All-Solution-Processed Multilayered White Polymer Light-Emitting Diodes (WPLEDs) Based on Cross-Linked [Ir(4-vb-PBI)2(acac)].

All-solution-processed multilayered white polymer light-emitting diodes (WPLEDs) are promising candidates for low-cost and large-area flexible full-color flat-panel displays and solid-state lighting. However, it is still challenging to improve their performance. In this work, based on an elegant strategy of orthogonal materials, the utilization of the cross-linked Ir3+ polymer film poly(NVK-co-[Ir(4-vb-PBI)2(acac)]-co-NVK) (NVK = N-vinyl-carbazole; 4-vb-HPBI = 1-(4-vinylbenzyl)-2-phenyl-1H-benzo[d]imidazole; and Hacac = acetylacetone) as the emitting layer (EML) between a hydrophilic polymer film poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the hole injection layer (HIL) and a hydrophobic polymer film poly(vinyl-PBD) (vinyl-PBD = 2-(4-(tert-butyl)phenyl)-5-(4'-vinyl-[1,1'-biphenyl]-4-yl)-2,5-dihydro-1,3,4-oxadiazole) as the electron transport layer (ETL) led to the successful fabrication of reliable all-solution-processed multilayered WPLEDs. The device exhibits a ηCEMax of 18.19 cd/A, a ηPEMax of 8.16 lm/W, and a ηEQEMax of 9.32% with stable white light (Commission International De L'Eclairage (CIE) coordinates x = 0.269-0.283, y = 0.317-0.330; corrected color temperatures (CCTs) of 7237-8199 K, and CRIs (color rendering indices) of 63-72) under a wide applied-voltage range. Its high performance, especially with record efficiencies among those of reported all-solution-processed WPLEDs, renders cross-linked Ir3+ polymers a new platform to all-solution-processed multilayered WPLEDs.

Efficient white polymer light-emitting diodes (WPLEDs) based on covalent-grafting of [Zn2(MP)3(OAc)] into PVK.

Thanks to the straightforward white light of single grafting-type polymers based on earth-abundant Zn(ii)-complexes, producing cost-effective flexible WOLEDs/WPLEDs with good device performance remains a formidable challenge. Herein, by using the polymer Poly(NVK-co-[Zn2(MP)3(OAc)]) with excellent physical properties for single-layer WPLEDs, record-high efficiencies (η Max c = 13.0 cd A-1, η Max p = 6.1 lm W-1 and η Max EQE = 9.2%) and low (ca. 25%) efficiency roll-off compared to previous organo-Zn2+-based WOLEDs/WPLEDs are realized. This finding renders single Zn(ii)-complex-grafted polymers a new route to low-cost and large-area flexible WPLEDs for potential full-colour flat displays.

BODIPY-functionalized 1,10-phenanthroline as a long wavelength sensitizer for near-infrared emission of the ytterbium(iii) ion.

Two BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) moieties were chemically appended to the 4,7-positions of 1,10-phenanhtroline resulting in two new ligands (BODIPY-Phen and 4I-BODIPY-Phen) with strong absorption at 507 nm and 540 nm, respectively. BODIPY-Phen emits fluorescence strongly centered at 507 nm, whereas the fluorescence of 4I-BODIPY-Phen was completely quenched due to the introduction of four I atoms at its 2,6 positions. The two ligands reacted readily with tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) ytterbium(iii) dihydrate through substitution reactions forming eight-coordinate complexes that emit strongly at 976 nm upon excitation at their absorption maximal positions. Both complexes exhibited a lifetime of ∼11 µs in dichloromethane at room temperature.

A BODIPY-functionalized PdII photoredox catalyst for Sonogashira C-C cross-coupling reactions.

We report for the first time a BODIPY-functionalized dichloro(1,10-phenanthroline)palladium(ii) complex as an efficient photoredox catalyst for the Sonogashira C-C cross-coupling between phenylacetylene derivatives and iodobenzene derivatives with yields up to 92% under visible light illumination at room temperature.

Methods and novel technology for microRNA quantification in colorectal cancer screening.

