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1.
Nanoscale ; 12(14): 7921-7926, 2020 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-32232243

RESUMO

Luminescent probes based on silicon nanocrystals (SiNCs) have many advantages for bioimaging compared to more conventional quantum dots: abundancy of silicon combined with its biocompatibility; tunability of the emission color of SiNCs in the red and NIR spectral region to gain deeper tissue penetration; long emission lifetimes of SiNCs (hundreds of µs) enabling time-gated acquisitions to avoid background noise caused by tissue autofluorescence and scattered excitation light. Here we report a new three-step synthesis, based on a low temperature thiol-ene click reaction that can afford SiNCs, colloidally stable in water, with preserved bright red and NIR photoluminescence (band maxima at 735 and 945 nm for nanocrystals with diameters of 4 and 5 nm, respectively) and long emission lifetimes. Their luminescence is insensitive to dioxygen and sensitive to pH changes in the physiological range, enabling pH sensing. In vivo studies demonstrated tumor accumulation, 48 hours clearance and a 3-fold improvement of the signal-to-noise ratio compared to steady-state imaging.

2.
Faraday Discuss ; 2020 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-32101208

RESUMO

When functionalised with amines, silicon nanocrystals (SiNCs) are known to have surface-state emission with loss of colour tunability, low quantum yield and short nanosecond lifetimes. These changes in optical properties are produced by direct amine bonding on the silicon surface. In this article, secondary amine functionalised SiNCs with bright, red (λmax = 750 nm) and long-lived emission (τ ca. 50 µs) are reported for the first time via a three-step synthetic approach. These SiNCs are colloidally stable in several polar solvents and can be further functionalised by reaction with carboxylic acid groups. We proved the feasibility of further functionalization with pyrene butyric acid: ca. 40 pyrene units per nanoparticle were attached via amide bond formation. The resulting hybrid system works as a light-harvesting antenna: excitation of pyrene units at 345 nm results in sensitised emission at 700 nm by the silicon core.

3.
Chem Commun (Camb) ; 55(79): 11860-11863, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31528890

RESUMO

An easy to synthesize azobenzene based amphiphile spontaneously self-assembles into monodisperse nanoaggregates in water. The large difference in the critical aggregation concentration between the E and Z stereoisomeric forms enables photocontrol of its aggregation state over a wide concentration range: light-triggered release and uptake of lipophilic molecules is achieved in aqueous solution.


Assuntos
Compostos Azo/química , Nanocápsulas/química , Corantes Fluorescentes/química , Interações Hidrofóbicas e Hidrofílicas , Luz , Tamanho da Partícula , Processos Fotoquímicos , Polietilenoglicóis/química , Estereoisomerismo , Água/química
4.
Chem Commun (Camb) ; 55(48): 6838-6841, 2019 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-31093623

RESUMO

Here we report the application of dual nickel/photoredox catalysis to the allylation of aliphatic, aromatic and heteroaromatic aldehydes by using commercially available reagents. The process utilizes the combination of a Ni(ii) complex, [Ru(bpy)3]2+ as a photoredox catalyst, and allylacetate under blue LED irradiation, and allows the synthesis of a large variety of homoallylic alcohols.

5.
Photochem Photobiol Sci ; 18(9): 2180-2190, 2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-30816403

RESUMO

The one-photon (1P) and two-photon (2P) absorption properties of three quadrupolar dyes, featuring thiophene as a donor and acceptors of varying strengths, are determined by a combination of experimental and computational methods employing the density functional theory (DFT). The emission shifts in different solvents are well reproduced by time-dependent DFT calculations with the linear response and state specific approaches in the framework of the polarizable continuum model. The calculations show that the energies of both 1P- and 2P-active states decrease with an increase of the strength of the acceptor. The 2P absorption cross-sections predicted by the response theory are accounted for by considering just one intermediate state (S1) in the sum-over-states formulation. For the chromophore featuring the stronger acceptor, the energetic positions of the 1P- and 2P-active states prevent the exploitation of the theoretically predicted very high 2P activity due to the competing 1P absorption into the S1 state.

