scholarly journals Deep NIR-I Emissive Iridium(III) Complex Bearing D-A Ligand: Synthesis, Photophysical Properties and DFT/TDDFT Calculation

Crystals ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1038
Author(s):  
Jia-Yang Jiang ◽  
Zi-Han Xu ◽  
Tang Li ◽  
Da-Hua Cai ◽  
Hui Zhou ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Density Function ◽  
Near Infrared ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Nir Dyes ◽  
Donor Acceptor ◽  
Nir Emission ◽  
Biological Performance

Near-infrared (NIR) phosphorescent iridium(III) complexes have been demonstrated to possess photophysical properties superior to those of traditional NIR dyes. However, the NIR emission wavelength is restricted in the range of 700–800 nm. For realizing deeper NIR emission, a novel type of iridium(III) complex was designed and synthesized in this work. The main ligand of the iridium(III) complex was constructed using a donor-acceptor structure containing benzothiophene as the donor and quinoxaline as the acceptor. The β-diketone derivative was chosen as the auxiliary ligand owing to its symmetrical structure and p-donating character. The complex exhibits deep NIR-I phosphorescence (764 nm in CH2Cl2, 811 nm in aqueous solution) and broad full width at half maximum (108 nm in CH2Cl2, 154 nm in aqueous solution). Theoretical calculations based on the density function and time-dependent density function were carried out to support the experimental data. Moreover, in vitro biological performance of the complex was determined as well. This work supports the possibility that via a systematic transformation between the D and A units, the photophysical performance of NIR emissive iridium(III) complexes can be greatly improved.

scholarly journals On the Aqueous Solution Behavior of C-Substituted 3,1,2-Ruthenadicarbadodecaboranes

Inorganics ◽  
2019 ◽  
Vol 7 (7) ◽  
pp. 91 ◽  
Author(s):  
Marta Gozzi ◽  
Benedikt Schwarze ◽  
Peter Coburger ◽  
Evamarie Hey-Hawkins
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Self Assembly ◽  
Self Assembling ◽  
Vis Spectroscopy ◽  
Assembly Behavior ◽  
Biological Performance ◽  
Type 3

3,1,2-Ruthenadicarbadodecaborane complexes bearing the [C2B9H11]2− (dicarbollide) ligand are robust scaffolds, with exceptional thermal and chemical stability. Our previous work has shown that these complexes possess promising anti-tumor activities in vitro, and tend to form aggregates (or self-assemblies) in aqueous solutions. Here, we report on the synthesis and characterization of four ruthenium(II) complexes of the type [3-(η6-arene)-1,2-R2-3,1,2-RuC2B9H9], bearing either non-polar (R = Me (2–4)) or polar (R = CO2Me (7)) substituents at the cluster carbon atoms. The behavior in aqueous solution of complexes 2, 7 and the parent unsubstituted [3-(η6-p-cymene)-3,1,2-RuC2B9H11] (8) was investigated via UV-Vis spectroscopy, mass spectrometry and nanoparticle tracking analysis (NTA). All complexes showed spontaneous formation of self-assemblies (108–109 particles mL−1), at low micromolar concentration, with high polydispersity. For perspective applications in medicine, there is thus a strong need for further characterization of the spontaneous self-assembly behavior in aqueous solutions for the class of neutral metallacarboranes, with the ultimate scope of finding the optimal conditions for exploiting this self-assembling behavior for improved biological performance.

Upconverting nanoparticle to quantum dot FRET for homogeneous double-nano biosensors

RSC Advances ◽  
2015 ◽  
Vol 5 (18) ◽  
pp. 13270-13277 ◽  
Author(s):  
Leena Mattsson ◽  
K. David Wegner ◽  
Niko Hildebrandt ◽  
Tero Soukka
Keyword(s):  
Quantum Dots ◽  
Quantum Dot ◽  
Near Infrared ◽  
Photophysical Properties ◽  
Semiconductor Quantum Dots ◽  
Optical Biosensing ◽  
Donor Acceptor

The unique photophysical properties of upconverting nanoparticles (UCNPs) and semiconductor quantum dots (QDs) render them an attractive donor–acceptor combination for near-infrared (NIR) excited FRET-based optical biosensing.

