Search

Graphyne, a theorized carbon allotrope possessing only sp- and sp 2 -hybridized carbon atoms, holds great potentials in many fields, especially in catalysis and energy-transfer/storage devices. Using a bottom-up strategy, we synthesized a new N-doped graphyne analogue, triazine- and 1,4-diethynylbenzene-based graphyne TA-BGY, in solution in gram-scale. The unique sp/sp 2 carbon-conjugated TA-BGY possesses an extended porous network structure with a BET surface area of approximately 300 m 2  g -1 . Owing to its low optical band gap (1.44 eV), TA-BGY was expected to have many applications, which were exemplified by the photodegradation of methyl orange and photocatalytic bacterial inactivation., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C 4 D allowed the quantification of the carboxylic acids formed. For the described experiments, aqueous solutions of 1-propanol were placed inside a photoreactor and oxidized upon the addition of TiO 2 and/or H 2 O 2 . According to the described results, the addition of H 2 O 2 (0.1% w/w) was the most significant variable, roughly tripled the amount of carboxylic acids generated and led to the conversion of up to 70% of the initially available 1-propanol (1 mmol/L). More importantly, the reaction yielded the formation (within 10 min) of propionate (50 µmol/L), acetate (400 µmol/L), formate (50 µmol/L), and malonate (200 µmol/L). The latter is critically important because it represents the first example of the photochemical oxidation of both terminal carbons of the C 3 -chain of 1-propanol under mild conditions, and opens new avenues for the production of this important chemical building block., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photochemistry is considered to be a promising strategy for hydrogels to mimic the complex and dynamic properties of natural extracellular matrix. However, it is seldom applied in 3D tissue engineering and regenerative medicine due to the attenuation of light. In this study, phenyl azide photchemistry and optical fiber technology are first used to localize adhesive protein on the inner surface of the nerve guidance conduit in a 3D hydrogel scaffold. In vitro coculture assay of neural stem cells (NSCs) shows that photoimmobilization of collagen significantly improves the adhesion and survival of NSCs in the conduit, and exhibits synergistic effect with the sustainable release of growth factor. After implantation in transected spinal cord, the optimized hydrogel scaffold is found to improve the locomotion recovery of rats 12 weeks after spinal cord injury (SCI). Histological analysis suggests that the designed hydrogel scaffold provides a favorable biological niche for neuronal regeneration, thus producing directional neuron tissue and promoting the repair of SCI. This study demonstrates a promising hydrogel scaffold for SCI repair and provides the first understanding of the photoimmobilization of adhesive protein in a 3D hydrogel conduit concerning its functions on spinal cord tissue restoration., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose-designed 2-phenylquinoline (PQ)-sugar hybrids 1 and 2 were synthesized and evaluated for their photodegradation activities against an α-glucosidase target. The results indicated that PQ-mannose hybrid 2 selectively and effectively photodegraded α-glucosidase and significantly inhibited its enzymatic activity upon irradiation with long-wavelength UV light in the absence of any additives under neutral and aqueous conditions. Furthermore, 2 selectively and effectively inhibited α-glucosidase activity only with photo-irradiation even in complex cell lysate., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photocleavable polymers have attracted much attention in drug delivery, photopatterning, and controlling cell behavior. Photolysis is usually induced by UV light. However, UV light cannot penetrate deeply into biological tissue and may damage biological components. Therefore, conventional UV-light-cleavable polymers are problematic for deep-tissue biomedical applications. In this feature article, red and near-infrared light-cleavable polymers are reviewed, and their potential applications are highlighted. The remaining challenges in the field of photocleavable polymers are discussed., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A surface disordered layer is a plausible approach to improve the photoelectrochemical performance of TiO 2 . However, the formation of a crystalline disordered layer in BiVO 4 and its effectiveness towards photoelectrochemical water splitting has remained a big challenge. Here, we report a rapid solution process (within 5 s) that is able to form a disordered layer of a few nanometers thick on the surface of BiVO 4 nanoparticles using a specific solution with a controllable reducing power. The disordered layer on BiVO 4 alleviates charge recombination at the electrode-electrolyte interface and reduces the onset potential greatly, which in turn results in a photocurrent density of approximately 2.3 mA cm -2 at 1.23 V versus the reversible hydrogen electrode (RHE). This value is 2.1 times higher than that of bare BiVO 4 . The enhanced photoactivity is attributed to the increased charge separation and transfer efficiencies, which resolve the intrinsic drawbacks of bare BiVO 4 such as the short hole diffusion length of around 100 nm and poor surface oxygen evolution reactivity., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A