6.
Med Dosim ; 44(4): 379-384, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30871864

RESUMO

Parotid gland (PG) shrinkage and neck volume reduction during radiotherapy of head and neck (H&N) cancer patients is a clinical issue that has prompted interest in adaptive radiotherapy (ART). This study focuses on the difference between planned dose and delivered dose and the possible effects of an efficient replanning strategy during the course of treatment. Six patients with H&N cancer treated by tomotherapy were retrospectively enrolled. Thirty daily dose distributions (DMVCT) were calculated on pretreatment megavoltage computed tomography (MVCT) scans. Deformable Image Registration which matched daily MVCT with treatment planning kilovoltage computed tomography was performed. Using the resulting deformation vector field, all daily DMVCT were deformed to the planning kilovoltage computed tomography and resulting doses were accumulated voxel per voxel. Cumulative DMVCT was compared to planned dose distribution performing γ-analysis (2 mm, 2% of 2.2 Gy). Two single-intervention ART strategies were executed on the 18th fraction whose previous data had suggested to be a suitable timepoint for a single replanning intervention: (1) replanning on the original target and deformed organ at risks (OARs) (a "safer" approach regarding tumor coverage) and (2) replanning on both deformed target and deformed OARs. DMVCT showed differences between planned and delivered doses (3D-γ 2mm/2%-passing rate = 85 ± 1%, p < 0.001). Voxel by voxel dose accumulation showed an increase in average dose of warped PG of 3.0 Gy ± 3.3 Gy. With ART the average dose of warped PG decreased by 3.2 Gy ± 1.7 Gy in comparison to delivered dose without replanning when both target and OARs were deformed. Average dose of warped PG decreased by 2.0 Gy ± 1.4 Gy when only OARs were deformed. Anatomical variations lead to increased doses to PGs. Efficient single-intervention ART-strategies with replanning on the 18th MVCT result a reduced PG dose. A strategy with deformation of both target and OAR resulted in the lowest PG dose, while formally maintaining PTV coverage. Deformation of only OAR nevertheless reduces PG dose and has less uncertainties regarding PTV coverage.

7.
Dalton Trans ; 48(12): 3815-3818, 2019 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-30785170

RESUMO

Hexakis(phenylthio)benzene compounds carrying six carboxylic acid groups at their periphery combine aggregation-induced phosphorescence, water-solubility and metal-binding properties: the para-isomer is a selective and sensitive turn-on phosphorescent sensor of Pb2+ ions in water.

8.
Chem Commun (Camb) ; 54(72): 10044-10047, 2018 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-30039815

RESUMO

Here we report the application of readily prepared and available coumarin dyes for photoredox catalysis, which are able to mimic powerful reductant [Ir(iii)] complexes. Coumarin derivatives 9 and 10 were employed as photoreductants in pinacol coupling and in other reactions, in the presence of Et3N as a sacrificial reducing agent. As the electronic, photophysical, and steric properties of coumarins could be varied, a wide applicability to several classes of photoredox reactions is predicted.

9.
Dalton Trans ; 47(26): 8507-8508, 2018 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-29915844
10.
Angew Chem Int Ed Engl ; 57(19): 5454-5458, 2018 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-29543370

RESUMO

The herein reported visible-light-activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63-99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis-cyclometalated chiral-at-metal rhodium complex (2-8 mol %) which after coordination to the cyclopropane generates the visible-light-absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single-electron-transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono-acceptor-substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives.

11.
Phys Chem Chem Phys ; 20(12): 8071-8076, 2018 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-29516066

RESUMO

A mechanism based on the sequential absorption of two photons by the components of a redox couple has been recently proposed for catalysis of the energetically demanding reduction of aryl halides. Here, we analyze the suggested photochemical mechanism of this reaction, which employs perylenediimide (PDI) as a photocatalyst, on the basis of spectroscopic, electrochemical and electron paramagnetic resonance data. Our results indicate that the photoexcited PDI radical anion (*PDI˙-) cannot play the role of a photosensitizer in the aforementioned process. Instead, the reduction of 4'-bromoacetophenone likely involves *PDI˙- decomposition products. The extremely short lifetime of the photoexcited transient species, as *PDI˙-, is a major general limitation for photocatalytic schemes based on sequential two-photon excitation. In order to better understand the potential of such schemes, we discuss them in the context of the Z-scheme in natural photosynthesis.

