Application Efficacy of Cluster Nursing in Patients Undergoing Gastrointestinal Endoscopy.

Background: Gastrointestinal endoscopy is a clinical examination of gastrointestinal diseases with pain, nausea, and other discomfort of the patient. Therefore, it is of practical significance to give corresponding nursing intervention for patients undergoing painless gastrointestinal endoscopy. Objective: To probe the application efficacy of cluster nursing in patients undergoing gastrointestinal endoscopy. Design: This was a retrospective study. Setting: This study was carried out in the Department of Endoscopy Room, Funan County Hospital of Traditional Chinese Medicine. Participants: From March 2020 to October 2022, 126 patients who underwent painless gastrointestinal endoscopy were chosen and randomly separated into a control group and research group. Interventions: The control group received routine safety nursing management. The research group adopted safety management guided by a cluster nursing strategy. Primary Outcome Measures: (1) the dosage of anesthetic drug use and examination time (2) hemodynamics (3) occurrence of common adverse events (4) score of bowel preparation (5) scores of anxiety and depression (6) comfort degree and (7) nursing satisfaction. Results: Compared to the control group, the dosage of anesthetic drug use and examination time in the research group were lessened (P < .001, 95% CI: -10.06--7.94 and P < .001, 95% CI: -7.10--4.88), the diastolic blood pressure, systolic blood pressure, and heart rate indexes in the research group were reduced (P = .03, 95% CI:-10.07--5.32; P < .001, 95% CI:-13.87--7.91 and P < .001, 95% CI:-12.23--6.27), the occurrence of adverse events during the examination in the research group was reduced (χ2=8.068, P = .005), the score of bowel preparation in the research group was elevated (P < .001, 95% CI: 1.06-1.56), the scores of anxiety as well as depression in the research group were reduced (P < .001, 95% CI: 10.77-13.35 and P < .001, 95% CI: 7.31-9.53), the comfort score of patients in the research group presented higher (P < .001, 95% CI: 17.77-22.91), and the nursing satisfaction in the research group was elevated (χ2=10.31, P = .001). Conclusion: Cluster nursing for patients with painless gastrointestinal endoscopy combined examination has a positive impact on ensuring the successful completion of the examination, effectively controlling the risk of adverse events, and improving patient satisfaction.

Mono-/Bimetallic Neutral Iridium(III) Complexes Bearing Diketopyrrolopyrrole-Substituted N-Heterocyclic Carbene Ligands: Synthesis and Photophysics.

The synthesis and photophysics (UV-vis absorption, emission, and transient absorption) of four neutral heteroleptic cyclometalated iridium(III) complexes (Ir-1-Ir-4) incorporating thiophene/selenophene-diketopyrrolopyrrole (DPP)-substituted N-heterocyclic carbene (NHC) ancillary ligands are reported. The effects of thiophene versus selenophene substitution on DPP and bis- versus monoiridium(III) complexation on the photophysics of these complexes were systematically investigated via spectroscopic techniques and density functional theory calculations. All complexes exhibited strong vibronically resolved absorption in the regions of 500-700 nm and fluorescence at 600-770 nm, and both are predominantly originated from the DPP-NHC ligand. Complexation induced a pronounced red shift of this low-energy absorption band and the fluorescence band with respect to their corresponding ligands due to the improved planarity and extended π-conjugation in the DPP-NHC ligand. Replacing the thiophene units by selenophenes and/or biscomplexation led to the red-shifted absorption and fluorescence spectra, accompanied by the reduced fluorescence lifetime and quantum yield and enhanced population of the triplet excited states, as reflected by the stronger triplet excited-state absorption and singlet oxygen generation.

Giant Concentric Metallosupramolecule with Aggregation-Induced Phosphorescent Emission.

Fluorescent metallosupramolecules have received considerable attention due to their precisely controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare and limited to small structures with low-temperature phosphorescence. Herein, we report the self-assembly and photophysical studies of a giant, discrete metallosupramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26 000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions and significant enhancement of emission to CO2 gas.

DNA-Targeting RuII -Polypyridyl Complex with a Long-Lived Intraligand Excited State as a Potential Photodynamic Therapy Agent.

Subtle ligand modifications on RuII -polypyridyl complexes may result in different excited-state characteristics, which provides the opportunity to tune their photo-physicochemical properties and subsequently change their biological functions. Here, a DNA-targeting RuII -polypyridyl complex (named Ru1) with highly photosensitizing 3 IL (intraligand) excited state was designed based on a classical DNA-intercalator [Ru(bpy)2 (dppz)]⋅2 PF6 by incorporation of the dppz (dipyrido[3,2-a:2',3'-c]phenazine) ligand tethered with a pyrenyl group, which has four orders of magnitude higher potency than the model complex [Ru(bpy)2 (dppz)]⋅2 PF6 upon light irradiation. This study provides a facile strategy for the design of organelle-targeting RuII -polypyridyl complexes with dramatically improved photobiological activity.

