https://hdl.handle.net/11000/7 Thu, 01 Oct 2026 05:38:07 GMT 2026-10-01T05:38:07Z https://hdl.handle.net/11000/40883 Título : Consecutive intrabronchial administration of Wharton’s jelly-derived mesenchymal stromal cells in ECMO-supported pediatric patients with end-stage interstitial lung disease: a safety and feasibility study (CIBA method) Autor : Dominguez-Pinilla, Nerea; González-Granado, Luis Ignacio; Gonzaga, Aitor; López Diaz, María; Castellano Yáñez, Cecilia; Aymerich, Clara; Freire, Xabier; Ordoñez, Olga; Gimeno Diaz de Atauri, Álvaro; Albi Rodríguez, María Salomé; Martínez López, Elisa; Iñiguez, Rodrigo; Serrano Garrote, Olga; Castro Frontiñán, Almudena; Andreu, Etelvina; Gutiérrez-Vílchez, Ana Mª; Anton-Bonete, Marga; Martínez-Navarrete, Gema; Castillo-Flores, Nerea; Prat-Vidal, Cristina; Blanco, Margarita; Morante Valverde, Rocío; Fernández, Eduardo; Querol, Sergi; Hernández-Blasco, Luis Manuel; Belda-Hofheinz, Sylvia; Soria, Bernat Resumen : Background: Patients ineligible for lung transplant with end-stage Interstitial Lung Disease (ILD) on Extra-Corporeal Membrane Oxygenation (ECMO) face an appalling prognosis with limited therapeutic options. Due to the beneficial effect of Mesenchymal Stromal Cells (MSC) on inflammatory, immunological and infectious diseases, cell therapy has been proposed as an option, but administration is hampered by the ECMO. Methods: Cryopreserved Wharton-jelly derived MSC (WJ-MSC) were conveniently diluted and directly applied consecutively on each lobule (5,1 ml = 107 cells) at a continuous slow rate infused over one hour via flexible bronchoscopy (Consecutive IntraBronchial Administration method, CIBA method). Results: Intrabronchial administration of MSC to a patient on ECMO was well tolerated by the patient even though it did not reverse the patient’s ILD. This manuscript presents preliminary evidence from ongoing clinical trials program on Cell Therapy of Inflammatory, Immune and Infectious Diseases and, to our knowledge, is the first report of intrabronchial administration of MSC in a paediatric ECMO patient with ILD. Even more, MSC administered by this method do not reach the systemic circulation and do get blocked on ECMO membrane. Conclusions: Direct intrabronchial administration of MSC in a patient on ECMO is feasible and safe, and may be a new avenue to be assayed in ECMO patients with inflammatory, immunological and infectious diseases of the lung. Tue, 29 Sep 2026 17:39:56 GMT https://hdl.handle.net/11000/40883 2026-09-29T17:39:56Z https://hdl.handle.net/11000/40882 Título : Tuning the Nonlinear Optical Properties of MoS2 by Interfacing with Bay- or Imide-Substituted Perylene Diimides Autor : Nikoli, Eleni; Canton-Vitoria, Ruben; Skentzos, Georgios; Pramatioti, Efrosyni; Zink-Lorre, Nathalie; Gutiérrez-Vílchez, Ana Mª; Fernández-Lázaro, Fernando; Arenal, Raul; Couris, Stelios; Tagmatarchis, Nikos Resumen : We have investigated the tuning of nonlinear optical (NLO) properties in semiconducting MoS2 nanosheets through covalent functionalization with bay- or imide-substituted perylene diimide (PDI) derivatives. Five MoS2−PDI hybrid nanomaterials 1a−5a were synthesized by attaching PDI variants featuring azobenzene or other substituents, characterized via Raman, IR, TGA, STEM-EDS, ultraviolet−visible (UV−vis), photoluminescence, and electrochemical analyses, and evaluated for NLO response under nanosecond (4 ns, 1064/532 nm) and femtosecond (70 fs, 800/400 nm) laser excitations. The hybrids exhibit enhanced and tunable NLO-absorptive (switching from saturable to reverse-saturable absorption with intensity) and NLO-refractive (self-focusing) responses compared to exfoliated MoS2, with 1a and 2a (azobenzene-substituted PDIs) showing the strongest effects due to efficient electron-transfer and -resonant excitations. Hybrids demonstrate superior NLO susceptibility (χ3) values, particularly under resonant 532 nm excitation, with Im{χ3} values of up to −514.7 ± 57.4 × 10−13 esu·mL/mg for 2a at low intensities, attributed to Pauli blocking, defect states, and two-photon processes. Hybrids having bay-substituted PDIs grafted on MoS2 enhance conjugation and