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Glycerophospholipids have hydrophobic and hydrophilic moieties. Previous studies suggest that phospholipids with different moieties have different effects on rodent behavior; however, the relationship between chemical structures and behavioral effects remains unclear. To clarify the functions of phospholipid moieties, we injected male rats with phospholipids with different moieties and conducted behavioral tests. Exploratory activity was reduced by phosphatidylethanolamine (PE)(18:0/22:6) but not PE(18:0/18:0) or PE(18:0/20:4). Conversely, exploratory activity was increased by plasmanyl PE(16:0/22:6), which harbors an alkyl-ether linkage, but not by phosphatidylcholine (PC)(16:0/22:6) or plasmanyl PC(16:0/22:6). Docosahexaenoic acid (DHA)(22:6) and an alkyl-ether linkage in PE were thus postulated to be involved in exploratory activity. Anxiety-like behavior was reduced by plasmenyl PC(18:0/20:4), which harbors a vinyl-ether linkage, but not by PC(18:0/20:4) or plasmanyl PC(18:0/20:4), suggesting the anxiolytic effects of vinyl-ether linkage. The activation of social interaction was suppressed by PE(18:0/18:0), PE(18:0/22:6), PC(16:0/22:6), plasmanyl PE(16:0/22:6), and plasmanyl PC(16:0/22:6) but not by PE(18:0/20:4), plasmenyl PE(18:0/20:4), or plasmanyl PC(18:0/22:6). DHA may suppress social interaction, whereas arachidonic acid(20:4) or a combination of alkyl-ether linkage and stearic acid(18:0) may restore social deficits. Our findings indicate the characteristic effects of different phospholipid moieties on rat behavior, and may help to elucidate patterns between chemical structures and their effects.
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AB-type and BAB-type betaine block copolymers composed of a carboxybetaine methacrylate and a sulfobetaine methacrylate, PGLBT-b-PSPE and PSPE-b-PGLBT-b-PSPE, respectively, were synthesized by one-pot RAFT polymerization. By optimizing the concentration of the monomer, initiator, and chain transfer agent, block extension with precise ratio control was enabled and a full conversion (~99%) of betaine monomers was achieved at each step. Two sets (total degree of polymerization: ~300 and ~600) of diblock copolymers having four different PGLBT:PSPE ratios were prepared to compare the influence of block ratio and molecular weight on the temperature-responsive behavior in aqueous solution. A turbidimetry and dynamic light scattering study revealed a shift to higher temperatures of the cloud point and micelle formation by increasing the ratio of PSPE, which exhibit upper critical solution temperature (UCST) behavior. PSPE-dominant diblocks created spherical micelles stabilized by PGLBT motifs, and the transition behavior diminished by decreasing the PSPE ratio. No particular change was found in the diblocks that had an identical AB ratio. This trend reappeared in the other set whose entire molecular weight approximately doubled, and each transition point was not recognizably impacted by the total molecular weight. For triblocks, the PSPE double ends provided a higher probability of interchain attractions and resulted in a more turbid solution at higher temperatures, compared to the diblocks which had similar block ratios and molecular weights. The intermediates assumed as network-like soft aggregates eventually rearranged to monodisperse flowerlike micelles. It is expected that the method for obtaining well-defined betaine block copolymers, as well as the relationship of the block ratio and the chain conformation to the temperature-responsive behavior, will be helpful for designing betaine-based polymeric applications.
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The catalytic organic-hydride transfer to CO2 was first achieved through the photoinduced two-electron reduction of the [Ru(bpy)2 (pbn)]2+ /[Ru(bpy)2 (pbnHH)]2+ (bpy=2,2'-bipyridine, pbn=2-(pyridin-2-yl)benzo[b]-1,5-naphthyridine, and pbnHH=2-(pyridin-2-yl)-5,10-dihydrobenzo[b]-1,5-naphthyridine) redox couple in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH). The active species for the catalytic hydride transfer to carbon dioxide giving formate is [Ru(bpy)(bpyâ - )(pbnHH)]+ formed by one-electron reduction of [Ru(bpy)2 (pbnHH)]2+ with BIâ .