Synthesis, Structures, and Properties of BN-Dinaphthothiophenes: Influence of B and N Placement on Photophysical Properties and Aromaticity.

Substitution of the C═C functionality with the isosteric and isoelectronic B-N moiety has emerged as a powerful way to expand the family of polycyclic aromatic hydrocarbons. In this paper, two types of BN-dinaphthothiophene (BN-DNT) derivatives with different B and N substitution patterns were synthesized in short steps from commercially available materials. X-ray crystallographic analysis revealed that BN-DNT 1 and 2 had rigid and planar frameworks. Their photophysical properties and the aromaticity of the BN rings of the BN-DNTs were slightly dependent on the B and N substitution patterns. However, their response toward fluoride anions was greatly dependent on the B and N substitution patterns.

Multinuclear 2-(Quinolin-2-yl)quinoxaline-Coordinated Iridium(III) Complexes Tethered by Carbazole Derivatives: Synthesis and Photophysics.

Five mono/di/trinuclear iridium(III) complexes (1-5) bearing the carbazole-derivative-tethered 2-(quinolin-2-yl)quinoxaline (quqo) diimine (N^N) ligand were synthesized and characterized. The photophysical properties of these complexes and their corresponding diimine ligands were systematically studied via UV-vis absorption, emission, and transient absorption (TA) spectroscopy and simulated by time-dependent density functional theory. All complexes possessed strong well-resolved absorption bands at <400 nm that have predominant ligand-based 1π,π* transitions and broad structureless charge-transfer (1CT) absorption bands at 400-700 nm. The energies or intensities of these 1CT bands varied pronouncedly when the number of tethered Ir(quqo)(piq)2+ (piq refers to 1-phenylisoquinoline) units, π conjugation of the carbazole derivative linker, or attachment positions on the carbazole linker were altered. All complexes were emissive at room temperature, with 1-3 showing near-IR (NIR) 3MLCT (metal-to-ligand charge-transfer)/3LLCT (ligand-to-ligand charge-transfer) emission at ∼710 nm and 4 and 5 exhibiting red or NIR 3ILCT (intraligand charge-transfer)/3LMCT (ligand-to-metal charge-transfer) emission in CH2Cl2. In CH3CN, 1-3 displayed an additional emission band at ca. 590 nm (3ILCT/3LMCT/3MLCT/3π,π* in nature) in addition to the 710 nm band. The different natures of the emitting states of 1-3 versus those of 4 and 5 also gave rise to different spectral features in their triplet TA spectra. It appears that the parentage and characteristics of the lowest triplet excited states in these complexes are mainly impacted by the π systems of the bridging carbazole derivatives and essentially no interactions among the Ir(quqo)(piq)2+ units. In addition, all of the diimine ligands tethered by the carbazole derivatives displayed a dramatic solvatochromic effect in their emission due to the predominant intramolecular charge-transfer nature of their emitting states. Aggregation-enhanced emission was also observed from the mixed CH2Cl2/ethyl acetate or CH2Cl2/hexane solutions of these ligands.

Synthesis, Photophysics, and Reverse Saturable Absorption of trans-Bis-cyclometalated Iridium(III) Complexes (C

Extending the bandwidth of triplet excited-state absorption in transition-metal complexes is appealing for developing broadband reverse saturable absorbers. Targeting this goal, five bis-terdentate iridium(III) complexes (Ir1-Ir5) bearing trans-bis-cyclometalating (C^N^C) and 4'-R-2,2':6',2″-terpyridine (4'-R-tpy) ligands were synthesized. The effects of the structural variation in cyclometalating ligands and substituents at the tpy ligand on the photophysics of these complexes have been systematically explored using spectroscopic methods (i.e., UV-vis absorption, emission, and transient absorption spectroscopy) and time-dependent density functional theory (TDDFT) calculations. All complexes exhibited intensely structured 1π,π* absorption bands at <400 nm and broad charge transfer (1CT)/1π,π* transitions at 400-600 nm. Ligand structural variations exerted a very small effect on the energies of the 1CT/1π,π* transitions; however, they had a significant effect on the molar extinction coefficients of these absorption bands. All complexes emitted featureless deep red phosphorescence in solutions at room temperature and gave broad-band and strong triplet excited-state absorption ranging from the visible to the near-infrared (NIR) spectral regions, with both originating from the 3π,π*/3CT states. Although alteration of the ligand structures influenced the emission energies slightly, these changes significantly affected the emission lifetimes and quantum yields, transient absorption spectral features, and the triplet excited-state quantum yields of the complexes. Except for Ir3, the other four complexes all manifested reverse saturable absorption (RSA) upon nanosecond laser pulse excitation at 532 nm, with the decreasing trend of RSA following Ir2 ≈ Ir4 > Ir1 > Ir5 > Ir3. The RSA trend corresponded well with the strength of the excited-state and ground-state absorption differences (ΔOD) at 532 nm for these complexes.