Molecular Engineering for Boosting AIE-active Free Radical Photogenerator and Its High-performance in Hypoxia via Photodynamic Therapy

2020 ◽  
Author(s):  
Qing Wan ◽  
Rongyuan Zhang ◽  
Zeyan Zhuang ◽  
Yuxuan Li ◽  
Zhiming Wang ◽  
...  
Keyword(s):  
Free Radical ◽  
High Performance ◽  
Near Infrared ◽  
Theoretical Calculations ◽  
Tumor Hypoxia ◽  
Molecular Engineering ◽  
Type I ◽  
Noninvasive Treatment ◽  
Nir Fluorescence

<div> <p>Serious hypoxia in solid tumor as well as vicious aggregation-caused fluorescence quenching (ACQ) of conventional photosensitizers (PSs) limit the progress of the fluorescence imaging-guided photodynamic (PDT) although it has obvious advantages in precise spatial-temporal control and noninvasive treatment. The photosensitizers featuring Type I reactive oxygen species (ROS) based on free radical and novel aggregation-induced emission (AIE) characteristic (AIE-PSs) could offer precious opportunity to resolve above problems, but there was rare feasible molecular engineering in previous reports. Herein, we proposed that the strategy of fabricating stronger intermolecular charge transfer (ICT) effect in electron-rich anion-π<sup>+ </sup>AIE-active luminogens (AIEgens) aimed to help suppressing nonradiative internal conversion (IC) as well as promote radiative and intersystem crossing (ISC) processes for boosting more free radical generation. Systematic and detailed experimental and theoretical calculations proved our ideas when the electron-donating abilities enhanced in collaborative donors, and the AIE-PSs exhibited higher performance in near-infrared red (NIR) fluorescence image-guided cancer PDT <i>in vitro/vivo</i>. This work would become an important reference to the design of AIE-active free radical generators for overcoming ACQ effect and tumor hypoxia in future PDT.</p> </div>

Fluorescein-Inspired Near-Infrared Chemodosimeter for Luminescence Bioimaging

2019 ◽  
Vol 26 (21) ◽  
pp. 4029-4041 ◽  
Author(s):  
Hai-Yan Wang ◽  
Huisheng Zhang ◽  
Siping Chen ◽  
Yi Liu
Keyword(s):  
Near Infrared ◽  
Living System ◽  
Tissue Penetration ◽  
Deep Tissue ◽  
Biological Targets ◽  
Nir Dyes ◽  
Photo Damage ◽  
Temporal And Spatial

Luminescence bioimaging is widely used for noninvasive monitoring of biological targets in real-time with high temporal and spatial resolution. For efficient bioimaging in vivo, it is essential to develop smart organic dye platforms. Fluorescein (FL), a traditional dye, has been widely used in the biological and clinical studies. However, visible excitation and emission limited their further application for in vivo bioimaging. Nearinfrared (NIR) dyes display advantages of bioimaging because of their minimum absorption and photo-damage to biological samples, as well as deep tissue penetration and low auto-luminescence from background in the living system. Thus, some great developments of near-infrared fluorescein-inspired dyes have emerged for bioapplication in vitro and in vivo. In this review, we highlight the advances in the development of the near-infrared chemodosimeters for detection and bioimaging based on the modification of fluoresceininspired dyes naphtho-fluorescein (NPF) and cyanine-fluorescein (Cy-FL).

Upconversion Luminescence Imaging of Tumors with EGFR-Affibody Conjugated Nanophosphors

MRS Advances ◽  
2019 ◽  
Vol 4 (46-47) ◽  
pp. 2461-2470 ◽  
Author(s):  
Majid Badieirostami ◽  
Colin Carpenter ◽  
Guillem Pratx ◽  
Lei Xing ◽  
Conroy Sun
Keyword(s):  
Near Infrared ◽  
Imaging System ◽  
Imaging Modality ◽  
Photophysical Properties ◽  
Upconversion Luminescence ◽  
Detection Sensitivity ◽  
Photon Absorption ◽  
Great Promise