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Seawater reverse osmosis (SWRO) is the most energy-efficient process for desalination to produce drinking water from seawater. However, its sustainability is still challenged by membrane fouling. Appropriate feed water quality is one of the crucial prerequisites for SWRO operation. In the current study, a ceramic adsorption filter (CAF), which was predominantly coated with an aluminum-based adsorbent (i.e., Alumina, Al2O3), was employed to enhance the pretreatment performance of SWRO. The fouling performance of SWRO pre-treated with a CAF was evaluated by feeding with real ultrafiltration (UF)-filtrated seawater collected from a seawater desalination R&D facility in Singapore. The flux decline profile showed that the presence of CAF after UF could mitigate around 10-30% of SWRO fouling. Based on the autopsy of the fouled SWRO membranes, it was observed that SWRO with CAF pre-treatment and daily regeneration could alleviate around 77.5% of Ca-induced inorganic fouling as well as 76% of lower biofouling. The present work highlights the potential of applying adsorption technology to enhance pre-treatment performance to extend the lifespan of SWRO membranes. Coupling the adsorbents on a ceramic filter should be a useful way to ease their implementation, i.e., inline adsorption and re-generation.
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Critical chain length that divides small molecule crystallization from macromolecular crystallization is an important index in macro-organic chemistry to predict chain-length dependent properties of oligomers and polymers. However, extensive research on crystallization behavior of individual oligomers has been inhibited by difficulties in their synthesis and crystallization. Here, we report on the determination of critical chain length of macromolecular crystallization for structurally flexible polyketones consisting of 3,3-dimethylpentane-2,4-dione. Discrete polyketone oligomers were synthesized via stepwise elongation up to 20-mer. Powder and single crystal X-ray diffraction showed that the critical chain length for polyketones existed at an unexpectedly short chain length, 5-mer. While shorter oligomers adopted unique conformations and packing structures in the solid state, higher oligomers longer than 4-mer produced helical conformations and similar crystal packing. The critical chain length helped with understanding the inexplicable changes in melting point in the shorter chain length region resulting from chain conformations and packing styles.
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Anion-responsive photofunctional materials have been extensively studied because anions are important for biotic activity and constitute the building blocks of elegant supramolecular architectures. A number of fluorescent anion receptors that can probe anions in their environments have been reported, but the excited states of many of these molecules remain elusive. Studies on excited-state dynamics provide fruitful information for optimizing the emission properties, minimizing the photodegradation and photorelease of anions, and exploring novel photofunctions. In this study, we investigated the excited-state dynamics of an aryl-substituted dipyrrolyldiketone difluoroboron complex, a π-conjugated anion receptor, by time-resolved visible and infrared absorption spectroscopy and emission decay measurements combined with quantum chemical calculations. Anion binding was found to alter the radiative and nonradiative rate constants and the excited-state absorption of the anion receptor. In contrast, the molecular structures and binding abilities were similar in the S0 and S1 states.
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OBJECTIVE: The surgical management of large and complex tumors of the posterior fossa poses a formidable challenge in neurosurgery. The standard retrosigmoid craniotomy approach has been performed at most neurosurgical centers; however, the retrosigmoid approach may not provide enough working space without significant retraction of the cerebellum. The transsigmoid approach provides wider and shallower surgical fields; however, there have been few clinical and no cadaveric studies on its usefulness. In the present study, the authors describe the transsigmoid approach in clinical cases and cadaveric specimens. METHODS: For the clinical study, the authors retrospectively reviewed the medical records and operative charts of patients who had been surgically treated for parabrainstem tumors using the transsigmoid approach between 1997 and 2019. They analyzed patient demographic and clinical data, as well as surgical and clinical outcomes. In the cadaveric study, they compared the surgical views obtained in different approaches (retrosigmoid, presigmoid, retrolabyrinthine, and transsigmoid) and measured the sigmoid sinus width at the level of the endolymphatic sac and the distance between the anterior edge of the sigmoid sinus and the endolymphatic sac on 35 sides in 19 cadaveric specimens. RESULTS: A total of 21 patients (6 males and 15 females) with a mean age of 42.2 (range 15-67) years were included in the clinical study. Eleven patients had meningioma, 7 had vestibular schwannoma, 2 had hemangioblastoma, and 1 had epidermoid cyst. Gross-total, near-total, and subtotal removal were achieved in 7 (33.3%), 3 (14.3%), and 11 (52.4%) patients, respectively. In the cadaveric study, 19 cadaveric specimens were used. The sigmoid sinus was cut in the middle, and the incision was extended from the retrosigmoid to the presigmoid dura. The dura was then retracted upward and downward like opening a door. The results indicated that this technique can widen the operative field anteriorly by approximately 2 cm as compared to the retrosigmoid approach and provides a better view anterior to the brainstem. CONCLUSIONS: The transsigmoid approach is useful for complex parabrainstem tumors in the posterior fossa because it provides a wider and shallower operative view with less retraction of the cerebellum. This enables safer tumor removal with less damage to important structures in the posterior fossa, resulting in better operative and clinical outcomes.