12.
Chem ; 2(4): 550-560, 2017 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-28966989

RESUMO

Silicon nanocrystals of the average diameter of 5 nm, functionalized with 4,7-di(2-thienyl)-2,1,3-benzothiadiazole chromophores (TBT) and dodecyl chains, exhibit near-infrared emission upon one-photon (1P) excitation at 515 nm and two-photon (2P) excitation at 960 nm. By using TBT chromophores as an antenna we were able to enhance both 1P and 2P absorption cross-sections of the silicon nanocrystals to more efficiently excite their long-lived luminescence. These results chart a path to two-photon-excitable imaging probes with long-lived oxygen-independent luminescence - a rare combination of properties that should allow for a substantial increase in imaging contrast.

13.
Angew Chem Int Ed Engl ; 56(42): 12820-12821, 2017 10 09.
Artigo em Inglês | MEDLINE | ID: mdl-28857385

RESUMO

The photocatalytic mechanism reported in a recent Communication to produce the radical anion of pyrenes postulates a highly endergonic electron transfer process. An analysis of the thermodynamics is reported together with the proposal of an alternative thermodynamically feasible mechanism.

14.
Phys Chem Chem Phys ; 19(39): 26507-26526, 2017 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-28956876

RESUMO

Silicon nanocrystals (SiNCs) synthesized by plasma-induced or high temperature processes (e.g., thermal disproportionation of hydrogen silsesquioxane at T > 1100 °C) display bright (photoluminescence quantum yield up to 70%) and long-lived luminescence (hundreds of µs), which can be tuned from green to red and near-infra-red spectral regions according to nanocrystal dimensions. The present review focuses on the parameters affecting the optical properties of these SiNCs, namely size, shape, surface, degree of crystallinity, and on a method to increase their brightness by functionalising SiNCs with dyes to build up a light-harvesting antenna. The final discussion presents some of the most recent examples of applications, which take advantage of the luminescence properties of SiNCs: energy conversion devices, sensors, and bioimaging probes.

15.
Chemistry ; 23(26): 6380-6390, 2017 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-28263437

RESUMO

A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond-like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments.

16.
Chem Commun (Camb) ; 53(13): 2081-2093, 2017 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-28111647

RESUMO

Phosphorescent materials are mostly based on metal complexes. Metal-free organic molecules usually display phosphorescence only in a rigid matrix at 77 K. In the last few years, there has been increasing interest in the design of organic molecules displaying long-lived and highly intense room-temperature phosphorescence, an extremely difficult task since these two properties are generally conflicting. This review reports the most recent and tutorial examples of molecules that are weakly or non-phosphorescent in deaerated fluid solution and whose room temperature phosphorescence is switched on upon aggregation. The examples are divided into two classes according to the mechanism responsible for switching on phosphorescence: (i) rigidification by crystallization or by encapsulation in a polymeric matrix and (ii) interaction with other molecules of the same type (self-aggregation) or a different type by taking advantage of heavy-atom effects.

17.
Chemistry ; 23(10): 2363-2378, 2017 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-27897357

RESUMO

The synthesis of O-doped polyaromatic hydro- carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high-yield ring-closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C-O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron-donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third-order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices.

18.
Top Curr Chem (Cham) ; 374(4): 53, 2016 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-27573405

RESUMO

Silicon (Si) nanocrystals are relatively strong light emitters, but are weak light absorbers as a result of their indirect band gap. One way to enhance light absorption is to functionalize the nanocrystals with chromophores that are strong light absorbers. By designing systems that enable efficient energy transfer from the chromophore to the Si nanocrystal, the brightness of the nanocrystals can be significantly increased. There have now been a few experimental systems in which covalent attachment of chromophores, efficient energy transfer and significantly increased brightness have been demonstrated. This review discusses progress on these systems and the remaining challenges.

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