performance over imide variants, enabling applications in optical-limiting, mode-locking, and photonic devices. Threshold intensities for NLA switching (150−250 MW/cm2) exceed those of MoS2, highlighting the stability for high-power uses. The developed hybrid materials advance two-dimensional transition-metal dichalcogenide-based optoelectronics by overcoming light−matter interaction limits through molecular antenna effects from PDIs. The study underscores the substituent position and azobenzene integration as levers for NLO optimization in hybrid nanoarchitectures. Tue, 29 Sep 2026 16:58:22 GMT https://hdl.handle.net/11000/40882 2026-09-29T16:58:22Z https://hdl.handle.net/11000/40880 Título : Functionalization tuning of the nonlinear optical response of perylene diimide derivativatives Autor : Skentzos, George; Pramatioti, Efrosyni; Zink-Lorre, Nathalie; Gutiérrez-Vílchez, Ana Mª; Nikoli, Eleni; Canton-Vitoria, Ruben; Fernández-Lázaro, Fernando; Couris, Stelios Resumen : The synthesis and characterization of perylene diimide (PDI) derivatives functionalized by electron donating groups at their bay and imide positions have been reported. Five different PDI derivatives were synthesized and their linear optical and third-order non-linear optical (NLO) properties were studied. The NLO measurements of the synthesized PDI derivatives were conducted under nanosecond (ns) and femtosecond (fs) laser excitation conditions, using the Z-scan technique employing 4 ns, 1064/532 nm and 70 fs, 800/400 nm laser pulses. A noticeable tuning of the NLO character between the synthesized PDI derivatives was observed, revealing the importance of the functionalization of the PDI core by the anchored electron donating units. The largest NLO value was achieved by the incorporation of p-aminoazobenzene at the PDI bay position. The experimental NLO findings and trends were further corroborated with theoretical computations of UV-Vis spectra and NLO response, performed using density functional theory (DFT). It was found that both experiments and simulations satisfactorily convey changes in the NLO response between the studied PDI derivatives. The mechanism that could lead to an efficient tuning of the PDIs’ NLO response, is associated with the modification of their electronic character resulting by the proper PDI core functionalization. Tue, 29 Sep 2026 16:41:37 GMT https://hdl.handle.net/11000/40880 2026-09-29T16:41:37Z https://hdl.handle.net/11000/40878 Título : Zinc Phthalocyanine N-Linked to Pyrroloperylenediimide Dyad: Significance of N-Connectivity in Modulating Photodynamics Toward Prolonging the Lifetime of Charge Separation Autor : Ileperuma, Chamari V.; Garcés-Garcés, Jose; Gutiérrez-Vílchez, Ana Mª; Sastre-Santos, Ángela; Fernández-Lázaro, Fernando; D'Souza, Francis Resumen : A zinc phthalocyanine–pyrroloperylenediimide dyad connected through a nitrogen heteroatom (PDI-N-ZnPc) has been newly synthesized and characterized. Solvent-polarity-dependent singlet–singlet energy transfer and electron-transfer quenching were envisioned from absorption and steady-state fluorescence studies. Electrochemical and spectroelectrochemical studies enabled the assessment of the redox potentials of the donor and acceptor entities, as well as the spectral characterization of the one-electron oxidation and reduction products. Density functional theory (DFT) studies were performed to investigate the geometry and electronic structure, as well as the role of N-connectivity in determining the relative orientation of the entities. Further, time-dependent DFT studies helped establish the different excited states responsible for promoting charge separation. An energy diagram was subsequently established to visualize different photophysical events. Finally, femtosecond transient absorption spectral studies were performed in both nonpolar and polar solvents to observe energy- and electron-transfer events. The kinetic data were subsequently analyzed using global and target analyses. The persistence of the charge-separated state in the present dyad, compared with earlier reported ZnPc–PDI dyads featuring carbon–carbon connectivity, was the primary