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Neoplasias Meníngeas , Neuroma Acústico , Adolescente , Adulto , Idoso , Cadáver , Craniotomia/métodos , Feminino , Humanos , Masculino , Neoplasias Meníngeas/cirurgia , Pessoa de Meia-Idade , Neuroma Acústico/cirurgia , Estudos Retrospectivos , Adulto JovemRESUMO
BACKGROUND: The development of diffuse cerebral vasospasm after the removal of a brain tumor is extremely rare. We report a case of cerebral vasospasm after the removal of a posterior fossa hemangioblastoma. CASE DESCRIPTION: A 62-year-old woman presented with a 1-month history of vertigo and nausea. Neurologic examination revealed that she was alert, with no paresis, and a mild left-sided cerebellar ataxia. Contrast-enhanced magnetic resonance imaging showed a cystic lesion with a strongly enhancing nodule, measuring 20 × 26 mm in diameter, in the cerebellar dorsal vermis. Angiography revealed that the lesion had feeding arteries from the left posterior inferior cerebellar artery. A diagnosis of hemangioblastoma was suspected and surgery was performed. On the first postoperative day, paresis of the right-sided extremities occurred. Diffusion-weighted imaging showed a high-intensity area in the medial side of the left frontal lobe. Magnetic resonance angiography indicated diffuse cerebrovascular stenosis. Considering these findings to be caused by vasospasm, we started the treatment used for vasospasm secondary to aneurysmal subarachnoid hemorrhage. Magnetic resonance angiography on the 13th postoperative day revealed an improvement in the cerebrovascular stenosis. In this case, it appears that the cause of vasospasm was intraoperative spillage of the contents of the cyst. CONCLUSIONS: Although the occurrence of diffuse cerebral vasospasm after the removal of brain tumors in the posterior fossa is rare, this complication should be noted as a potential postoperative complication after tumor removal; this should lead to earlier diagnosis and treatment and a potentially better prognosis.
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Hemangioblastoma/cirurgia , Neoplasias Infratentoriais/cirurgia , Complicações Pós-Operatórias/terapia , Vasoespasmo Intracraniano/etiologia , Vasoespasmo Intracraniano/terapia , Constrição Patológica , Imagem de Difusão por Ressonância Magnética , Feminino , Hemangioblastoma/complicações , Hemangioblastoma/diagnóstico por imagem , Humanos , Neoplasias Infratentoriais/complicações , Neoplasias Infratentoriais/diagnóstico por imagem , Angiografia por Ressonância Magnética , Imageamento por Ressonância Magnética , Pessoa de Meia-Idade , Procedimentos Neurocirúrgicos , Paresia/diagnóstico por imagem , Paresia/etiologia , Complicações Pós-Operatórias/diagnóstico por imagem , Resultado do Tratamento , Vasoespasmo Intracraniano/diagnóstico por imagemRESUMO
The susceptibility to neurological and psychiatric disorders reveals sexual dimorphism in the structure and function of human brains. Recent evidence has also demonstrated the sex-related differences in cellular components of the brain, including neurons, microglia, astrocytes, and endothelial cells. Oligodendrocyte precursor cells (OPCs) regulate the neuronal system in various ways and play crucial roles in brain homeostasis beyond their well-known role as a reservoir for mature oligodendrocytes. Although recent studies have shown regional diversities and heterogeneities of OPCs, sex-related differences in OPCs are largely unknown. Here, we revealed transcriptomic differences in OPCs isolated from male and female neonatal rat brains. Furthermore, we demonstrated sex-dependent differences in OPCs regarding proliferation, migration, differentiation, tolerance against ischemic stress, energy metabolism, and the ability to regulate the blood-brain barrier integrity.