The screening and diagnosis of colorectal cancer (CRC) currently relies heavily on invasive endoscopic techniques as well as imaging and antigen detection tools. More accessible and reliable biomarkers are necessary for early detection in order to expedite treatment and improve patient outcomes. Recent studies have indicated that levels of specific microRNA (miRNA) are altered in CRC; however, measuring miRNA in biological samples has proven difficult, given the complicated and lengthy PCR-based procedures used by most laboratories. In this manuscript, we examine the potential of miRNA as CRC biomarkers, summarize the methods that have commonly been employed to quantify miRNA, and focus on novel strategies that can improve or replace existing technology for feasible implementation in a clinical setting. These include isothermal amplification techniques that can potentially eliminate the need for specialized thermocycling equipment. Additionally, we propose the use of near-infrared (NIR) probes which can minimize autofluorescence and photobleaching and streamline quantification without tedious sample processing. We suggest that novel miRNA quantification tools will be necessary to encourage new discoveries and facilitate their translation to clinical practice.

BODIPYs for Dye-Sensitized Solar Cells.

BODIPY, abbreviation of boron-dipyrromethene, is one class of robust organic molecules that has been used widely in bioimaging, sensing, and logic gate design. Recently, BODIPY dyes have been explored for dye-sensitized solar cells (DSCs). Studies demonstrate their potential as light absorbers for the conversion of solar energy to electricity. However, their photovoltaic performance is inferior to many other dyes, including porphyrin dyes. In this review, several synthetic strategies of BODIPY dyes for DSCs and their further functionalization are described. The photophysical properties of dye molecules and their photovoltaic performances in DSCs are summarized. We aim to provide readers a clear picture of the field and expect to shed light on the next generation of BODIPY dyes for their applications in solar energy conversion.

Correction: Sisters together: co-sensitization of near-infrared emission of ytterbium(iii) by BODIPY and porphyrin dyes.

Correction for 'Sisters together: co-sensitization of near-infrared emission of ytterbium(iii) by BODIPY and porphyrin dyes' by Hongshan He et al., Chem. Commun., 2017, 53, 10120-10123.

Sisters together: co-sensitization of near-infrared emission of ytterbium(iii) by BODIPY and porphyrin dyes.

A ytterbium(iii) acetate complex with a BODIPY and a porphyrin as co-sensitizers emits strongly at 978 nm over a broader excitation window between 450-560 nm.

p-Type mesoscopic NiO as an active interfacial layer for carbon counter electrode based perovskite solar cells.

Replacement of the ZrO2 insulator layer in the state-of-the-art TiO2/ZrO2/carbon structure by mesoscopic p-type NiO particles led to 39% increase of energy conversion efficiency of hole-conductor-free organometallic perovskite heterojunction solar cells with carbon counter electrodes. In these cells, the light absorber, CH3NH3PbI3, formed instantly inside the pores of the entire TiO2/NiO/carbon layer upon sequential deposition of PbI2 and CH3NH3I. Photoluminescence, impedance spectroscopy and transient photovoltage decay measurements have revealed that introduction of NiO extended the electron lifetime and augmented the hole extraction of the counter electrode. As a result, the photocurrent and open-circuit voltage both increased, resulting in a cell with impressive energy conversion efficiency of 11.4% under AM1.5G conditions.

Fine tuning of fluorene-based dye structures for high-efficiency p-type dye-sensitized solar cells.

We report on an experimental study of three organic push-pull dyes (coded as zzx-op1, zzx-op1-2, and zzx-op1-3) featuring one, two, and three fluorene units as spacers between donors and acceptors for p-type dye-sensitized solar cells (p-DSSC). The results show increasing the number of spacer units leads to obvious increases of the absorption intensity between 300 nm and 420 nm, a subtle increase in hole driving force, and almost the same hole injection rate from dyes to NiO nanoparticles. Under optimized conditions, the zzx-op1-2 dye with two fluorene spacer units outperforms other two dyes in p-DSSC. It exhibits an unprecedented photocurrent density of 7.57 mA cm(-2) under full sun illumination (simulated AM 1.5G light illumination, 100 mW cm(-2)) when the I(-)/I3(-) redox couple and commercial NiO nanoparticles were used as an electrolyte and a semiconductor, respectively. The cells exhibited excellent long-term stability. Theoretical calculations, impedance spectroscopy, and transient photovoltage decay measurements reveal that the zzx-op1-2 exhibits lower photocurrent losses, longer hole lifetime, and higher photogenerated hole density than zzx-op1 and zzx-op1-3. A dye packing model was proposed to reveal the impact of dye aggregation on the overall photovoltaic performance. Our results suggest that the structural engineering of organic dyes is important to enhance the photovoltaic performance of p-DSSC.

