C₆₀ dimers connected through pleiadene bridges: fullerenes talking to each other

Sastre-Santos, Á,ngela,Parejo, Concepció,n,Martí,n-Gomis, Luis,Ohkubo, Kei,Ferná,ndez-Lá,zaro, Fernando,Fukuzumi, Shunichi Royal Society of Chemistry 2011 Journal of materials chemistry Vol.21 No.5

<P>New C<SUB>60</SUB> dimers 1, 2 and 3 that differ in the distance between the two balls, connected through pleiadene bridges have been synthesized. Different synthetic strategies have been used to prepare C<SUB>60</SUB> dimers 1–3. A diastereoisomeric mixture was obtained for C<SUB>60</SUB> dimer 1, which was separated by column chromatography and characterized by NMR. By CV measurements, no interaction between the two balls was found in the ground state in any type of C<SUB>60</SUB> dimer. By reduction with dimeric benzylnicotinamide [(BNA)<SUB>2</SUB>], a two electron reductant, the interaction between both C<SUB>60</SUB> units has been analyzed using electron paramagnetic resonance (EPR). For C<SUB>60</SUB> dimer 3, upon addition of 1 equivalent (BNA)<SUB>2</SUB> no electronic interaction in the C<SUB>60</SUB>˙<SUP>−</SUP>–C<SUB>60</SUB>˙<SUP>−</SUP> was observed due to the long distance between the C<SUB>60</SUB> balls (20 Å). However, for C<SUB>60</SUB> dimer 1, where the distance between radicals is shorter, 10 Å, the electronic interaction in the di(radical anion), C<SUB>60</SUB>˙<SUP>−</SUP>–C<SUB>60</SUB>˙<SUP>−</SUP> in the presence of 1 equivalent of (BNA)<SUB>2</SUB> was observed by EPR, corresponding to a triplet biradical.</P> <P>Graphic Abstract</P><P>Addition of 1 equivalent of (BNA)<SUB>2</SUB> to dimer 1 yields the C<SUB>60</SUB>˙<SUP>−</SUP>–C<SUB>60</SUB>˙<SUP>−</SUP> triplet biradical where electronic interaction is observed. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0jm02635b'> </P>

Anti-Atherogenic Effects of a Phenol-Rich Fraction from Brazilian Red Wine (Vitis labrusca L.) in Hypercholesterolemic Low-Density Lipoprotein Receptor Knockout Mice

Mariana Appel Hort,Elke Zuleika Schuldt,ˆ ngela Cristina Bet,Silvia DalBo,Jarbas Mota Siqueira,,Carla Ianssen,Fa´tima Abatepaulo,Heraldo Possolo de Souza,Beatriz Veleirinho,Marcelo Maraschin,Rosa Mari 한국식품영양과학회 2012 Journal of medicinal food Vol.15 No.10

Moderate wine intake (i.e., 1–2 glasses of wine a day) is associated with a reduced risk of morbidity and mortality from cardiovascular disease. The aim of this study was to evaluate the anti-atherosclerotic effects of a nonalcoholic ethyl acetate fraction (EAF) from a South Brazilian red wine obtained from Vitis labrusca grapes. Experiments were carried out on low-density lipoprotein (LDL) receptor knockout (LDLr−/−) mice, which were subjected to a hypercholesterolemic diet and treated with doses of EAF (3, 10, and 30 mg/kg) for 12 weeks. At the end of the treatment, the level of plasma lipids, the vascular reactivity, and the atherosclerotic lesions were evaluated. Our results demonstrated that the treatment with EAF at 3 mg/kg significantly decreased total cholesterol, triglycerides, and LDL plus very low-density lipoprotein levels compared with control hypercholesterolemic mice. The treatment of mice with EAF at 3 mg/kg also preserved the vasodilatation induced by acetylcholine on isolated thoracic aorta from hypercholesterolemic LDLr−/− mice. This result is in agreement with the degree of lipid deposit on arteries. Taken together, the results show for the first time that the lowest concentration of an EAF obtained from a red wine produced in southern Brazil significantly reduced the progression of atherosclerosis in mice.

Light harvesting zinc naphthalocyanine–perylenediimide supramolecular dyads: long-lived charge-separated states in nonpolar media

El-Khouly, Mohamed E.,Gutié,rrez, Ana M.,Sastre-Santos, Á,ngela,Ferná,ndez-Lá,zaro, Fernando,Fukuzumi, Shunichi The Royal Society of Chemistry 2012 Physical chemistry chemical physics Vol.14 No.10

