Lanthanide-tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications.

Tetrapyrrole derivatives such as porphyrins, phthalocyanines, naphthalocyanines, and porpholactones, are highly stable macrocyclic compounds that play important roles in many phenomena linked to the development of life. Their complexes with lanthanides are known for more than 60 years and present breath-taking properties such as a range of easily accessible redox states leading to photo- and electro-chromism, paramagnetism, large non-linear optical parameters, and remarkable light emission in the visible and near-infrared (NIR) ranges. They are at the centre of many applications with an increasing focus on their ability to generate singlet oxygen for photodynamic therapy coupled with bioimaging and biosensing properties.

Heavy weather events, water quality and gastroenteritis in Norway.

Climate change will lead to more extreme weather events in Europe. In Norway, little is known about how this will affect drinking water quality and population's health due to waterborne diseases. The aim of our work was to generate new knowledge on the effect of extreme weather conditions and climate change on drinking water and waterborne disease.

Facile Preparation of Phthalocyanine-Based Nanodots for Photoacoustic Imaging and Photothermal Cancer Therapy In Vivo.

The development of near-infrared (NIR)-absorbing nanoagents for personalized multifunctional phototheranostics has attracted considerable attention in the past decade. Recently, the organic nanomaterials with good biosafety are considered as promising phototheranostic agents, while their facile synthesis remains challenging. Inspired by the preparation of carbon nanodots, we fabricate the NIR-absorbing phthalocyanine-based nanodots (ZnPc-NDs) using a facile method for multifunctional phototheranostics.

Campylobacter infections expected to increase due to climate change in Northern Europe.

Global climate change is predicted to alter precipitation and temperature patterns across the world, affecting a range of infectious diseases and particularly foodborne infections such as Campylobacter. In this study, we used national surveillance data to analyse the relationship between climate and campylobacteriosis in Denmark, Finland, Norway and Sweden and estimate the impact of climate changes on future disease patterns. We show that Campylobacter incidences are linked to increases in temperature and especially precipitation in the week before illness, suggesting a non-food transmission route.

Impressive near-infrared brightness and singlet oxygen generation from strategic lanthanide-porphyrin double-decker complexes in aqueous solution.

Although lanthanide double-decker complexes with hetero-macrocyclic ligands as functional luminescent and magnetic materials have promising properties, their inferior water solubility has negated their biomedical applications. Herein, four water-soluble homoleptic lanthanide (  , , and ) sandwiches with diethylene-glycol-disubstituted porphyrins () are reported, with their structures proven by both quantum chemical calculations and scanning tunneling microscopy. Our findings demonstrate that the near-infrared emission intensity and singlet oxygen (O) quantum yields of and in aqueous media are higher than those of the reported capped lanthanide monoporphyrinato analogues, and ; the brightness and luminescence lifetime in water of are greater than those of .

Facile synthesis of N-rich carbon quantum dots from porphyrins as efficient probes for bioimaging and biosensing in living cells.

N-rich metal-free and metal-doped carbon quantum dots (CQDs) have been prepared through one-step hydrothermal method using tetraphenylporphyrin or its transition metal (Pd or Pt) complex as precursor. The structures and morphology of the as-prepared nanoparticles were analyzed by X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectra. Three kinds of nanocomposites show similar structures except for the presence of metal ions in Pd-CQDs and Pt-CQDs indicated by X-ray photoelectron spectroscopy.

Study of Arylamine-Substituted Porphyrins as Hole-Transporting Materials in High-Performance Perovskite Solar Cells.

To develop new hole-transporting materials (HTMs) for efficient and stable perovskite solar cells (PSCs), 5,10,15,20-tetrakis{4-[N,N-di(4-methoxylphenyl)amino-phenyl]}-porphyrin was prepared in gram scale through the direct condensation of pyrrole and 4-[bis(4-methoxyphenyl)amino]benzaldehyde. Its Zn(II) and Cu(II) complexes exhibit excellent thermal and electrochemical stability, specifically a high hole mobility and very favorable energetics for hole extraction that render them a new class of HTMs in organometallic halide PSCs. As expected, ZnP as HTM in PSCs affords a competitive power conversion efficiency (PCE) of 17.

