosphate phototrigger compounds.

Ultrafast time-resolved transient absorption and resonance raman spectroscopy study of the photodeprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates.

Pico- and nanosecond time-resolved resonance Raman (TR3) spectroscopy have been utilized to study the dynamics and structure of p-hydroxyacetophenone (HA) and the p-hydroxyphenacyl-caged phototrigger compound p-hydroxyphenacyl diethyl phosphate (HPDP) in acetonitrile solution. Transient intermediates were detected and attributed to the triplet states of HA and HPDP. Nanosecond-TR3 measurements were done for two isotopically substituted HA molecules to help better assign the triplet state carbonyl CO stretching and the ring related vibrational modes. The dynamics of formation and the spectral characteristics for the triplet states were found to be similar for the HA and HPDP. The temporal evolution at very early picosecond time scale indicates there is rapid intersystem crossing (ISC) conversion and subsequent relaxation of the excess energy of the initially produced energetic triplet state. B3LYP/6-311G** density functional theory (DFT) calculations were done to determine the structures and vibrational fr...

Jovi Tze Wai Kan

Papers

Ultrafast time-resolved study of photophysical processes involved in the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds.

Ultrafast time-resolved transient absorption and resonance raman spectroscopy study of the photodeprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates.

Time-resolved resonance Raman study of the triplet states of p-hydroxyacetophenone and the p-hydroxyphenacyl diethyl phosphate phototrigger compound.

Poly(ethylene glycol)-supported α,α,α-trifluoroacetophenone in dioxirane mediated alkene epoxidation reactions

Sulfur- and selenium-based linkers in polymer-supported organic synthesis