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1.
Br J Ophthalmol ; 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32554442

RESUMO

AIM: To determine the outcomes of Aurolab aqueous drainage implant (AADI) placed in the superotemporal versus the inferonasal quadrant in adult eyes with refractory glaucoma. METHODS: This was a retrospective study of eyes that had AADI placement and completed a minimum of 2-year follow-up. The choice of the quadrant was at the surgeon's discretion and mainly depended on the amount of scarring and conjunctival mobility. The cumulative failure rate of the AADI was defined as intraocular pressure (IOP) >21 mm Hg or not reduced by 20% below baseline on two consecutive follow-up visits after 3 months, IOP ≤5 mm Hg on two consecutive follow-up visits after 3 months, reoperation for glaucoma or a complication, or loss of light perception vision. RESULTS: We included 84 eyes with AADI in the inferonasal quadrant versus 69 eyes in the superotemporal quadrant. A significant drop in IOP was seen in both groups (18.4±10.4 mm Hg in the inferonasal group vs 17.7±11.1 mm Hg in the superotemporal group; p=0.63) at 3-month follow-up and this was maintained until last follow-up. Best-corrected visual acuity, IOP, number of IOP-lowering medications and complications were similar between the two groups at all time points. The cumulative success rate at 2-year follow-up without IOP-lowering medications was 57.1% (47.1%-68.1%) in the inferonasal group and 50.7% (39.8%-63.1%) in the superotemporal group (p=0.47). CONCLUSIONS: Inferonasal AADI placement appears to be an equally safe and effective surgical option compared with superotemporal AADI placement and may be helpful in certain clinical situations.

2.
Chempluschem ; 85(3): 411-425, 2020 03.
Artigo em Inglês | MEDLINE | ID: mdl-32119196

RESUMO

The synthesis and characterization of six triarylisocyanurates, featuring 2,7-fluorenyl or 9,10-anthracenyl groups incorporated in their peripheral arms are reported. Photophysical studies reveal that these new octupolar derivatives are more fluorescent (ΦF ≥0.60 for all new compounds except for 1,3,5-tri(9H-fluoren-2-yl)-1,3,5-triazinane-2,4,6-trione 3) and present a red-shifted lowest absorption and emission compared to their known phenyl analogues of comparable size. Depending on the nature of the terminal substituent, fast intramolecular energy transfer among the three arms or localization of the excitation on a single branch occurs after population of their first singlet excited state. The latter effect was only observed in the presence of strongly electron-releasing substituents in polar media. These new chromophores are also better two-photon absorbers than the 1,4-phenylene-based isocyanurates reported so far, with cross sections σ2 ≥500 GM at 770 nm for 4-NPh2 the fluorenyl group containing (13) and the anthracenyl group containing (14) chromophores. All these spectroscopic features, analyzed with the help of quantum chemical calculations, are crucial for the design of new biphotonic fluorescent dyes.

3.
Chem Commun (Camb) ; 2020 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-32104794

RESUMO

Two 1,1,4,4-tetracyanobutadiene (TCBD) derivatives were prepared by [2+2]cycloaddition-retroelectrocyclization from ynamides bearing either a pyrene (1) or a perylene unit (2). In addition to panchromatic absorptions in 2, in the solid state, both compounds unexpectedly display NIR photoluminescence that could be detected up to about 1350 nm.