Neutral iridium(iii) complexes bearing BODIPY-substituted N-heterocyclic carbene (NHC) ligands: synthesis, photophysics, in vitro theranostic photodynamic therapy, and antimicrobial activity.

The synthesis, photophysics, and photobiological activities of a series of novel neutral heteroleptic cyclometalated iridium(iii) complexes incorporating boron dipyrromethene (BODIPY) substituted N-heterocyclic carbene (NHC) ligands (Ir1-Ir5) are reported. The effect of the substitution position of BODIPY on the NHC ligands, either on C4 of the phenyl ring (Ir1-Ir3) or C5 of the benzimidazole unit (Ir4 and Ir5), and its linker type (single or triple bond) on the photophysical properties was studied. Ir1-Ir5 exhibited BODIPY-localized intense 1IL (intraligand transition)/1MLCT (metal-to-ligand charge transfer) absorption at 530-543 nm and 1,3IL/1,3CT (charge transfer) emission at 582-610 nm. The nanosecond transient absorption results revealed that the lowest triplet excited states of these complexes were the BODIPY-localized 3π,π* states. Complexes Ir4 and Ir5 exhibited blue-shifted 1IL absorption and 1,3IL/1,3CT emission bands compared to the corresponding absorption and emission bands in complexes Ir1 and Ir3. However, replacing the methyl substituents on N3 of benzimidazole in complexes Ir1 and Ir4 with oligoether substituents in Ir3 and Ir5, respectively, did not impact the energies of the low-energy absorption and emission bands in the corresponding complexes. Water-soluble complexes Ir3 and Ir5 have been explored as photosensitizers for in vitro photodynamic therapy (PDT) effects toward human SKMEL28 melanoma cells. Ir3 showed no dark cytotoxicity (EC50 > 300 µM) but good photocytotoxic activity (9.66 ± 0.28 µM), whereas Ir5 exhibited a higher dark cytotoxicity (20.2 ± 1.26 µM) and excellent photocytotoxicity (0.15 ± 0.01 µM). The phototherapeutic indices with visible light (400-700 nm) activation were >31 for Ir3 and 135 for Ir5. Ir3 and Ir5 displayed 1O2 quantum yields of 38% and 22% in CH3CN, respectively, upon 450 nm excitation. Ir5 was more effective at generating reactive oxygen species (ROS) in vitro. Ir5 was also active against Staphylococcus aureus upon visible light activation, with a phototherapeutic index of >15 and EC50 value of 6.67 µM. These photobiological activities demonstrated that these neutral Ir(iii) complexes are promising in vitro PDT reagents, and substitution at C5 on the benzimidazole group of the NHC ligand was superior to C4 substitution on the phenyl ring.

Effects of Varying the Benzannulation Site and π Conjugation of the Cyclometalating Ligand on the Photophysics and Reverse Saturable Absorption of Monocationic Iridium(III) Complexes.

A series of monocationic iridium(III) complexes, [Ir(C^N)2(pqu)]+PF6- [pqu = 2-(pyridin-2-yl)quinoline, C^N = 2-phenylquinoline (1), 3-phenylisoquinoline (2), 1-phenylisoquinoline (3), benzo[ h]quinoline (4), 2-(pyridin-2-yl)naphthalene (5), 1-(pyridin-2-yl)naphthalene (6), 2-(phenanthren-9-yl)pyridine (7), 2-phenylbenzo[ g]quinoline (8), 2-(naphthalen-2-yl)quinoline (9), and 2-(naphthalen-2-yl)benzo[ g]quinoline (10)], were synthesized in this work. These complexes bear C^N ligands with varied degrees of π conjugation and sites of benzannulation, allowing for elucidation of the effects of the benzannulation site at the C^N ligand on the photophysics of the complexes. Ultraviolet-visible (UV-vis) absorption and emission of the complexes were systematically investigated via spectroscopic techniques and time-dependent density functional theory calculations. Their triplet excited-state absorption and reverse saturable absorption (RSA) were studied by nanosecond transient absorption (TA) spectroscopy and nonlinear transmission techniques. The fusion of phenyl ring(s) to the phenyl ring or the 4 and 5 positions of the pyridyl ring of the C^N ligand resulted in red-shifted UV-vis absorption and emission spectra in complexes 2, 5-7, 9, and 10 compared to those of the parent complex 0, while their triplet lifetimes and emission quantum yields were significantly reduced. In contrast, the fusion of one phenyl ring to the other sites of the pyridyl group of the C^N ligand showed an insignificant impact on the energies of the lowest singlet (S1) and triplet (T1) excited states in complexes 1, 3, and 4 but noticeably affected their TA spectral features. The fusion of the naphthyl group to the 5 and 6 and positions at the pyridyl ring did not influence the S1 energy of complex 8 but altered the nature of the T1 states in 8 and 10 by switching them to the benzo[ g]quinoline-localized 3π,π* state, which resulted in completely different emission and TA spectra in these two complexes. The site-dependent variations of the ground- and excited-state absorption induced strong but varied RSA from these complexes for 4.1-ns laser pulses at 532 nm, with the RSA strength decreasing in the trend of 3 > 7 ≈ 4 ≈ 9 ≈ 6 > 8 ≈ 1 ≈ 2 ≈ 5 > 10.