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Células Precursoras de Oligodendrócitos , Diferenciação Celular , Células Endoteliais , Feminino , Humanos , Masculino , Oligodendroglia , Caracteres Sexuais , TranscriptomaRESUMO
Background Oligodendrocyte precursor cells ( OPC s) regulate neuronal, glial, and vascular systems in diverse ways and display phenotypic heterogeneity beyond their established role as a reservoir for mature oligodendrocytes. However, the detailed phenotypic changes of OPC s after cerebral ischemia remain largely unknown. Here, we aimed to investigate the roles of reactive OPC s in the ischemic brain. Methods and Results The behavior of OPC s was evaluated in a mouse model of ischemic stroke produced by transient middle cerebral artery occlusion in vivo. For in vitro experiments, the phenotypic change of OPC s after oxygen glucose derivation was examined using a primary rat OPC culture. Furthermore, the therapeutic potential of hypoxic OPC s was evaluated in a mouse model of middle cerebral artery occlusion in vivo. Perivascular OPC s in the cerebral cortex were increased alongside poststroke angiogenesis in a mouse model of middle cerebral artery occlusion. In vitro RNA -seq analysis revealed that primary cultured OPC s increased the gene expression of numerous pro-angiogenic factors after oxygen glucose derivation. Hypoxic OPC s secreted a greater amount of pro-angiogenic factors, such as vascular endothelial growth factor and angiopoietin-1, compared with normoxic OPC s. Hypoxic OPC -derived conditioned media increased the viability and tube formation of endothelial cells. In vivo studies also demonstrated that 5 consecutive daily treatments with hypoxic OPC -conditioned media, beginning 2 days after middle cerebral artery occlusion, facilitated poststroke angiogenesis, alleviated infarct volume, and improved functional disabilities. Conclusions Following cerebral ischemia, the phenotype of OPC s in the cerebral cortex shifts from the parenchymal subtype to the perivascular subtype, which can promote angiogenesis. The optimal use of hypoxic OPC s secretome would provide a novel therapeutic option for stroke.
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Proteínas Angiogênicas/metabolismo , Encéfalo/irrigação sanguínea , Células Endoteliais/metabolismo , Infarto da Artéria Cerebral Média/metabolismo , Neovascularização Fisiológica , Oligodendroglia/metabolismo , Células-Tronco/metabolismo , Proteínas Angiogênicas/genética , Animais , Comportamento Animal , Hipóxia Celular , Células Cultivadas , Meios de Cultivo Condicionados/metabolismo , Modelos Animais de Doenças , Células Endoteliais/patologia , Infarto da Artéria Cerebral Média/patologia , Infarto da Artéria Cerebral Média/fisiopatologia , Infarto da Artéria Cerebral Média/psicologia , Masculino , Camundongos Endogâmicos C57BL , Atividade Motora , Oligodendroglia/patologia , Comunicação Parácrina , Fenótipo , Ratos Sprague-Dawley , Recuperação de Função Fisiológica , Transdução de Sinais , Células-Tronco/patologiaRESUMO
Extant eukaryote ecology is primarily sustained by oxygenic photosynthesis, in which chlorophylls play essential roles. The exceptional photosensitivity of chlorophylls allows them to harvest solar energy for photosynthesis, but on the other hand, they also generate cytotoxic reactive oxygen species. A risk of such phototoxicity of the chlorophyll must become particularly prominent upon dynamic cellular interactions that potentially disrupt the mechanisms that are designed to quench photoexcited chlorophylls in the phototrophic cells. Extensive examination of a wide variety of phagotrophic, parasitic, and phototrophic microeukaryotes demonstrates that a catabolic process that converts chlorophylls into nonphotosensitive 132,173-cyclopheophorbide enols (CPEs) is phylogenetically ubiquitous among extant eukaryotes. The accumulation of CPEs is identified in phagotrophic algivores belonging to virtually all major eukaryotic assemblages with the exception of Archaeplastida, in which no algivorous species have been reported. In addition, accumulation of CPEs is revealed to be common among phototrophic microeukaryotes (i.e., microalgae) along with dismantling of their secondary chloroplasts. Thus, we infer that CPE-accumulating chlorophyll catabolism (CACC) primarily evolved among algivorous microeukaryotes to detoxify chlorophylls in an early stage of their evolution. Subsequently, it also underpinned photosynthetic endosymbiosis by securing close interactions with photosynthetic machinery containing abundant chlorophylls, which led to the acquisition of secondary chloroplasts. Our results strongly suggest that CACC, which allowed the consumption of oxygenic primary producers, ultimately permitted the successful radiation of the eukaryotes throughout and after the late Proterozoic global oxygenation.