4.
Molecules ; 25(2)2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31936003

RESUMO

: A series of free base and Zn(II) phthalocyanines featuring fluorenyl antennae linked by methoxy or oxo bridges to the phthalocyanine core (Pc) were synthesized and characterized. Selected linear and nonlinear (two-photon absorption) optical properties of these new compounds were subsequently studied. As previously observed for related porphyrin dendrimers bearing 2-fluorenyl peripheral dendrons, an efficient energy transfer occurs from the peripheral antennae to the central phthalocyanine core following excitation in the fluorenyl-based π-π* absorption band of these chromophores. Once excited, these compounds relax to the ground state, mostly by emitting intense red light or by undergoing intersystem crossing. As a result, the tetrafunctionalized Zn(II) phthalocyanines are fluorescent, but can also efficiently photosensitize molecular oxygen in tetrahydrofurane (THF), forming singlet oxygen with nearly comparable yields to bare Zn(II) phthalocyanine (ZnPc). In comparison with the latter complex, the positive role of the fluorenyl-containing antennae on one- and two-photon brightness (2PA) is presently demonstrated when appended in peripheral (ß) position to the phthalocyanine core. Furthermore, when compared to known porphyrin analogues, the interest in replacing the porphyrin by a phthalocyanine as the central core to obtain more fluorescent two-photon oxygen photosensitizers is clearly established. As such, this contribution paves the way for the future development of innovative biphotonic photosensitizers usable in theranostics.


Assuntos
Fluorenos/química , Indóis/química , Fármacos Fotossensibilizantes/química , Oxigênio Singlete/química , Transferência de Energia , Fluorenos/síntese química , Indóis/síntese química , Luz , Luminescência , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Fótons , Porfirinas/química , Oxigênio Singlete/isolamento & purificação , Análise Espectral
5.
Br J Ophthalmol ; 2019 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-31585962

RESUMO

AIM: To report the intermediate-term outcomes of Aurolab aqueous drainage implant (AADI) surgery in paediatric eyes with refractory glaucoma. METHODS: Case records of patients below 18 years, who underwent AADI surgery between 2012 and 2015 with >2 years follow-up, were analysed. The intraocular pressure (IOP), visual acuity, number of antiglaucoma medications, complications and resurgery if any were recorded at baseline, day 1and then at months 1, 3, 6, 9, 12, 18, 24 and at the last visit. Failure was defined as IOP >18 mm Hg or not reduced by at least 30% below baseline, IOP ≤5 mm Hg on two consecutive follow-up visits after 3 months, reoperation for a complication or loss of light perception vision. RESULTS: 101 eyes of 101 patients were included with a mean age of 10.4±4.7 years at the time of surgery and a mean follow-up of 40.9±15.1 months. Glaucoma following cataract surgery was the most common type of glaucoma (n=31, 30%), followed by primary congenital glaucoma (n=29, 29%). The cumulative probability of failure was 15.8% (95% CI 10.1% to 24.5%) at 1 year, 22.7% (95% CI 15.7% to 32.2%) at 2 years, 42.5% (95% CI 32.6% to 53.9%) at 3 years and 62.1% (95% CI 49.5% to 74.8%) at the 4 years time point. CONCLUSION: The AADI showed excellent success until 2 years after surgery in paediatric eyes after which failure rates increased. Further prospective studies with longer follow-up are required to evaluate the long-term success of the AADI for paediatric glaucomas.

6.
Chem Commun (Camb) ; 55(81): 12231-12234, 2019 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-31553001

RESUMO

The photophysical properties of a new series of fluorenyl porphyrins bearing water-solubilising oligoethyleneglycol chains are described. These biocompatible compounds present very good two-photon absorption and singlet oxygen generation properties, while retaining some fluorescence in water. After testing in vitro on breast cancer cells, some of them were shown to be efficient non-toxic two-photon photosensitisers allowing for fluorescence imaging, thus demonstrating their theranostic potential.