Impact of Benzannulation Site at the Diimine (N

Ten biscyclometalated monocationic Ir(III) complexes were synthesized and studied to elucidate the effects of extending π-conjugation of the diimine ligand (N^N = 2,2'-bipyridine in Ir1, 2-(pyridin-2-yl)quinoline in Ir2, 2-(pyridin-2-yl)[6,7]benzoquinoline in Ir3, 2-(pyridin-2-yl)-[7,8]benzoquinoline in Ir4, phenanthroline in Ir5, benzo[ f][1,10]phenanthroline in Ir6, naphtho[2,3- f][1,10]phenanthroline in Ir7, 2,2'-bisquinoline in Ir8, 3,3'-biisoquinoline in Ir9, and 1,1'-biisoquinoline in Ir10) via benzannulation at 2,2'-bipyridine on the excited-state properties and reverse saturable absorption (RSA) of these complexes. Either a bathochromic or a hypsochromic shift of the charge-transfer absorption band and emission spectrum was observed depending on the benzannulation site at the 2,2'-bipyridine ligand. Benzannulation at the 3,4-/3',4'-position or 5,6-/5',6'-position of 2,2'-bipyridine ligand or at the 6,7-position of the quinoline ring on the N^N ligand caused red-shifted charge-transfer absorption band and emission band for complexes Ir2, Ir8, Ir10 vs Ir1 and Ir3 vs Ir2, while benzannulation at the 4,5-/4',5'-position of 2,2'-bipyridine ligand or at the 7,8-position of the quinoline ring on the N^N ligand induced a blue shift of the charge-transfer absorption and emission bands for complex Ir9 vs Ir1 and Ir4 vs Ir2. However, benzannulation at the 2,2',3,3'-position of 2,2'-bipyridine or 5,6-position of phenanthroline ligand had no impact on the energy of the charge-transfer absorption band and emission band of complexes Ir5-Ir7 compared with those of Ir1. The observed phenomenon was explained by the frontier molecular orbital (FMO) symmetry analysis. Site-dependent benzannulation also impacted the spectral feature and intensity of the triplet transient absorption spectra and lifetimes drastically. Consequently, the RSA strength of these complexes varied with a trend of Ir7 > Ir5 ≈ Ir6 ≈ Ir1 > Ir3 > Ir2 > Ir10 > Ir4 > Ir8 > Ir9 at 532 nm for 4.1 ns laser pulses.

Neutral Cyclometalated Iridium(III) Complexes Bearing Substituted N-Heterocyclic Carbene (NHC) Ligands for High-Performance Yellow OLED Application.

The synthesis, crystal structure, and photophysics of a series of neutral cyclometalated iridium(III) complexes bearing substituted N-heterocyclic carbene (NHC) ancillary ligands ((C∧N)2Ir(R-NHC), where C∧N and NHC refer to the cyclometalating ligand benzo[h]quinoline and 1-phenylbenzimidazole, respectively) are reported. The NHC ligands were substituted with electron-withdrawing or -donating groups on C4' of the phenyl ring (R = NO2 (Ir1), CN (Ir2), H (Ir3), OCH3 (Ir4), N(CH3)2 (Ir5)) or C5 of the benzimidazole ring (R = NO2 (Ir6), N(CH3)2 (Ir7)). The configuration of Ir1 was confirmed by a single-crystal X-ray diffraction analysis. The ground- and excited-state properties of Ir1-Ir7 were investigated by both spectroscopic methods and time-dependent density functional theory (TDDFT) calculations. All complexes possessed moderately strong structureless absorption bands at ca. 440 nm that originated from the C∧N ligand based 1π,π*/1CT (charge transfer)/1d,d transitions and very weak spin-forbidden 3MLCT (metal-to-ligand charge transfer)/3LLCT (ligand-to-ligand charge transfer) transitions beyond 500 nm. Electron-withdrawing substituents caused a slight blue shift of the 1π,π*/1CT/1d,d band, while electron-donating substituents induced a red shift of this band in comparison to the unsubstituted complex Ir3. Except for the weakly emissive nitro-substituted complexes Ir1 and Ir6 that had much shorter lifetimes (≤160 ns), the other complexes are highly emissive in organic solutions with microsecond lifetimes at ca. 540-550 nm at room temperature, with the emitting states being predominantly assigned to 3π,π*/3MLCT states. Although the effect of the substituents on the emission energy was insignificant, the effects on the emission quantum yields and lifetimes were drastic. All complexes also exhibited broad triplet excited-state absorption at 460-700 nm with similar spectral features, indicating the similar parentage of the lowest triplet excited states. The highly emissive Ir2 was used as a dopant for organic light-emitting diode (OLED) fabrication. The device displayed a yellow emission with a maximum current efficiency (ηc) of 71.29 cd A-1, a maximum luminance (Lmax) of 32747 cd m-2, and a maximum external quantum efficiency (EQE) of 20.6%. These results suggest the potential of utilizing this type of neutral Ir(III) complex as an efficient yellow phosphorescent emitter.