ABSTRACTNear infrared (NIR) optical imaging has demonstrated significant potential as an effective modality for cancer molecular imaging. Among various NIR probes currently under investigation, upconversion nanophosphors (UCNPs) possess great promise due to their anti-Stokes emission and sequential photon absorption which result in superior detection sensitivity and a simple imaging setup, respectively. Here we investigated the utility of this imaging modality to detect tumor cells expressing the epidermal growth factor receptor (EGFR) using affibody functionalized nanophosphors and a custom built imaging system. Initially, aqueous dispersible NaYF4: Tm+3, Yb+3 UCNPs were synthesized and their photophysical properties were characterized. Then, their luminescence response as a function of concentration and their depth resolving capability in a tissue-simulating phantom were examined. Finally, we demonstrated the use of bioconjugated UCNPs for imaging EGFR-expressing tumors both in vitro and in vivo. Our data suggests that NIR imaging with UCNPs may be useful for noninvasive imaging of tumors.

scholarly journals Sustained Release of Protein Therapeutics from Subcutaneous Thermosensitive Biocompatible and Biodegradable Pentablock Copolymers (PTSgels)

2016 ◽  
Vol 2016 ◽  
pp. 1-15 ◽  
Author(s):  
Elizabeth Schaefer ◽  
Santhi Abbaraju ◽  
Mary Walsh ◽  
Donna Newman ◽  
Jacklyn Salmon ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Drug Release ◽  
Sustained Release ◽  
Near Infrared ◽  
Structural Integrity ◽  
Polymer Composition ◽  
Sds Page ◽  
Pentablock Copolymers

Objective. To evaluate thermosensitive, biodegradable pentablock copolymers (PTSgel) for sustained release and integrity of a therapeutic protein when injected subcutaneously. Materials and Methods. Five PTSgels with PEG-PCL-PLA-PCL-PEG block arrangements were synthesized. In vitro release of IgG from PTSgels and concentrations was evaluated at 37°C. Released IgG integrity was characterized by SDS-PAGE. In vitro disintegration for 10GH PTSgel in PBS was monitored at 37°C over 72 days using gravimetric loss and GPC analysis. Near-infrared IgG in PTSgel was injected subcutaneously and examined by in vivo imaging and histopathology for up to 42 days. Results. IgG release was modulated from approximately 7 days to more than 63 days in both in vitro and in vivo testing by varying polymer composition, concentration of PTSgel aqueous solution, and concentration of IgG. Released IgG in vitro maintained structural integrity by SDS-PAGE. Subcutaneous PTSgels were highly biocompatible and in vitro IgG release occurred in parallel with the disappearance of subcutaneous gel in vivo. Conclusions. Modulation of release of biologics to fit the therapeutic need can be achieved by varying the biocompatible and biodegradable PTSgel composition. Release of IgG parallels disappearance of the polymeric gel; hence, little or no PTSgel remains after drug release is complete.

Molecular Engineering for Boosting AIE-active Free Radical Photogenerator and Its High-performance in Hypoxia via Photodynamic Therapy

2020 ◽  
Author(s):  
Qing Wan ◽  
Rongyuan Zhang ◽  
Zeyan Zhuang ◽  
Yuxuan Li ◽  
Zhiming Wang ◽  
...  
Keyword(s):  
Free Radical ◽  
High Performance ◽  
Near Infrared ◽  
Theoretical Calculations ◽  
Tumor Hypoxia ◽  
Molecular Engineering ◽  
Type I ◽  
Noninvasive Treatment ◽  
Nir Fluorescence

<div> <p>Serious hypoxia in solid tumor as well as vicious aggregation-caused fluorescence quenching (ACQ) of conventional photosensitizers (PSs) limit the progress of the fluorescence imaging-guided photodynamic (PDT) although it has obvious advantages in precise spatial-temporal control and noninvasive treatment. The photosensitizers featuring Type I reactive oxygen species (ROS) based on free radical and novel aggregation-induced emission (AIE) characteristic (AIE-PSs) could offer precious opportunity to resolve above problems, but there was rare feasible molecular engineering in previous reports. Herein, we proposed that the strategy of fabricating stronger intermolecular charge transfer (ICT) effect in electron-rich anion-π<sup>+ </sup>AIE-active luminogens (AIEgens) aimed to help suppressing nonradiative internal conversion (IC) as well as promote radiative and intersystem crossing (ISC) processes for boosting more free radical generation. Systematic and detailed experimental and theoretical calculations proved our ideas when the electron-donating abilities enhanced in collaborative donors, and the AIE-PSs exhibited higher performance in near-infrared red (NIR) fluorescence image-guided cancer PDT <i>in vitro/vivo</i>. This work would become an important reference to the design of AIE-active free radical generators for overcoming ACQ effect and tumor hypoxia in future PDT.</p> </div>

scholarly journals A near-infrared fluorescent probe with an improved Stokes shift achieved by tuning the donor–acceptor–donor character of the rhodamine skeleton and its applications