Assuntos
Fluorenos/química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Porfirinas/química , Materiais Biocompatíveis/química , Permeabilidade da Membrana Celular , Sobrevivência Celular/efeitos dos fármacos , Humanos , Raios Infravermelhos , Células MCF-7 , Microscopia de Fluorescência por Excitação Multifotônica/métodos , Estrutura Molecular , Imagem Óptica/métodos , Polietilenoglicóis/química , Oxigênio Singlete/química , Relação Estrutura-Atividade
7.
Dalton Trans ; 48(31): 11897-11911, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31310264

RESUMO

Two dyads containing tris- and tetrakis-meso-fluorenyl-substituted porphyrin and ethynylruthenium units, 1 and 2, were investigated by emission spectro-electrochemical (SEC) methods for their potential use as fluorescence switches. The ruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor are connected by a phenylene bridge in 1 and by a fluorenylene bridge in 2. The new fluorenyl-linked dyad 2 was probed by UV-visible, near-infrared (NIR) and infrared (IR) absorption SEC methods, and the properties interpreted with the aid of hybrid-DFT computations, for comparison with reported data for 1. The porphyrin-based fluorescence of 1 decreased in intensity upon oxidation to 1+ and decreased further on oxidising 1+ to 12+. A much weaker change in the fluorescence intensity of 2 was observed upon oxidation to 2+ but the intensity decreased upon subsequent oxidation of 2+ to 22+. These findings contrast with data reported for some other porphyrins appended with redox-active ruthenium or iron units, where fluorescence intensities increase upon oxidation of the peripheral metal centers, but they match data reported more recently for closely related arrays. A rationale for these apparently contrasting observations is proposed.

8.
Subst Use Misuse ; 54(5): 841-851, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30648459

RESUMO

BACKGROUND: Stressful deployments in combat areas are known to increase the risk of substance abuse in military personnel. OBJECTIVES: The aim of the study was to compare deployment on stressful, high-intensity missions (HIMs) to deployment on low-intensity missions (LIMs) in order to understand factors associated with substance use variations across the mission. METHODS: A retrospective cohort study based on a one-shot self-questionnaire was performed four months after their return on two samples of male French Army service members: one returning from an HIM and one from an LIM. The questionnaire focused on tobacco, alcohol, cannabis, cocaine, and psychoactive medication use at three times: before, during, and after the mission. RESULTS: During an HIM, the frequency of tobacco use increased, alcohol use remained stable - although 38% declared a decrease in consumption - and illicit drug use decreased. During an LIM, tobacco and alcohol use increased, cannabis use remained stable, and only cocaine and medication use decreased. After their return, use levels among both samples reverted to values similar to those reported before the mission, except for a decrease in tobacco use observed at return from an HIM. The main factors perceived as related to variations were stress in an HIM and low cost in an LIM. Conclusions/importance: The study suggests a differential impact of deployment on substance use according to the operational intensity of the mission. Variations in use are predominant during the mission with a washout effect after returning home.


Assuntos
Consumo de Bebidas Alcoólicas/psicologia , Transtornos Relacionados ao Uso de Substâncias/diagnóstico , Uso de Tabaco/psicologia , Adulto , Estudos de Coortes , Humanos , Masculino , Militares/estatística & dados numéricos , Estudos Retrospectivos , Fatores de Risco , Transtornos Relacionados ao Uso de Substâncias/psicologia , Inquéritos e Questionários , Adulto Jovem
9.
Dalton Trans ; 47(32): 11123-11135, 2018 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-30043792

RESUMO

A new Zn(ii) porphyrin-based dendrimer (52) containing twelve Ru(ii) alkynyl fragments, has been prepared following a convergent approach in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) (6). The cubic nonlinear optical (NLO) properties of 52 and other derivatives of 6 have been measured by third-harmonic generation (THG) at 1907 nm and by Z-scan over the spectral range 500-1700 nm, revealing the remarkable NLO response of 52 in the near-IR range. These results highlight the beneficial role of the extended "cross fourchée"-like polymetallic structure of 52 on its third-order NLO properties.

10.
Chemistry ; 23(11): 2635-2647, 2017 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-27976827

RESUMO

A series of three conjugated meso-porphyrin dendrimers containing conjugated dendrons featuring 2,7-fluorenyl groups, incorporating overall 8, 12, or 28 fluorenyl units have been synthesized and characterized. The photophysical properties of these new compounds were studied in the context of photodynamic therapy. The relevant linear and nonlinear optical properties were measured in organic media and useful structure-properties relationships were derived.