outcome of the present study, highlighting the role of heteroatom linkage in regulating electron-transfer dynamics in donor–acceptor conjugates. Tue, 29 Sep 2026 16:13:07 GMT https://hdl.handle.net/11000/40878 2026-09-29T16:13:07Z https://hdl.handle.net/11000/40877 Título : Occurrence of excited state charge separation in a N-doped graphene–perylenediimide hybrid formed via ‘click’ chemistry Autor : Gobeze, Habtom B.; Arellano, Luis M.; Gutiérrez-Vílchez, Ana Mª; Gómez-Escalonilla, María J.; Sastre-Santos, Ángela; Fernández-Lázaro, Fernando; Langa, Fernando; D'Souza, Francis Resumen : Hetero-atom doped graphene is a two-dimensional material with a band gap, needed to build optoelectronic devices. However, research progress in this area has been sluggish due to synthetic challenges to build energy harvesting materials, especially donor–acceptor type hybrids. In the present study, using click chemistry, we have successfully synthesized a donor–acceptor hybrid comprised of Ndoped graphene and perylenediimide (PDI), a well-known electron-accepting photosensitizer. The TGA and XPS results revealed the attachment of the PDI moiety in the hybrid. Ground and excited state interactions were monitored by a variety of spectral and electrochemical techniques. Finally, the ability of the present donor–acceptor hybrid to undergo photoinduced charge separation from singlet excited PDI was systematically probed using femtosecond transient spectral techniques. Evidence of charge separation was possible to achieve from comparison of transient and spectroelectrochemical results. These results suggest the potential use of covalently functionalized, substitutional N-doped graphene as a functional material for building optoelectronic devices. Tue, 29 Sep 2026 15:46:58 GMT https://hdl.handle.net/11000/40877 2026-09-29T15:46:58Z https://hdl.handle.net/11000/40854 Título : La comedia televisiva Autor : Gómez Morales, Beatriz Maria; Hidalgo Marí, Tatiana; Ferrer Ceresola, Rosa Tue, 29 Sep 2026 11:16:11 GMT https://hdl.handle.net/11000/40854 2026-09-29T11:16:11Z https://hdl.handle.net/11000/40851 Título : A zinc phthalocyanine–benzoperylenetriimide conjugate for solvent dependent ultrafast energy vs. electron transfer Autor : Navarro-Pérez, Valeria; Gutiérrez-Vílchez, Ana Mª; Ortiz, Javier; Sastre-Santos, Ángela; Fernández-Lázaro, Fernando; Seetharaman, Sairaman; Duffy, M. J.; Karr, Paul A.; D’Souza, Francis Resumen : A novel zinc phthalocyanine–benzoperylenetriimide conjugate has been synthesized and its ability to undergo ultrafast energy and electron transfer as a function of solvent polarity has been demonstrated using the femtosecond transient absorption (fs-TA) technique operating at a femto- to nanosecond time scale. Mon, 28 Sep 2026 18:29:17 GMT https://hdl.handle.net/11000/40851 2026-09-28T18:29:17Z https://hdl.handle.net/11000/40848 Título : Light harvesting zinc naphthalocyanine–perylenediimide supramolecular dyads: long-lived charge-separated states in nonpolar media - Autor : El-Khouly, Mohamed E.; Gutiérrez, Ana Mª; Sastre-Santos, Ángela; Fernández-Lázaro, Fernando; Fukuzumi, Shunichi Resumen : Photoinduced electron-transfer dynamics of self-assembled donor–acceptor dyads formed by axial coordination of zinc naphthalocyanine, ZnNc, and perylenediimide (PDI) bearing either pyridine (py) or imidazole (im) coordinating ligands were investigated. The PDIim unit was functionalized with tertoctylphenoxy groups at the bay positions, which avoid aggregation providing solubility, to examine the effect of the bulky substituents at the bay positions on the rates of electron-transfer reactions. The combination between zinc naphthalocyanine and perylenediimide entities absorbs light over a wide region of the visible and near infrared (NIR) spectrum. The binding constants of the self-assembled ZnNc:PDIpy (1) and ZnNc:PDIim (2) in toluene were found to be 2.40 104 and 1.10 105 M 1, respectively, from the steady-state absorption and emission measurements, indicating formation of moderately stable complexes. The geometric and electronic calculations by using an ab initio B3LYP/6-311G method showed the majority of the highest