αβ-Isoform specific erbium complexes highly specific for bladder cancer imaging and photodynamic therapy.

We have synthesized a bifunctional erbium-porphyrin tumor imaging and PDT agent (Er-R3) that is capable of killing bladder cancer cells via its selective binding to the integrin αβ isoform overexpressed on the cell membrane.

Near-infrared emissive lanthanide hybridized carbon quantum dots for bioimaging applications.

Lanthanide hybridized carbon quantum dots (Ln-CQDs) were synthesized by a facile one-pot hydrothermal method using citric acid as a carbon precursor and Yb or Nd as a doping ion. The morphology and chemical structures of Ln-CQDs were investigated by TEM, XRD, XPS, and FTIR spectroscopy. The obtained Ln-CQDs are spherical and well dispersed in water, and their aqueous solutions emit strong blue emission under UV excitation.

New Terthiophene-Conjugated Porphyrin Donors for Highly Efficient Organic Solar Cells.

To mimic the natural photosynthetic systems utilizing chlorophylls to absorb light and store light energy, two new porphyrin-based small molecules of PTTR and PTTCNR have been developed for photovoltaic applications. The highest power conversion efficiency of 8.21% is achieved, corresponding to a short-circuit current of 14.

Structural engineering of porphyrin-based small molecules as donors for efficient organic solar cells.

Porphyrin-based small molecules as donors have long been ignored in bulky heterojunction organic solar cells due to their unfavorable aggregation and the low charge mobility. With the aim of striking a delicate balance between molecular design, morphology, interfacial layer and device fabrication to maximize the power conversion efficiency (PCE) of organic solar cells, three comparable porphyrin-based small molecules with an acceptor-donor-acceptor configuration have been developed for use as donor materials in solution processed small molecule bulk heterojunction organic solar cells. In these molecules, electron-deficient 3-ethylrhodanine is introduced into the electron-rich porphyrin core through 5,15-bis(phenylethynyl) linkers.

Gallium and Functionalized-Porphyrins Combine to Form Potential Lysosome-Specific Multimodal Bioprobes.

A water-soluble bimetallic normal ("cold") and radiochemical ("hot") gallium-porphyrin-ruthenium-bipyridine complex (GaporRu-1) has been synthesized by microwave methodology in short reaction times with good (>85%) yields. (68)GaporRu-1 is demonstrated to be a potential multimodal and functional bioprobe for positron emission tomography (PET), lysosome specific optical imaging, and photodynamic therapy.

Room temperature molecular up conversion in solution.

Up conversion is an Anti-Stokes luminescent process by which photons of low energy are piled up to generate light at a higher energy. Here we show that the addition of fluoride anions to a D2O solution of a macrocyclic erbium complex leads to the formation of a supramolecular [(ErL)2F](+) assembly in which fluoride is sandwiched between two complexes, held together by the synergistic interactions of the Er-F-Er bridging bond, four intercomplex hydrogen bonds and two aromatic stacking interactions. Room temperature excitation into the Er absorption bands at 980 nm of a solution of the complex in D2O results in the observation of up converted emission at 525, 550 and 650 nm attributed to Er centred transitions via a two-step excitation.

pH-Dependent Cancer-Directed Photodynamic Therapy by a Water-Soluble Graphitic-Phase Carbon Nitride-Porphyrin Nanoprobe.

Theranostic photodynamic nanomaterials suffer from poor water solubility and nontargeted toxicity. A water-soluble graphitic-phase carbon nitride-based material (g-C N ) conjugated to a positively charged porphyrin P2 (conjugating concentration: 60 μm mg  mL ) is shown to be a new concept of photodynamic therapeutic agent (g-C N -P2). The pH-sensitive emission of g-C N is the driving force for the generation of O from g-C N -P2.