11.
Chemistry ; 22(29): 10155-67, 2016 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-27297358

RESUMO

The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives (1-3 and 2') incorporating 2- or 2,7-fluorenyl and diphenylamino moieties are reported. The electroactivity of 1-3 and 2' was studied by cyclic voltammetry (CV), while the linear optical and (third-order) nonlinear optical (NLO) properties were investigated by electronic spectroscopy and Z-scan studies, respectively. All experimental investigations were rationalized by DFT computations, providing an insight into the electronic structure of these derivatives and on their application potential. We show that these derivatives are nonluminescent in solution at ambient temperatures, but become fluorescent in solvent glasses. This finding constitutes an unprecedented observation for TCBD derivatives. Also, we show by Z-scan studies that these derivatives behave as two-photon absorbers in the near-IR range (800-1050 nm). These third-order NLO properties are discussed and compared with those of their alkynyl precursors (4-6), which have been investigated by two-photon excited fluorescence (TPEF).

12.
Angew Chem Int Ed Engl ; 55(28): 8062-6, 2016 07 04.
Artigo em Inglês | MEDLINE | ID: mdl-27193483

RESUMO

The combination of a bis-alkynyl-helicene moiety with two iron centers leads to novel electroactive species displaying unprecedented redox-triggered chiroptical switching. Upon oxidation, strong changes of vibrational modes (either local or extended coupled modes) are detected by vibrational circular dichroism and Raman optical activity. Remarkably, the sign of the optical rotation at 1.54 µm (that is, at wavelengths typically used for telecommunications) changes upon oxidation while the topology and stereochemistry of the helicene remain unchanged.

13.
Front Neurol Neurosci ; 38: 228-36, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27035830

RESUMO

During the 20th century, the management of war-related psychological trauma shifted from neurology to psychiatry. After September 11, 2001, the French forces participated in a multinational force deployed in Afghanistan to fight against terrorism. Post-traumatic stress disorder (PTSD) became a priority. We report the daily work of the psychiatrists involved in this mission and the organization developed to psychologically support wounded military personnel. The doctrine of early intervention psychiatrization and the technique of collective debriefing are the key points of this procedure. The psychiatrist is also responsible for the healthcare community, particularly vulnerable when confronted with severe ballistic injuries. One aim of this organization is also to screen PTSD in soldiers returning from Afghanistan. The military general practitioner is a pivotal point of this procedure built to detect PTSD, anxiety, depressive reaction and behavioral problems. The French health service has developed a genuine care strategy aimed at identifying patients, accompanying them in the formalities for recognition and compensation, and offering them treatment locally by arranging clinical psychology consultations near their home.


Assuntos
Distúrbios de Guerra/etiologia , Militares/psicologia , Transtornos de Estresse Pós-Traumáticos , Afeganistão , Distúrbios de Guerra/história , França , História do Século XXI , Humanos , Transtornos de Estresse Pós-Traumáticos/complicações , Transtornos de Estresse Pós-Traumáticos/epidemiologia , Transtornos de Estresse Pós-Traumáticos/história
14.
Chemistry ; 22(16): 5583-97, 2016 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-26933931

RESUMO

A new family of conjugated meso-tetraphenylporphyrin-based dendrimers with four (TPP1, TPP2), eight (TPP3, TPP4, TPP5) and up to sixteen (TPP6) fluorenyl groups has been synthesized and fully characterized. These tetraphenylporphyrin-cored dendrimers present peripheral alkynyl π-conjugated dendrons with fluorenyl termini. The meso-aryl rings of these porphyrins are functionalized either in para- (TPP1, TPP2, and TPP3) or meta-positions (TPP4, TPP5, and TPP6). Their detailed luminescence properties are discussed in reference to two porphyrins lacking fluorenyl dendrons (TPP-H1,2,3 and TPP-H4,5,6). A strong dependence of their luminescence quantum yield and lifetime on their structures is stated, their nonlinear optical properties were also discussed.