Post-contrast 3D-FLAIR in idiopathic sudden sensorineural hearing loss.

PURPOSE: Our study investigated correlations between clinical characteristics, particularly hearing recovery, interval time between onset and three-dimensional fluid attenuation inversion recovery magnetic resonance imaging (3D-FLAIR MRI), and the signal intensity of post-contrast 3D-FLAIR MRI in patients with idiopathic sudden sensorineural hearing loss (SSNHL). METHODS: The study enrolled 100 SSNHL patients. The signal intensities and asymmetry ratios of the inner ear structures, including the cochleae, vestibules and vestibulocochlear nerve, were evaluated and calculated. The relationships between the clinical characteristics and MRI findings were assessed. RESULTS: After intravenous gadolinium (Gd) injection, 3D-FLAIR revealed high signal intensities in 65 patients. The corrected asymmetry ratios of cochlea correlated closely with interval time between onset and MRI. The asymmetry ratios of the inner ear structures were significantly lower in patients with final complete to partial hearing recovery. The corrected asymmetry ratios of the inner ear structures correlated with initial/final pure tone audiometry (PTA) and hearing recovery in the affected ear. Notably, it was shown that the corrected asymmetry ratios identified a poor prognosis for hearing recovery, with a sensitivity and specificity of 67.9% and 75.0% in the cochlea, 83.3% and 75.0% in the vestibule, and 52.4% and 81.2% in the vestibulocochlear nerve, respectively. CONCLUSIONS: Post-contrast 3D-FLAIR after intravenous Gd injection in SSNHL can be used to assess the permeability of the blood-labyrinth and blood-nerve barriers. The asymmetry ratios of the inner ear structures may identify patients with poor prognosis for hearing recovery. Signal characteristics are closely related to interval time between onset and MRI.

Quantitative evaluation of endolymphatic hydrops with MRI through intravenous gadolinium administration and VEMP in unilateral definite Meniere's disease.

PURPOSE: To help clinicians to further understand the significance of vestibular-evoked myogenic potential (VEMP) examinations to diagnose MD and the quantitative relationship between VEMP and MRI in assessing the location and degree of endolymphatic hydrops (EH) in definite Meniere's disease (MD) patients. METHODS: Fifty-six patients with unilateral definite MD participated in this study, which used MRIs through intravenous gadolinium administration (IV-Gd), audiometry, caloric tests and VEMP tests. The VEMP results of 26 healthy volunteers were used as a normal reference value. RESULTS: The participants were found through MRI to have differing degrees of vestibular and cochlear EH. Quantitative comparison of MRI and VEMP results found that the response rates of oVEMP decreased with cochlear EH increasing; the asymmetry ratio (AR) of oVEMP can be used to find whether cochlear EH or not, and the P1-N1 amplitude was lower in the extreme cochlear EH group (P < 0.01). The AR of cVEMP was larger in severe vestibular EH group than that of the mild or no vestibular EH group (P < 0.01). The correlation between the degree of cochlear EH and the mean PTA threshold was statistically significant (P < 0.05). The duration of MD correlated positively with vestibular EH (P < 0.05). The abnormal rate of caloric tests was higher in severe vestibular EH group than that of the mild or no vestibular EH group (P < 0.05). CONCLUSIONS: The advantages of MRIs by IV-Gd administration were obvious in assessing the location and degree of EH. oVEMP and PTA can be indirectly used to evaluate the extent of cochlear EH, cVEMP and caloric tests can be used to assess the extent of vestibular EH on the condition of absent MRIs.

Stable 2D Bisthienoacenes: Synthesis, Crystal Packing, and Photophysical Properties.