occupied frontier molecular orbital (HOMO) on the zinc naphthalocyanine entity, while the lowest unoccupied molecular orbital (LUMO) was on the perylenediimide entities, suggesting that the charge-separated states of the supramolecular dyads are ZnNc +:PDI . The electrochemical results suggest the exothermic charge-separation process via the singlet states of both ZnNc and PDI entities in nonpolar toluene. Upon coordination of perylenediimide to ZnNc, the main quenching pathway involved charge separation via the singlet-excited states of ZnNc and PDIs. Clear evidence of the intramolecular electron transfer from the singlet-excited state of ZnNc to PDI within the supramolecular dyads in toluene was monitored by the femtosecond laser photolysis by observing the characteristic absorption band of the PDI radical anion (PDI ) and the ZnNc radical cation (ZnNc +) in the visible and NIR regions. The rate constants of charge-separation (kCS) processes of the self-assembled dyads 1 and 2 were determined to be 4.05 1010 and 1.20 109 s 1, respectively. The rate constant of charge recombination (kCR) and the lifetime of charge-separated states (tCS) of dyad 1 were determined to be 2.34 108 s 1 and 4.30 ns, respectively. Interestingly, a slower charge recombination (2.20 107 s 1) and a longer lifetime of the charge separated state (45 ns) were observed in dyad 2 in nonpolar toluene by utilizing the nanosecond transient measurements. The absorption in a wide section of the solar spectrum and the high charge-separation/charge-recombination ratio suggest the usefulness of the self-assembled zinc naphthalocyanine–perylenediimide dyads as good photosynthetic models. Mon, 28 Sep 2026 18:14:21 GMT https://hdl.handle.net/11000/40848 2026-09-28T18:14:21Z https://hdl.handle.net/11000/40845 Título : Control of Photoinduced Electron Transfer in Zinc Phthalocyanine-Perylenediimide Dyad and Triad by the Magnesium Ion Autor : Fukuzumi, Shunichi; Ohkubo, Kei; Ortiz, Javier; Gutiérrez, Ana Mª; Fernández-Lázaro, Fernando; Sastre-Santos, Ángela Resumen : Photoexcitation of a zinc phthalocyanine-perylenediimide (ZnPc-PDI) dyad and a bis(zinc phthalocyanine)- perylenediimide [(ZnPc)2-PDI] triad results in formation of the triplet excited state of the PDI moiety without the fluorescence emission, whereas addition of Mg2+ ions to the dyad and triad results in formation of longlived charge-separated (CS) states (ZnPc•+-PDI•-/Mg2+ and (ZnPc)2 •+-PDI•-/Mg2+) in which PDI•- forms a complex with Mg2+. Formation of the CS states in the presence of Mg2+ was confirmed by appearance of the absorption bands due to ZnPc•+ and PDI•-/Mg2+ complex in the time-resolved transient absorption spectra of the dyad and triad. The one-electron reduction potential (Ered) of the PDI moiety in the presence of a metal ion is shifted to a positive direction due to the binding of Mg2+ to PDI•-, whereas the one-electron oxidation potential of the ZnPc moiety remains the same. The binding of Mg2+ to PDI•- was confirmed by the ESR spectrum, which is different from that of PDI•- without Mg2+. The energy of the CS state (ZnPc•+-PDI•-/ Mg2+) is determined to be 0.79 eV, which becomes lower that of the triplet excited state (ZnPc-3PDI*: 1.07 eV). This is the reason why the long-lived CS states were attained in the presence of Mg2+ instead of the triplet excited state of the PDI moiety. Mon, 28 Sep 2026 17:48:47 GMT https://hdl.handle.net/11000/40845 2026-09-28T17:48:47Z https://hdl.handle.net/11000/40843 Título : Formation of a long-lived charge-separated state of a zinc phthalocyanine-perylenediimide dyad by complexation with magnesium ion Autor : Fukuzumi, Shunichi; Ohkubo, Kei; Ortiz, Javier; Gutiérrez, Ana Mª; Fernández-Lázaro, Fernando; Sastre-Santos, Ángela Resumen : Photoexcitation of a zinc phthalocyanine–perylenediimide (ZnPc–PDI) dyad affords the triplet excited state without the fluorescence emission, whereas addition of Mg2+ to the photoexcited ZnPc–PDI results in formation of a long-lived charge-separated state (ZnPc˙+–PDI˙−/Mg2+) in which PDI˙− forms a complex with Mg2+. Mon, 28 Sep 2026 17:34:04 GMT https://hdl.handle.net/11000/40843 2026-09-28T17:34:04Z