15.
Dalton Trans ; 44(17): 7748-51, 2015 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-25854620

RESUMO

A new Zn(ii) porphyrin-cored ruthenium alkynyl dendrimer (2) containing twelve Ru(κ(2)-dppe)2 bis-alkynyl fragments has been prepared in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) and shown to be highly active for third-harmonic generation (THG) at 1907 nm.

16.
Dalton Trans ; 44(20): 9470-85, 2015 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-25915654

RESUMO

Reactions of the 16-electron ruthenium complex [Ru(dppe)2Cl][PF6] with metal-free and zinc ethynylphenyltrifluorenylporphyrins and respectively, gave the new dyads and with ethynylruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor. The redox properties of the porphyrins were investigated by cyclic voltammetry and UV spectroelectrochemistry (SEC), which reveal that the monocation and monoanion of metal-free porphyrin are stable under these conditions whereas the formation of the corresponding radical cation or anion of the zinc porphyrin was accompanied by partial decomplexation of the zinc ion. Oxidations of the dyads and gave stable radical cations as probed using IR, NIR and UV SEC methods. These cations show similar NIR and IR bands to those reported for the known 17-electron [Ru(dppe)2(C[triple bond, length as m-dash]CPh)Cl](+) radical cation. Remarkably, the dyad has four stable redox states +2/+1/0/-1 where the second oxidation and first reduction processes take place at the porphyrin unit. Simulated absorption spectra on at optimised geometries obtained by TD-DFT computations with the CAM-B3LYP functional are shown to be in very good agreement with the observed UV absorption spectra of . The spectra of and their oxidised and reduced species were interpreted with the aid of the TD-DFT data. Fluorescence measurements reveal that the dyads and are only weakly emitting compared to and , indicative of quenching of the porphyrinic singlet excited state by the ruthenium centre.

17.
Chem Commun (Camb) ; 51(7): 1316-9, 2015 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-25483340

RESUMO

A series of paramagnetic di(aryl)alkynylphosphine oxides [PF6] featuring an open-shell [Fe(κ(2)-dppe)(η(5)-C5Me5)](+) endgroup were obtained by oxidation of their neutral Fe(II) parents 3a-c, themselves obtained in a simple and nearly quantitative fashion from the corresponding Fe(II) metallophosphines 1a-c. The new organometallic radicals were characterised by NMR and ESR and were shown to be perfectly stable in solution, in contrast to species such as 1a-b[PF6] which readily dimerise.

18.
Dalton Trans ; 43(19): 7002-5, 2014 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-24710466

RESUMO

The redox-active metallaphosphine [Fe(dppe)(η(5)-C5Me5)(C≡C-PPh2)] reacts with [Pd(1,5-cod)Cl2] to give mono- and bis-phosphine coordinated palladium centres as a function of stoichiometry, and these complexes provide a stable redox-active platform which allows reversible one-electron {Fe(II)→Fe(III)(+)} oxidations within the palladium coordination sphere.

19.
Inorg Chem ; 52(15): 8993-9004, 2013 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-23869668

RESUMO

The synthesis of four triaylphosphine ligands featuring electron-rich Fe(II) "Fe(κ(2)-dppe)(η(5)-C5Me5)C≡C-" pendant substituents in para and meta position(s) (1-4) is reported along with that of their corresponding radical cations (1-2[PF6] or 3-4[PF6]3). These triarylphosphines possessing redox-active organometallic substituents constitute a new class of phosphorus-based metallo-ligands. In contrast to many related ferrocenylphosphines, these metallo-ligands are stable and isolable in two redox-states. Their steric and electronic properties are also briefly discussed.

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