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Clorofila/metabolismo , Eucariotos/metabolismo , Oxigênio/metabolismo , Cloroplastos/metabolismo , Ecossistema , Eucariotos/classificação , Eucariotos/genética , Microalgas/classificação , Microalgas/genética , Microalgas/metabolismo , Fotossíntese , Filogenia , SimbioseRESUMO
For photosynthetic organisms that nourish the earth's biosphere, chlorophylls (Chls) are the major pigments utilized for light harvesting and primary charge separation. Although Chl molecules are effective photosensitizers, they are inevitably phototoxic to living organisms due to the facile generation of highly oxidative singlet oxygen (1O2) through triplet energy transfer from their photoexcited states to oxygen molecules. Such phototoxicity of Chls is a major problem for translucent microbes that feed on photosynthetic algae. Recently, it has been reported that the metabolic conversion of Chls-a/b to 132,173-cyclopheophorbide-a/b enols (cPPB-a/bEs) is the detoxification mechanism for algivorous protists. cPPB-a/bEs are colored π-conjugated cyclic tetrapyrroles but are nonfluorescent due to efficient nonradiative decay. In this study, femtosecond time-resolved transient absorption spectroscopy was applied to cPPB-aE with the aim of understanding its quenching mechanism. As a result, we have captured the ultrafast generation of an intermediate state (â¼140 fs) that leads to the rapid internal conversion to the ground state (â¼450 fs).
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C3-(Trans-2-arylethenyl)carbonylated chlorophyll derivatives possessing a bacteriochlorin or chlorin π-system were synthesized by cross-aldol (Claisen-Schmidt) condensation of methyl pyrobacteriopheophorbide-a or 3-acetyl-3-devinyl-pyropheophorbide-a bearing the C3-acetyl group with p-(un)substituted benzaldehydes under basic conditions. The corresponding porphyrin-type chlorophyll derivatives were prepared by the oxidation (17,18-didehydrogenation) of the chlorin-type. Their Qy absorption and fluorescence emission maxima in dichloromethane correlated well with Hammett substituent constants of the p-substituents. Several electron-withdrawing p-substituents suppressed the emission due to photoinduced electron transfer quenching in a molecule. The substitution sensitivities for their maxima and fluorescence quantum yields decreased in the order of bacteriochlorin-, chlorin- and porphyrin-type derivatives.
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Chalcona/química , Clorofila/química , Porfirinas/química , Espectrometria de Massas , Espectrometria de Fluorescência , Espectrofotometria UltravioletaRESUMO
Divinyl-132,173-cyclopheophorbide-a enol was in vivo produced as a metabolite of divinyl-chlorophyll-a by protists and in vitro prepared by the intramolecular cyclization of methyl divinyl-pyropheophorbide-a, one of the divinyl-chlorophyll-a derivatives. The 1H NMR spectra in CDCl3 showed that the obtained product took exclusively its enol form in the solution. The intramolecular cyclization of chlorin π-system at the C132 and C173 positions affected the optical properties of such chlorophyll derivatives including the non-fluorescent emission of the enol.
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Clorofila/análogos & derivados , Compostos de Vinila/química , Clorofila/síntese química , Clorofila/química , Clorofila/metabolismo , Conformação Molecular , Compostos de Vinila/metabolismoRESUMO
Glial cytoplasmic inclusions (GCIs), commonly observed as α-synuclein (α-syn)-positive aggregates within oligodendrocytes, are the pathological hallmark of multiple system atrophy. The origin of α-syn in GCIs is uncertain; there is little evidence of endogenous α-syn expression in oligodendrocyte lineage cells, oligodendrocyte precursor cells (OPCs), and mature oligodendrocytes (OLGs). Here, based on in vitro analysis using primary rat cell cultures, we elucidated that preformed fibrils (PFFs) generated from recombinant human α-syn trigger multimerization and an upsurge of endogenous α-syn in OPCs, which is attributable to insufficient autophagic proteolysis. RNA-seq analysis of OPCs revealed that α-syn PFFs interfered with the expression of proteins associated with neuromodulation and myelination. Furthermore, we detected cytoplasmic α-syn inclusions in OLGs through differentiation of OPCs pre-incubated with PFFs. Overall, our findings suggest the possibility of endogenous α-syn accumulation in OPCs that contributes to GCI formation and perturbation of neuronal/glial support in multiple system atrophy brains.