family of five neutral cyclometalated iridium(III) tetrazolato complexes and their methylated cationic analogues have been synthesised and characterised. The complexes are distinguished by variations of the substituents or degree of π conjugation on either the phenylpyridine or tetrazolato ligands. The photophysical properties of these species have been evaluated in organic and aqueous media, revealing predominantly a solvatochromic emission originating from mixed metal-to-ligand and ligand-to-ligand charge transfer excited states of triplet multiplicity. These emissions are characterised by typically long excited-state lifetimes (∼hundreds of ns), and quantum yields around 5-10 % in aqueous media. Methylation of the complexes caused a systematic red-shift of the emission profiles. The behaviour and the effects of the different complexes were then examined in cells. The neutral species localised mostly in the endoplasmic reticulum and lipid droplets, whereas the majority of the cationic complexes localised in the mitochondria. The amount of complexes found within cells does not depend on lipophilicity, which potentially suggests diverse uptake mechanisms. Methylated analogues were found to be more cytotoxic compared to the neutral species, a behaviour that might to be linked to a combination of uptake and intracellular localisation., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Vinyl ketone polymers, including phenyl vinyl ketone (PVK), are an important class of polymers due to their ability to degrade upon irradiation with ultraviolet light which makes them useful for a variety of applications. However, traditional radical methods for synthesizing PVK polymers give rise to poor control or are unable to produce block copolymers. This work uses reversible addition-fragmentation chain transfer polymerization (RAFT) and photochemistry to polymerize PVK. When visible blue radiation of 440 ± 10 nm is used as the light source for the photopolymerization, rapid polymerization and well-defined polymers are created. This RAFT method uses PVK as both monomer and radical initiator, exciting the PVK mono-mer by 440 ± 10 nm irradiation to avoid the use of an additional radical initiator. Once the poly-mer is synthesized, it is stable against degradation by blue light (440 ± 10 nm), but upon exposure to ultraviolet (UV) radiation (310 ± 20 nm) significant decrease in molecular weight is observed. The degradation is observed for all poly(PVK) materials synthesized., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The design, synthesis, and in vitro biological studies of a biotin-carbazole-dicyanovinyl-chlorambucil conjugate (Bio-CBZ-DCV-CBL; 6) are reported. This conjugate (6) is a multifunctional single-molecule appliance composed of a thiol-sensor DCV functionality, a CBZ-derived phototrigger as well as fluorescent reporter, and CBL as the anticancer drug, and Bio as the cancer-targeting ligand. In conjugate 6, the DCV bond undergoes a thiol-ene click reaction at pH<7 with intracellular thiols, thereby shutting down internal charge transfer between the donor CBZ and acceptor DCV units, resulting in a change of the fluorescence color from green to blue, and thereby, sensing the tumor microenvironment. Subsequent photoirradiation results in release of the anticancer drug CBL in a controlled manner., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Absolute rate coefficients for the reaction between the important environmental free radical oxidant NO 3 . and a series of N- and C-protected amino acids, di- and tripeptides were determined using 355 nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the respective substrates in acetonitrile at 298±1 K. Through combination with computational studies it was revealed that the reaction with acyclic aliphatic amino acids proceeds through hydrogen abstraction from the α-carbon, which is associated with a rate coefficient of about 1.8×10 6  m -1  s -1 per abstractable hydrogen atom. The considerably faster reaction with phenylalanine [k=(1.1±0.1)×10 7  m -1  s -1 ] is indicative for a mechanism involving electron transfer. An unprecedented amplification of the rate coefficient by a factor of 7-20 was found with di- and tripeptides that contain more than one phenylalanine residue. This suggests a synergistic effect between two aromatic rings in close vicinity, which makes such peptide sequences highly vulnerable to oxidative damage by this major environmental pollutant., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The ability to remotely trigger CRISPR/Cas9 activity would enable new strategies to study cellular events with greater precision and complexity. In this work, we have developed a method to photocage the activity of the guide RNA called "CRISPR-plus" (CRISPR-precise light-mediated unveiling of sgRNAs). The photoactivation capability of our CRISPR-plus method is compatible with the simultaneous targeting of multiple DNA sequences and supports numerous modifications that can enable guide RNA labeling for use in imaging and mechanistic investigations., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The use of light-sensitive polymers for the release of therapeutics is an important approach allowing the timing and amount of the release to be controlled precisely. The use of light has been pioneered to control insulin release from a dermal photoactivated depot, or PAD. One of the main impediments to the use of light-sensitive polymers in this