Two novel 2D bisthienoacenes with annulated thiophene units at different positions were developed. Both 1,2- and 1,4-addition of the α,ß-unsaturated ketone moieties lead to the major formation of four-fold alkylsilylethynyl substituted 2D heteroacenes (namely BTT-4TIPS and BTP-4TIPS). The photophysical, electrochemical properties, crystal packing structures, and charge carrier transport performances were investigated in detail.

Photophysical and Photobiological Properties of Dinuclear Iridium(III) Bis-tridentate Complexes.

A series of cationic dinuclear iridium(III) complexes (Ir1-Ir5) bearing terpyridine-capped fluorenyl bridging ligands and different polypyridyl or cyclometalating terminal tridentate ligands were synthesized, characterized, and evaluated for their photophysical and photobiological activities. The influence of the bridging and terminal ligands on the photophysical properties of the complexes was investigated by UV-vis absorption, emission, and transient absorption spectroscopy and simulated by TDDFT calculations. All of the complexes displayed strong bridging-ligand localized visible 1π,π* absorption and red- or near-infrared phosphorescence as well as broad triplet excited-state absorption across both visible and NIR wavelengths. These triplet states were assigned as predominantly 3π,π* for Ir1 (τ = 3.1 µs) and Ir4 (τ = 48 µs) and 3CT (charge transfer) for Ir2, Ir3, and Ir5 (τ = 1.7-2.7 µs). Complexes Ir1-Ir5 acted as in vitro photodynamic therapy (PDT) agents toward human SK-MEL-28 melanoma cells when activated with visible light, with submicromolar photocytotoxicity and phototherapeutic indices ranging from 20 to almost 300. The in vitro PDT effects with visible light did not correlate with singlet oxygen (1O2) quantum yields or DNA photocleaving capacity probed under cell-free conditions. All of the Ir(III) complexes phosphoresced brightly when associated with compromised cells (with or without light treatment) and exhibited photoactivated cellular uptake, highlighting the theranostic potential of this new class of Ir(III) complex photosensitizers.

Prognostic and influencing factors of tinnitus in chronic otitis media after tympanoplasty.

The purpose of this study is to investigate what characteristics of tinnitus in patients with chronic otitis media was reduced after tympanoplasty and to assess the relationship between post-operative tinnitus reduction and pre-operative tinnitus tone, tinnitus duration, post-operative hearing recovery, and tympanogram. Medical records were prospective between March 2013 and May 2016. Audiologic evaluation by pure tone audiometry and acoustic impedance and tinnitus assessment using scores on the Tinnitus Handicap Inventory (THI) was conducted preoperatively and 6 months post-operatively. The data were analyzed using the Wilcoxon test, Student's and paired t test, and ANOVA. The pre-operative incidence of tinnitus in patients with COM was 47%. There was a very significant difference between pre-operative and post-operative mean THI scores (p < 0.05). Tinnitus was reduced or alleviated in 83% of tinnitus patients. Pre-operative low-tone tinnitus was significantly reduced 6 months after surgery. After surgery, air-conducted hearing improvement at 250, 500, and 1000 Hz in the tinnitus significant recovery group was greater than the tinnitus non-significant recovery group (p < 0.05). Tinnitus reduction in tympanogram A was significantly greater than in tympanograms B or C (p < 0.05). There was no statistically significant correlation between tinnitus duration and tinnitus reduction (p > 0.05). There was no significant effect of presence cholesteatoma and dry period on the gain THI (p > 0.05). The types of tympanoplasty had no effect on tinnitus improvement (p > 0.05). No patients experienced new tinnitus after surgery. Following tympanoplasty, most patients experienced a reduction in tinnitus. Pre-operative low-tone tinnitus is easier to reduce after tympanoplasty. Post-operative normal tympanogram and improved low-frequency AC hearing were important to tinnitus reduction.

Multifunctional Cationic Iridium(III) Complexes Bearing 2-Aryloxazolo[4,5-f][1,10]phenanthroline (N