<P>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 <I>tert</I>-octylphenoxy 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 (<B>1</B>) and ZnNc:PDIim (<B>2</B>) in toluene were found to be 2.40 × 10<SUP>4</SUP> and 1.10 × 10<SUP>5</SUP> M<SUP>−1</SUP>, respectively, from the steady-state absorption and emission measurements, indicating formation of moderately stable complexes. The geometric and electronic calculations by using an <I>ab initio</I> 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&z.rad;<SUP>+</SUP>:PDI&z.rad;<SUP>−</SUP>. The electrochemical results suggest the exothermic charge-separation process <I>via</I> 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 <I>via</I> 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&z.rad;<SUP>−</SUP>) and the ZnNc radical cation (ZnNc&z.rad;<SUP>+</SUP>) in the visible and NIR regions. The rate constants of charge-separation (<I>k</I><SUB>CS</SUB>) processes of the self-assembled dyads <B>1</B> and <B>2</B> were determined to be 4.05 × 10<SUP>10</SUP> and 1.20 × 10<SUP>9</SUP> s<SUP>−1</SUP>, respectively. The rate constant of charge recombination (<I>k</I><SUB>CR</SUB>) and the lifetime of charge-separated states (<I>τ</I><SUB>CS</SUB>) of dyad <B>1</B> were determined to be 2.34 × 10<SUP>8</SUP> s<SUP>−1</SUP> and 4.30 ns, respectively. Interestingly, a slower charge recombination (2.20 × 10<SUP>7</SUP> s<SUP>−1</SUP>) and a longer lifetime of the charge separated state (45 ns) were observed in dyad <B>2</B> 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.</P> <P>Graphic Abstract</P><P>Good combination! Efficient electron transfer and relatively long-lived charge-separated states are achieved of light harvesting zinc naphthalocyanine:perylenediimide supramolecular dyads using the femtosecond transient absorption technique in nonpolar toluene. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cp23285e'> </P>

Early-diagnosed silent sinus syndrome and cone-beam computed tomography in a pediatric patient: a case report

Natali Leidens,Ademir Franco,Marco C.J. Santos,Irina M. Makeeva,Â,ngela Fernandes 대한구강악안면외과학회 2020 대한구강악안면외과학회지 Vol.46 No.2

Chronic maxillary atelectasis (CMA) is a progressive alteration in the volume of the maxillary sinuses that may result in facial asymmetry. CMA in asymptomatic patients is known as silent sinus syndrome (SSS) and is a rare entity, especially in pediatric patients. This study reports a case of SSS in a pediatric patient who received an early diagnosis through cone-beam computed tomography (CBCT). An asymptomatic 12-year-old female patient in orthodontic treatment presented with opacification of the left maxillary sinus on a panoramic radiograph. Clinically, the patient had discrete hypoglobus and enophthalmos. CBCT and nasal video-endoscopy revealed ostiomeatal obstruction with bone deformity, leading to diagnosis of SSS. Endonasal endoscopic maxillary sinusotomy was performed. Two years later, the patient remained asymptomatic, and a second CBCT exam confirmed a stable condition. This case highlights the role of optimal radiographic interpretation for early diagnosis of maxillofacial alterations in pediatric patients.

Multistep electron transfer systems based on silicon phthalocyanine, [60]fullerene and trinitrofluorenone

Martí,n-Gomis, Luis,Ohkubo, Kei,Ferná,ndez-Lá,zaro, Fernando,Fukuzumi, Shunichi,Sastre-Santos, Á,ngela Royal Society of Chemistry 2010 Chemical communications Vol.46 No.22

<P>The synthesis and photodynamics in the absence and in the presence of Mg<SUP>2+</SUP> ions of a novel TNF-C<SUB>60</SUB>-SiPc-C<SUB>60</SUB>-TNF pentad are reported. The redox gradient approach allows to obtain a long-lived CS state of 160 ns and 200 μs in the absence and in the presence of Mg<SUP>2+</SUP> ions, respectively.</P> <P>Graphic Abstract</P><P>The redox gradient approach in a TNF-C<SUB>60</SUB>-SiPc-C<SUB>60</SUB>-TNF pentad allows the generation of a long-lived CS state of 160 ns/200 μs in the absence/presence of Mg<SUP>2+</SUP> ions respectively. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c002077j'> </P>

Supramolecular Zinc Phthalocyanine-Imidazolyl Perylenediimide Dyad and Triad: Synthesis, Complexation, and Photophysical Studies

Cé,spedes-Guirao, F. Javier,Ohkubo, Kei,Fukuzumi, Shunichi,Ferná,ndez-Lá,zaro, Fernando,Sastre-Santos, Á,ngela Wiley (John WileySons) 2011 Chemistry, an Asian journal Vol.6 No.11