Pure white-light and colour-tuning of Eu(3+)-Gd(3+)-containing metallopolymer.

Direct white-light (CIE coordinate of x = 0.333, y = 0.335, CCT of 5455 K and CRI of 82) with a high luminous efficiency (18.

An Amphiphilic BODIPY-Porphyrin Conjugate: Intense Two-Photon Absorption and Rapid Cellular Uptake for Two-Photon-Induced Imaging and Photodynamic Therapy.

The new amphiphilic BODPY-porphyrin conjugate BZnPP and its precursor BZnPH were synthesised, and their linear and two-photon photophysical properties, together with their cellular uptake and photo-cytotoxicity, were studied. This amphiphilic conjugate consists of a hydrophobic BODIPY moiety and a hydrophilic tetra(ethylene glycol) chain bridging a cationic triphenylphosphonium group to an amphiphilic porphyrin ZnP through acetylide linkers at its meso positions. A large two-photon absorption cross-section (σ=1725 GM) and a high singlet oxygen quantum yield (0.

Photocytotoxicity, cellular uptake and subcellular localization of amidinophenylporphyrins as potential photodynamic therapeutic agents: An in vitro cell study.

The cell-based studies of 5, 10, 15, 20-Tetrakis (4-amidinophenyl) porphyrin (Por1), its Zn complex (Por2) and amidinophenyl bisporphyrin (Por3) were carried out to examine their photocytotoxicity, cellular uptake and sub-cellular localization with human nasopharyngeal carcinoma cell (HK-1), using 5, 10, 15, 20-Tetrakis (N-methyl-4-pyridyl) porphyrin (H2TMPyP) as a reference. These porphyrins showed low dark-cytotoxicity and high photo-cytotoxicity against HK-1. The amphiphilic amidinophenyl bisporphyrin (Por3) displayed better cellular uptake than the single hydrophilic Por1, Por2 and H2TMPyP.

A novel bifunctional mitochondria-targeted anticancer agent with high selectivity for cancer cells.

Mitochondria have recently emerged as novel targets for cancer therapy due to its important roles in fundamental cellular function. Discovery of new chemotherapeutic agents that allow for simultaneous treatment and visualization of cancer is urgent. Herein, we demonstrate a novel bifunctional mitochondria-targeted anticancer agent (FPB), exhibiting both imaging capability and anticancer activity.

SILAC-based quantitative proteomics identified lysosome as a fast response target to PDT agent Gd-N induced oxidative stress in human ovarian cancer IGROV1 cells.

Biological systems have developed an intact network and strategies in response to various environmental pressures such as irradiation, viral invasion and oxidative stress. Therefore, elucidation of the cellular response mechanism toward oxidative stress can contribute to the knowledge of redox regulation. By using a newly developed gadolinium based photodynamic therapy (PDT) agent Gd-N and SILAC quantified proteomic analysis, we observed 485 proteins dysregulated in expression, 106 in phosphorylation and 1050 in oxidation.

Solution-processed new porphyrin-based small molecules as electron donors for highly efficient organic photovoltaics.

A series of unsymmetrical π-conjugated small molecules have been constructed from meso-alkyl substituted porphyrins as the central unit and 3-ethylrhodanine as the terminal group. Using PC71BM as an acceptor, and these small molecules as electron donors in solution-processed bulk-heterojunction solar cells, a high power conversion efficiency of 6.49% has been achieved.

A-D-A Type Small Molecules Based on Boron Dipyrromethene for Solution-Processed Organic Solar Cells.

The unique properties of boron dipyrromethene (BODIPY) dyes including facile synthesis, high absorption coefficients, and delocalized molecular orbitals as well as excellent photochemical and thermal stability, make them promising as materials for organic solar cells. Accordingly, in this study three A-D-A structural small molecules of BDTT-BODIPY, FL-BODIPY, and TT-BODIPY have been synthesized, in which two BODIPY acceptor units are symmetrically conjugated to 4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)benzo[1,2-b:4,5-b]dithiophene (BDTT), 9,9-dioctyl-9H-fluorene (FL), and thieno[3,2-b]thiophene (TT) donor cores, respectively. The manipulation of the structural parameters significantly improves the performances of the BHJ OSCs, which show power conversion efficiencies of 4.