Porphyrin dyes on TiO2 surfaces with different orientations: a photophysical, photovoltaic, and theoretical investigation.

Porphyrin dyes with a triphenylamino group as an electron donor, para- or meta-benzoic acids as electron acceptors, and hydrogen (H) or mesityl (M) substituents on the meso position as auxiliary groups were synthesized. Their photophysical properties and photovoltaic performance in dye-sensitized solar cells were investigated. All four porphyrins exhibited similar photophysical properties in the solution and dye-loading densities on the surface of TiO2 nanoparticles; however, the p-benzoic acid functionalized porphyrins, p-H(M)PZn, gave better photovoltaic performance than m-benzoic acid functionalized porphyrins, m-H(M)PZn. Theoretical calculations indicated that the electron density on the frontier molecular orbital was more delocalized to p-benzoic acid than to m-benzoic acid. Absorption spectra indicated the stronger H-aggregation in m-H(M)PZn than that in p-H(M)PZn on the surface of TiO2 nanoparticles. The mesityl groups in the meso positions reduced the dye-loading density due to steric hindrance between dyes. As a result, the p-MPZn exhibited the best energy conversion efficiency among the four porphyrins studied. This efficiency was further enhanced when a complementary dye BET was used.

Modulated charge injection in p-type dye-sensitized solar cells using fluorene-based light absorbers.

In this study, new pull-push arylamine-fluorene based organic dyes zzx-op1, zzx-op2, and zzx-op3 have been designed and synthesized for p-type dye-sensitized solar cells (p-DSCs). In zzx-op1, a di(p-carboxyphenyl)amine (DCPA) was used as an electron donor, a perylenemonoimide (PMID) as an electron acceptor, and a fluorene (FLU) unit with two aliphatic hexyl chains as a π-conjugated linker. In zzx-op2 and zzx-op3, a 3,4-ethylenedioxythiophene (EDOT) and a thiophene were inserted consecutively between PMID and FLU to tune the energy levels of the frontier molecular orbitals of the dyes. The structural modification broadened the spectral coverage from an onset of 700 nm for zzx-op1 to 750 nm for zzx-op3. The electron-rich EDOT and thiophene lifted up the HOMO (highest occupied molecular orbital) levels of zzx-op2 and zzx-op3, making their potential more negative than zzx-op1. When three dyes were employed in p-type DSCs with I(-)/I3(-) as a redox couple and NiO nanoparticles as hole materials, zzx-op1 exhibited impressive energy conversion efficiency of 0.184% with the open-circuit voltage (VOC) of 112 mV and the short-circuit current density (JSC) of 4.36 mA cm(-2) under AM 1.5G condition. Density functional theory calculations, transient photovoltage decay measurements, and electrochemical impedance spectroscopic studies revealed that zzx-op1 sensitized solar cell exhibited much higher charge injection efficiency (90.3%) than zzx-op2 (53.9%) and zzx-op3 (39.0%), indicating a trade-off between spectral broadening and electron injection driving force in p-type DSCs.

A simple acrylic acid functionalized zinc porphyrin for cost-effective dye-sensitized solar cells.

A simple zinc porphyrin with an acrylic acid at the meso position exhibits an energy conversion efficiency of 5.1%, demonstrating its potential for cost-effective dye-sensitized solar cells.

8-Hydroxylquinoline as a strong alternative anchoring group for porphyrin-sensitized solar cells.

8-Hydroxylquinoline (OQ) is demonstrated for the first time as a strong alternative anchoring group porphyrin dyes to improve the long-term stability of solar cells.

Iodized BODIPY as a long wavelength light sensitizer for the near-infrared emission of ytterbium(III) ion.

Novel 8-HOQ-BODIPY-3I was developed as an efficient sensitizer for the near-infrared emission of ytterbium(III) ion at 980 nm under long wavelength excitation.

BODIPY chromophores as efficient green light sensitizers for lanthanide-induced near-infrared emission.