A series of 2-aryloxazolo[4,5-f][1,10]phenanthroline ligands (N^N ligands) and their cationic iridium(III) complexes (1-11, aryl = 4-NO2-phenyl (1), 4-Br-phenyl (2), Ph (3), 4-NPh2-phenyl (4), 4-NH2-phenyl (5), pyridin-4-yl (6), naphthalen-1-yl (7), naphthalen-2-yl (8), phenanthren-9-yl (9), anthracen-9-yl (10), and pyren-1-yl (11)) were synthesized and characterized. By introducing different electron-donating or electron-withdrawing substituents at the 4-position of the 2-phenyl ring (1-5), or different aromatic substituents with varied degrees of π-conjugation (6-11) on oxazolo[4,5-f][1,10]phenanthroline ligand, we aim to understand the effects of terminal substituents at the N^N ligands on the photophysics of cationic Ir(III) complexes using both spectroscopic methods and quantum chemistry calculations. Complexes with the 4-R-phenyl substituents adopted an almost coplanar structure with the oxazolo[4,5-f][1,10]phenanthroline motif, while the polycyclic aryl substituents (except for naphthalen-2-yl) were twisted away from the oxazolo[4,5-f][1,10]phenanthroline motif. All complexes possessed strong absorption bands below 350 nm that emanated from the ligand-localized 1π,π*/1ILCT (intraligand charge transfer) transitions, mixed with 1LLCT (ligand-to-ligand charge transfer)/1MLCT (metal-to-ligand charge transfer) transitions. At the range of 350-570 nm, all complexes exhibited moderately strong 1ILCT/1LLCT/1MLCT transitions at 350-450 nm, and broad but very weak 3LLCT/3MLCT absorption at 450-570 nm. Most of the complexes demonstrated moderate to strong room temperature phosphorescence both in solution and in the solid state. Among them, complex 7 also manifested a drastic mechanochromic and vapochromic luminescence effect. Except for complexes 1 and 4 that contain NO2 or NPh2 substituent at the phenyl ring, respectively, all other complexes exhibited moderate to strong triplet excited-state absorption in the spectral region of 440-750 nm. Moderate to very strong reverse saturable absorption (RSA) of these complexes appeared at 532 nm for 4.1 ns laser pulses. The RSA strength followed the trend of 7 > 11 > 9 > 3 > 2 ≈ 4 > 5 ≈ 10 ≈ 6 ≈ 8 > 1. The photophysical studies revealed that the different 2-aryl substituents on the oxazole ring impacted the singlet and triplet excited-state characteristics dramatically, which in turn notably influenced the RSA of these complexes.

Tuning the Ground State and Excited State Properties of Monocationic Iridium(III) Complexes by Varying the Site of Benzannulation on Diimine Ligand.

Extending π-conjugation of the diimine ligand (N^N ligand) via benzannulation is a common way to tune the absorption and emission energies of cationic iridium(III) complexes. However, it can cause either a red- or blue-shift of the absorption and emission bands depending on the site of benzannulation. To understand the mechanism of changes in optical transitions upon benzannulation on the diimine ligand, a series of new cationic iridium(III) complexes [Ir(dppi)2(N^N)]PF6 (1-6) (where dppi =1,2-diphenylpyreno[4,5-d]imidazole; N^N = 2-(pyridin-2-yl)quinoline (1), 2-(pyridin-2-yl)[7,8]benzoquinoline (2), 2,2'-bisquinoline (3), 2-(quinolin-2-yl)[7,8]benzoquinoline (4), 2-(pyridin-2-yl)[6,7]benzoquinoline (5), 2-(quinolin-2-yl)[6,7]benzoquinoline (6)) containing diimine ligand with varied degrees of π-conjugation via benzannulation at different sites of the 2-(pyridin-2-yl)quinoline ligand were synthesized. Experimental results and density functional theory (DFT) calculations revealed that benzannulation at the 6,7-position of quinoline and/or the 5',6'-position of pyridine (3, 5, and 6) induced red-shifts in their absorption and emission bands with respect to the parent complex 1; while benzannulation at the 7,8-position of quinoline resulted in blue-shifts (2 vs 1 and 4 vs 3). This phenomenon was rationalized by the symmetry of the frontier molecular orbitals at the site of benzannulation, which stabilized or destabilized the lowest unoccupied molecular orbital (LUMO) upon interactions with 1,3-butadiene, while the energy of the highest occupied molecular orbital (HOMO) remained nearly the same. This discovery would enable a rational design of organic or organometallic compounds that have predetermined absorption and emission energies.

π-Expansive Heteroleptic Ruthenium(II) Complexes as Reverse Saturable Absorbers and Photosensitizers for Photodynamic Therapy.