Directional Plk1 inhibition-driven cell cycle interruption using amphiphilic thin-coated peptide-lanthanide upconversion nanomaterials as in vivo tumor suppressors.

Polo-like kinase 1 (Plk1) is a major serine/threonine protein kinase which regulates key mitotic events such as centrosome duplication, spindle assembly and chromosome separation. Overexpression and aberrant activities of Plk1 can be detected in different types of cancer. Given that the unique polo box domain (PBD) pocket provides an excellent drug target for Plk1 binding and inhibition, we have rationally designed multifunctional lanthanide-doped upconversion nanomaterials.

The first example of Tb₃-containing metallopolymer-type hybrid materials with efficient and high color-purity green luminescence.

In the series of homo-leptic trinuclear complexes {[Ln3(L)4Cl4(MeOH)(H2O)]·Cl} (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3 or Ln = Gd, 4) self-assembled from the allyl-modified benzimidazole-type ligand HL (4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol) and LnCl3·6H2O, a suitable energy level match endows efficient green luminescence (Φ(overall) = 72%) of Tb3-arrayed complex 3. The copolymerization between each of these complex monomers 1-4 and C=C-containing MMA (methyl methacrylate) or NBE (norbornene) shows that degradative chain transfer of the terminal four flexible allyl groups within restrains their radical polymerization with MMA while it does not hinder their effective ring-opening metathesis polymerization (ROMP) with NBE. Thus, two kinds of PMMA-supported doping hybrid materials 1@PMMA, 2@PMMA, 3@PMMA and 4@PMMA and PNBE-supported metallopolymer-type hybrid materials Poly(NBE-1), Poly(NBE-2), Poly(NBE-3) and Poly(NBE-4) are obtained, respectively.

Synthesis, characterization and oscillator-vibrated near-infrared (NIR) luminescence of two pseudo-polymorphic [Yb4((OH)2-Salophen)4] complexes.

Through the self-assembly of the (OH)2-Salophen H4L (H4L=N,N'-bis(3-hydroxylsalicylidene)benzene-1,2-diamine) with LnCl3·6H2O or Ln(NO3)3·6H2O (Ln=La, Yb or Gd) in different solvent systems MeCN-EtOH and MeCN-DMF, the mixed (L)(4-) and (H2L)(2-) coordination modes induce the formation of anion-independent while pseudo-polymorphic homoleptic linear tetranuclear complexes [Ln4(H2L)2(L)2(EtOH)2] (Ln=La, 1; Ln=Yb, 2 or Ln=Gd, 3) and [Ln4(H2L)2(L)2(DMF)2] (Ln=La, 4; Ln=Yb, 5 or Ln=Gd, 6), respectively. The result of their photophysical properties shows the characteristic NIR luminescence for both Yb(3+)-based complexes 2 and 5 with emissive lifetimes in microsecond ranges, while the difference of nearby and/or distant oscillator-based (OH and/or CH) vibrations from two coordinated EtOH or DMF molecules within the inner coordination spheres of Yb(3+) ions in the two complexes has a decisive effect on their NIR luminescent properties.

In vivo selective cancer-tracking gadolinium eradicator as new-generation photodynamic therapy agent.

In this work, we demonstrate a modality of photodynamic therapy (PDT) through the design of our truly dual-functional--PDT and imaging--gadolinium complex (Gd-N), which can target cancer cells specifically. In the light of our design, the PDT drug can specifically localize on the anionic cell membrane of cancer cells in which its laser-excited photoemission signal can be monitored without triggering the phototoxic generation of reactive oxygen species--singlet oxygen--before due excitation. Comprehensive in vitro and in vivo studies had been conducted for the substantiation of the effectiveness of Gd-N as such a tumor-selective PDT photosensitizer.