A new boron dipyrromethene (BODIPY) modified 8-hydroxylquinoline ligand (8-HOQ-BODIPY) is synthesized for the sensitization of near-infrared emission of lanthanide(III) ions. The BODIPY unit, as revealed by single-crystal X-ray diffraction analysis, aligns almost perpendicularly to the 8-HOQ unit. The ligand exhibits strong absorption at ~506 nm and fluorescence at 510 nm in organic solvents with quantum yields ranging from ~0.45 in dichloromethane to 0.015 in ethanol. It forms stable ytterbium(III), erbium(III) and neodymium(III) complexes with 3:1 ligand-to-metal molar ratios. Upon excitation (~522 nm), the neodymium(III) and erbium(III) complexes emit weakly at 1060 and 1382 nm, respectively, whereas the ytterbium(III) complex exhibits strong emission at 976 and 1003 nm. The results demonstrate the potential of BODIPY dyes as efficient and robust visible light sensitizers for lanthanide-based NIR emitters in medical diagnosis.

TiO2 nanotube membranes on transparent conducting glass for high efficiency dye-sensitized solar cells.

Crack-free TiO(2) nanotube (NT) membranes were obtained by short time re-anodization of a sintered TiO(2) NT array on Ti foil, followed by dilute HF etching at room temperature. The resulting freestanding TiO(2) membranes were opaque with a slight yellow color having one end open and another end closed. The membranes were then fixed on transparent fluorine-tin-oxide glass using a thin layer of screen-printed TiO(2) nanoparticles (NPs) as a binding medium. It was found that low temperature treatment of the resulting NT/NP film under appropriate pressure before sintering at 450 °C was critical for successful fixation of the NT membrane on the NP layer. The resulting films with open-ends of NT membranes facing the NP layer (open-ends down, OED, configuration) exhibited better interfacial contact between NTs and NPs than those with closed-ends facing the NP layer (closed-ends down, CED, configuration). The cells with an OED configuration exhibit higher external quantum efficiency, greater charge transfer resistance from FTO/TiO(2) to electrolyte, and better dye loading compared to CED configurations. The solar cells with the OED configuration gave 6.1% energy conversion efficiency under AM1.5G condition when the commercial N719 was used as a dye and I(-)/I(3)(-) as a redox couple, showing the promise of this method for high efficiency solar cells.

Hexa-µ(2)-chlorido-µ(4)-oxido-tetra-kis-[(3-methyl-5-phenyl-1H-pyrazole-κN)copper(II)].

The title compound, [Cu(4)Cl(6)O(C(10)H(10)N(2))(4)], contains four Cu(II) atoms which are bridged by six chloride anions. The central O atom is located on a crystallographic fourfold roto-inversion axis. Each Cu(II) atom is coordinated by an N atom of a neutral monodentate 3-methyl-5-phenyl-pyrazole ligand, three Cl(-) anions, and one O(2-) anion. The geometry at each Cu(II) atom is distorted trigonal-bipyramidal, with the three Cl(-) ions in the equatorial plane and the N and O atoms in the axial positions.

4-tert-Butyl-pyridinium triiodide-4-tert-butyl-pyridine (1/1).

The title compound, C(9)H(14)N(+)·I(3) (-)·C(9)H(13)N, consists of monoprotonated 4-tert-butyl-pyridinium cations and triiodide anions. The triiodide ion has near-symmetric linear geometry, with bond lengths of 2.9105 (4) Š(I-I) and a bond angle of 177.55 (3)° (I-I-I). For this room-temperature structure, the butyl group on the pyridine ring is disordered and has been treated as a rigid rotator, modeled in three separate positions with 1/3, 1/3, 1/3 occupancies. The cations assemble into dimeric forms by way of N-H⋯N hydrogen bonds.

Hybridization of near-infrared emitting erbium(III) and ytterbium(III) monoporphyrinate complexes with silica xerogel: synthesis, structure and photophysics.

The new erbium(III) and ytterbium(III) monoporphyrinate complexes were synthesized and hybridized into silica xerogel frameworks though the coordination of 5-(N,N-bis(3-propyl)ureyl-1,10-phenanthroline to the lanthanide ions. The complexes are eight-coordinate with strong emissions in solution in the near-infrared region. The resulting silica films are transparent, homogenous, and exhibit strong mechanical strength. The scanning electron microscope and atomic force microscope study reveals that the surface of the film is porous with the silica in particulate or rod shapes. Upon visible light excitation, the fluorescence of the porphyrin at approximately 649 nm with lifetimes of approximately 3.4 and 3.8 ns for erbium(III) and ytterbium-hybridized films were observed, respectively. The erbium- and ytterbium-hybridized films gave characteristic emissions at 1538 nm with a lifetime of 0.6 micros and at 980 nm with a lifetime of 6.6 micros, respectively. They exhibited a 50 to 70% decrease in lifetime compared to their parent complexes in toluene.