Five heteroleptic tris-diimine ruthenium(II) complexes [RuL(N^N)2](PF6)2 (where L is 3,8-di(benzothiazolylfluorenyl)-1,10-phenanthroline and N^N is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), 1,4,8,9-tetraazatriphenylene (tatp) (3), dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4), or benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) (5), respectively) were synthesized. The influence of π-conjugation of the ancillary ligands (N^N) on the photophysical properties of the complexes was investigated by spectroscopic methods and simulated by density functional theory (DFT) and time-dependent DFT. Their ground-state absorption spectra were characterized by intense absorption bands below 350 nm (ligand L localized 1π,π* transitions) and a featureless band centered at ∼410 nm (intraligand charge transfer (1ILCT)/1π,π* transitions with minor contribution from metal-to-ligand charge transfer (1MLCT) transition). For complexes 4 and 5 with dppz and dppn ligands, respectively, broad but very weak absorption (ε < 800 M-1 cm-1) was present from 600 to 850 nm, likely emanating from the spin-forbidden transitions to the triplet excited states. All five complexes showed red-orange phosphorescence at room temperature in CH2Cl2 solution with decreased lifetimes and emission quantum yields, as the π-conjugation of the ancillary ligands increased. Transient absorption (TA) profiles were probed in acetonitrile solutions at room temperature for all of the complexes. Except for complex 5 (which showed dppn-localized 3π,π* absorption with a long lifetime of 41.2 µs), complexes 1-4 displayed similar TA spectral features but with much shorter triplet lifetimes (1-2 µs). Reverse saturable absorption (RSA) was demonstrated for the complexes at 532 nm using 4.1 ns laser pulses, and the strength of RSA decreased in the order: 2 ≥ 1 ≈ 5 > 3 > 4. Complex 5 is particularly attractive as a broadband reverse saturable absorber due to its wide optical window (430-850 nm) and long-lived triplet lifetime in addition to its strong RSA at 532 nm. Complexes 1-5 were also probed as photosensitizing agents for in vitro photodynamic therapy (PDT). Most of them showed a PDT effect, and 5 emerged as the most potent complex with red light (EC50 = 10 µM) and was highly photoselective for melanoma cells (selectivity factor, SF = 13). Complexes 1-5 were readily taken up by cells and tracked by their intracellular luminescence before and after a light treatment. Diagnostic intracellular luminescence increased with increased π-conjugation of the ancillary N^N ligands despite diminishing cell-free phosphorescence in that order. All of the complexes penetrated the nucleus and caused DNA condensation in cell-free conditions in a concentration-dependent manner, which was not influenced by the identity of N^N ligands. Although the mechanism for photobiological activity was not established, complexes 1-5 were shown to exhibit potential as theranostic agents. Together the RSA and PDT studies indicate that developing new agents with long intrinsic triplet lifetimes, high yields for triplet formation, and broad ground-state absorption to near-infrared (NIR) in tandem is a viable approach to identifying promising agents for these applications.

Tuning the Photophysics and Reverse Saturable Absorption of Heteroleptic Cationic Iridium(III) Complexes via Substituents on the 6,6'-Bis(fluoren-2-yl)-2,2'-biquinoline Ligand.

To understand the effects of the terminal substituent at the diimine ligand on the photophysics of heteroleptic cationic Ir(III) complexes and to obtain Ir(III) complexes with extended ground-state absorption to the near-IR region while retaining the long-lived and broadly absorbing triplet excited state, we synthesized three heteroleptic cationic iridium(III) complexes bearing cyclometalating 1-phenylisoquinoline (C^N) ligands and substituted 6,6'-bis(7-R-fluoren-2-yl)-2,2'-biquinoline (N^N) ligand (R = H, NO2, or NPh2). The photophysics of these complexes was systematically investigated via spectroscopic methods and time-dependent density functional theory. All complexes possess strong ligand-localized 1π,π* transitions mixed with ligand-to-ligand charge transfer (1LLCT)/metal-to-ligand charge transfer (1MLCT) transitions below 400 nm, and a broad and featureless absorption band above 400 nm that arises from the N^N ligand-localized 1π,π*/1ILCT (intraligand charge transfer) transitions as well as the very weak 1,3LLCT/1,3MLCT transitions at longer wavelengths. The electron-withdrawing NO2 substituent on the N^N ligand leads to a blue-shift of the 1π,π*/1ILCT absorption band, while the electron-donating NPh2 substituent causes a pronounced red-shift of this band. The unsubstituted and NO2-substituted complexes (complexes 1 and 2, respectively) are moderately emissive at room temperature (RT) in solution as well as at 77 K in the glassy matrix, while the NPh2-substituted complex (3) is weakly emissive at RT, but the emission becomes much brighter at 77 K. Complexes 1 and 2 show very broad and strong triplet excited-state absorption from 460 to 800 nm with moderately long lifetimes, while complex 3 exhibits weak but broad absorption bands from 384 to 800 nm with a longer lifetime than those of 1 and 2. The nonlinear transmission experiment manifests that complexes 1 and 2 are strong reverse saturable absorbers (RSA) at 532 nm, while 3 shows weaker RSA at this wavelength. These results clearly demonstrate that it is feasible to tune the ground-state and excited-state properties of the Ir(III) complexes via the terminal substituents at the diimine ligand. By introducing the fluoren-2-yl groups to the 2,2'-biquinoline ligand to extend the diimine ligand π-conjugation, we can obtain Ir(III) complexes with reasonably long-lived and strongly absorbing triplet excited state while red-shifting their 1,3LLCT/1,3MLCT absorption band into the near-IR region. These features are critical in developing visible to near-IR broadband reverse saturable absorbers.