RSC Advances ◽  
2020 ◽  
Vol 10 (49) ◽  
pp. 29536-29542 ◽  
Author(s):  
Jin Gong ◽  
Chang Liu ◽  
Xiaojie Jiao ◽  
Song He ◽  
Liancheng Zhao ◽  
...  
Keyword(s):  
Fluorescent Probe ◽  
Near Infrared ◽  
Stokes Shift ◽  
Large Stokes Shift ◽  
Donor Acceptor ◽  
Nir Emission ◽  
Donor Character

A novel mitochondrion-targeting Hg2+ probe, RQS, with NIR emission (680 nm) and a large Stokes shift (96 nm) was developed by tuning the D–A–D character of the rhodamine skeleton.

scholarly journals Photophysical Properties of Donor-Acceptor Stenhouse Adducts and Their Inclusion Complexes with Cyclodextrins and Cucurbit[7]uril

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 4928
Author(s):  
Liam Payne ◽  
Jason D. Josephson ◽  
R. Scott Murphy ◽  
Brian D. Wagner
Keyword(s):  
Aqueous Solution ◽  
Fluorescence Spectroscopy ◽  
Inclusion Complex ◽  
Charge Separation ◽  
Photophysical Properties ◽  
Protic Solvents ◽  
Mechanistic Insight ◽  
Donor Acceptor ◽  
Strong Inclusion ◽  
Supramolecular Complexation

Donor-acceptor Stenhouse adducts (DASAs) are a novel class of solvatochromic photoswitches with increasing importance in photochemistry. Known for their reversibility between open triene and closed cyclized states, these push-pull molecules are applicable in a suite of light-controlled applications. Recent works have sought to understand the DASA photoswitching mechanism and reactive state, as DASAs are vulnerable to irreversible “dark switching” in polar protic solvents. Despite the utility of fluorescence spectroscopy for providing information regarding the electronic structure of organic compounds and gaining mechanistic insight, there have been few studies of DASA fluorescence. Herein, we characterize various photophysical properties of two common DASAs based on Meldrum’s acid and dimethylbarbituric acid by fluorescence spectroscopy. This approach is applied in tandem with complexation by cyclodextrins and cucurbiturils to reveal the zwitterionic charge separation of these photoswitches in aqueous solution and the protective nature of supramolecular complexation against degradative dark switching. DASA-M, for example, was found to form a weak host-guest inclusion complex with (2-hydroxypropyl)-γ-cyclodextrin, with a binding constant K = 60 M−1, but a very strong inclusion complex with cucurbit[7]uril, with K = 27,000 M−1. This complexation within the host cavity was found to increase the half-life of both DASAs in aqueous solution, indicating the significant and potentially useful stabilization of these DASAs by host encapsulation.

scholarly journals NIR Photosensitizer for Two-Photon Fluorescent Imaging and Photodynamic Therapy of Tumor

2021 ◽  
Vol 9 ◽  
Author(s):  
Lujia Chen ◽  
Meijuan Chen ◽  
Yuping Zhou ◽  
Changsheng Ye ◽  
Ruiyuan Liu
Keyword(s):  
Photodynamic Therapy ◽  
Near Infrared ◽  
Fluorescent Imaging ◽  
Deep Tissue ◽  
Two Photon ◽  
Nir Emission ◽  
Good Biocompatibility ◽  
Fluorescent Agent

Preparation of near-infrared (NIR) emissive fluorophore for imaging-guided PDT (photodynamic therapy) has attracted enormous attention. Hence, NIR photosensitizers of two-photon (TP) fluorescent imaging and photodynamic therapy are highly desirable. In this contribution, a novel D-π-A structured NIR photosensitizer (TTRE) is synthesized. TTRE demonstrates near-infrared (NIR) emission, good biocompatibility, and superior photostability, which can act as TP fluorescent agent for clear visualization of cells and vascular in tissue with deep-tissue penetration. The PDT efficacy of TTRE as photosensitizer is exploited in vitro and in vivo. All these results confirm that TTRE would serve as potential platform for TP fluorescence imaging and imaging-guided photodynamic therapy.

Sign in / Sign up

Export Citation Format

Share Document