<P>Two new supramolecular architectures based on zinc phthalocyanine (Pc) and imidazolyl-substituted perylenediimide (PDI), ZnPc/DImPDI/ZnPc 1 and ZnPc/ImPDI 2, have been prepared. A strong electron-donor, ZnPc-8, which contained eight tert-octylphenoxy groups was synthesized to ensure high solubility, thereby reducing aggregation in solution and providing ??-donor features while avoiding regioisomeric mixtures. Also, PDI units were functionalized with tert-octylphenoxy groups at the bay positions, which provide solubility to avoid aggregation in solution, together with one and two imidazole moieties in the amide position, PDI-6 and PDI-4, respectively, to be able to strongly coordinate with the ZnPc complex. Supramolecular complexation studies by (1)H NMR spectroscopy and ESI-MS demonstrate a high coordinative binding constant between imidazole-substituted PDI-4 or PDI-6 and ZnPc-8. The same results were confirmed by UV/Vis and fluorescence titration studies. UV/Vis titration studies revealed the formation of a 1:1 complex ZnPc/ImPDI 2 for the systems ZnPc-8 and PDI-6 and a 2:1 complex ZnPc/DImPDI/ZnPc 1 for the interaction of ZnPc-8 and PDI-4. The binding constant in both cases was determined to be on the order of 10(5) M(-1). Femtosecond laser flash photolysis measurements provided a direct proof of the charge-separated state within both supramolecular assemblies by observing the transient absorption band at 820 nm due to the zinc phthalocyanine radical cation. The lifetimes of charge-separated states are (9.8±3) ns for triad 1 and (3±1) ns for dyad 2. As far as we know, this is the first time that a radical ion pair has been detected in a supramolecular assembled ZnPc-PDI system and has obtained the longest lifetime of a charge-separated state published for ZnPc-PDI assemblies.</P>

Rational design of a phthalocyanine–perylenediimide dyad with a long-lived charge-separated state

Blas-Ferrando, Vicente M.,Ortiz, Javier,Bouissane, Latifa,Ohkubo, Kei,Fukuzumi, Shunichi,Ferná,ndez-Lá,zaro, Fernando,Sastre-Santos, Á,ngela The Royal Society of Chemistry 2012 Chemical communications Vol.48 No.50

<P>A new ZnPc–PDI dyad presenting for the first time a charge-separated state lower in energy than the triplet excited state of the ZnPc and PDI has been synthesized. The rational design implies the substitution of the ZnPc with phenoxy groups and the bay substitution of the PDI with sulfonyl substituents. The lifetime of the charge-separated state was 72 μs.</P> <P>Graphic Abstract</P><P>The longest charge-separated state so far, 72 μs, without the addition of external components, for phthalocyanine–perylenediimide arrays has been described. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cc31087b'> </P>

Thermo and pH-Responsive Poly(DEGMA-co-OEGMA)-b-Poly(DEAEM) Synthesized by RAFT Polymerization and Its Self-Assembly Study

Ángela M. López,Antonio Tirado-Guizar,Angel Licea-Claverie,Alejandro Ramírez-Jiménez 한국고분자학회 2022 Macromolecular Research Vol.30 No.12

Drug delivery and release systems using stimuli-responsive nanostructures based on amphiphilic copolymers have gained great importance. In this work copolymers from oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and di(ethylene glycol) methyl ether methacrylate (DEGMA) as thermo-responsive moiety and block copolymers incorporating N,N′-diethylaminoethyl methacrylate (DEAEM) as pH-responsive one, were synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT) using 5-amino-4-methyl-4-(propylthiocarbonothioylthio)- 5-oxo pentanoic acid as chain transfer agent (CTA). The number average molecular weights (Mn), and dispersity Đ confirmed a good RAFT control. Polymers were characterized by Fourier transform infrared spectroscopy using a attenuated total reflection (FTIR-ATR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic light scattering (DLS), transmission electron microscope (TEM), and Turbidimetry. Their self-assembly behavior is described by its hydrodynamic diameter (Dh), its ζ-potential and as well as its cloud point temperature (Tcp). The results showed thermo-responsive and pH-responsive systems with Tcp in phosphate-buffered saline (PBS) pH=7.4 around 37 and 42℃ the isoelectric point was found in a pH range between 7.0 and 7.5, further the critical micelle concentration (CMC) indicated very low values between 5.85 to 4.20 × 10-4 mg mL-1. The developed block copolymeric systems have potential to be used for drug transport and delivery.

Design of intelligent control strategies using a magnetorheological damper for span structure

Ángela Hernández,Graciliano N. Marichal,Alfonso V. Poncela,Isidro Padrón 국제구조공학회 2015 Smart Structures and Systems, An International Jou Vol.15 No.4

This paper focuses on the design of an intelligent control system. The used techniques are basedon Neuro Fuzzy approaches applied to a magnetorheological damper in order to reduce the vibrations overfootbridges; it has been applied to the Science Museum Footbridge of Valladolid, particularly. A model ofthe footbridge and of the damper has been built using different simulation tools, and a successful comparisonwith the real footbridge and the real damper has been carried out. This simulated model has allowed thereproduction of the behaviour of the footbridge and damper when a pedestrian walks across the footbridge. Once it is determined that the simulation results are similar to real data, the control system is introduced intothe model. In this sense, different strategies based on Neuro Fuzzy systems have been studied. In fact, anANFIS (Artificial Neuro Fuzzy Inference System) method has also been used, in addition to an alternativeNeuro Fuzzy approach. Several trials have been carried out, using both techniques, obtaining satisfactoryresults after using these techniques.

Rejection of a kidney graft revealed by positron emission tomography

( Aidana Barrera-herrera ),( Ángela Gonzalez-rojas ),( Andrés Perissinotti ),( Ana Belen Larque ),( Frederic Cofan ),( Fritz Diekmann ),( David Cucchiari ) 대한신장학회 2023 Kidney Research and Clinical Practice Vol.42 No.2