context is the density of the materials: The large majority of the material is the carrier polymer, with the minority being the therapeutic. In this work, the feasibility of using insulin itself as a monomer in the polymerization process is demonstrated. Insulin modified with either one or two light cleavable azide groups is polymerized with a tridentate alkyne-bridging monomer using a click reaction. The resulting material called a "macropolymer" is ≈85% insulin, is insoluble in aqueous solvent, and releases native, soluble insulin upon irradiation., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Uniform multishelled NiO, Co3 O4 , ZnO, and Au@NiO hollow spheres were synthesized (NiO and Co3 O4 hollow spheres for the first time) by a simple shell-by-shell self-assembly allowing for tuning of the the size, thickness and shell numbers by controlling the heat treatment, glucose/metal salt molar ratio, and hydrothermal reaction time. These findings further the development of synthetic methodologies for multishelled hollow structures and could open up new opportunities for deeper understanding of the mechanisms of shell-by-shell self-assembly. Moreover, the double-shelled NiO hollow sphere exhibits a higher photocatalytic activity for degradation of methyl orange than its morphological counterparts., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The binding of vitamin B12 derivatives to human B12 transporter proteins is strongly influenced by the type and site of modification of the cobalamin original structure. We have prepared the first cobalamin derivative modified at the phosphate moiety. The reaction conditions were fully optimized and its limitations examined. The resulting derivatives, particularly those bearing terminal alkyne and azide groups, were isolated and used in copper-catalyzed alkyne-azide cycloaddition reactions (CuAAC). Their sensitivity towards light revealed their potential as photocleavable molecules. The binding abilities of selected derivatives were examined and compared with cyanocobalamin. The interaction of the alkylated derivatives with haptocorrin was less affected than the interaction with intrinsic factor. Furthermore, the configuration of the phosphate moiety was irrelevant to the binding process., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The antibiotic puromycin, which inhibits protein translation, is used in a broad range of biochemical applications. The synthesis, characterization, and biological applications of NVOC-puromycin, a photocaged derivative that is activated by UV illumination, are presented. The caged compound had no effect either on prokaryotic or eukaryotic translation or on the viability of HEK 293 cells. Furthermore, no significant release of ribosome-bound polypeptide chains was detected in vitro. Upon illumination, cytotoxic activity, in vitro translation inhibition, and polypeptide release triggered by the uncaging of NVOC-puromycin were equivalent to those of the commercial compound. The quantum yield of photolysis was determined to be 1.1±0.2% and the NVOC-puromycin was applied to the detection of newly translated proteins with remarkable spatiotemporal resolution by using two-photon laser excitation, puromycin immunohistochemistry, and imaging in rat hippocampal neurons., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photodegradable hydrogels have emerged as powerful platforms for studying and directing cellular behavior in a spatiotemporally controlled manner. Photodegradable hydrogels have previously been formed by free radical polymerizations, Michael-type addition reactions, and orthogonal click reactions. Here, an ester-activated photocleavable crosslinker is presented for preparing photodegradable hydrogels by means of a one-step mixing reaction between the crosslinker and a biocompatible polymer containing amino moieties (amino-terminated tetra-arm poly(ethylene glycol) or gelatin). It is demonstrated that photodegradable hydrogels micropatterned by photolithography can be used to culture cells with high viability and proliferation rates. The resulting micropatterned cell-laden structures can potentially be used to create 3D biomaterials for various tissue-engineering applications., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bis(cyclopentadienyl)titanium dichloride (Cp2TiCl2) is a high performance additive under UV light activation for both i) radical photopolymerization reactions (when added to a Type I photo-initiator such as 2,2-dimethoxy-2-phenylacetophenone, the oxygen inhibition is reduced) and ii) a concomitant in situ photoinduced and oxygen mediated formation of Ti-based nanoparticles (diameters ranging from 45 to 220 nm). The photochemical properties of Cp2TiCl2 are investigated by steady state photolysis and electron spin resonance, and its photoinitiation ability checked. The nanoparticles (NPs) are well characterized by transmission electron microscopy. The high reactivity of Cp2TiCl2 under air is ascribed to a bimolecular homolytic substitution (the SH2 process is clearly demonstrated by density functional theory calculations and ESR experiments), which converts the peroxyls into new efficient initiating radicals. The photochemical in situ incorporation of Ti NPs has never previously been reported. The synthesis of metal nanoparticles by a SH2 approach instead of the reduction of a metal salt appears to be a promising original method., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)