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Corpos de Inclusão/genética , Atrofia de Múltiplos Sistemas/genética , Células Precursoras de Oligodendrócitos/metabolismo , alfa-Sinucleína/genética , Animais , Encéfalo/metabolismo , Encéfalo/patologia , Técnicas de Cultura de Células , Diferenciação Celular/genética , Humanos , Corpos de Inclusão/patologia , Atrofia de Múltiplos Sistemas/metabolismo , Atrofia de Múltiplos Sistemas/patologia , Neuroglia/metabolismo , Neuroglia/patologia , Neurônios/metabolismo , Neurônios/patologia , Células Precursoras de Oligodendrócitos/patologia , Oligodendroglia/metabolismo , Ratos , alfa-Sinucleína/metabolismoRESUMO
The supramolecular organogelation of bacteriochlorophyll(BChl)-c carrying an isobutyl substituent at the 8-position was observed in carbon tetrachloride at a concentration of about 10â mm at room temperature. The BChl-c gel was evaluated by several spectroscopic measurements: the electronic absorption spectrum exhibited a far-red shift of the Qy-absorption from 660 to 748â nm and the FTIR spectrum showed a shorter frequency shift of the 13-C=O stretching from 1683 to 1643â cm-1 compared to the shifts of the corresponding monomer solution in tetrahydrofuran. These observations strongly indicate that the gelating BChl-c molecules form self-aggregates that are reminiscent of light-harvesting chlorosomes of green photosynthetic bacteria. The present supramolecular organogel prepared from natural chlorophylls is promising for the creation of an intelligent soft material involving artificial photosynthesis.
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The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3-diketonate group at the C3 position were synthesized from methyl pyropheophorbide-d through Barbier acylmethylation of the C3-formyl moiety, oxidation of the C3-carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400-500â nm, with a Qy band shifted to a longer wavelength of λ≈700â nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C3(3) -position of the conjugate afforded an additional charge-transfer band over λ=500â nm, producing a pigment that bridged the green gap in standard chlorophylls.
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BACKGROUND: We conducted a randomized, double-blind, sham-controlled study to assess the efficacy in motor recovery and safety of daily repetitive transcranial magnetic stimulation (rTMS) in subacute stroke patients. METHODS: Forty-one patients were randomly assigned to a real or sham stimulation group. Each patient underwent regular rehabilitation accompanied by a series of 10 daily 5-Hz rTMS of the ipsilesional primary motor cortex (M1) or sham stimulation. The primary outcome was motor recovery evaluated by the Brunnstrom stages (BS). The secondary outcomes were improvement in the Fugl-Meyer Assessment (FMA), grip power, National Institutes of Health Stroke Scale (NIHSS), Functional Independence Measure (FIM), a quantitative measurement of finger tapping movement, and the incidence of adverse events. RESULTS: Thirty-nine patients completed the study and were included in the analyses. The real rTMS group demonstrated additional improvement in the BS hand score at the last follow-up compared to the sham. The grip power, the NIHSS motor score, and the number of finger taps in the affected hand improved in the real stimulation group but not in the sham group. The BS upper limb scores, the FMA distal upper limb score, the NIHSS total score, and the FIM motor score showed improvement from baseline at the earlier time points after the real rTMS. There were no additional improvements in the other scores after the real rTMS compared to the sham. No serious adverse events were observed. CONCLUSIONS: Our results suggest that dailyhigh-frequency rTMS of the ipsilesional M1 is tolerable and modestly facilitates motor recovery in the paralytic hand of subacute stroke patients.
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Atividade Motora , Córtex Motor/fisiopatologia , Paresia/reabilitação , Reabilitação do Acidente Vascular Cerebral/métodos , Acidente Vascular Cerebral/terapia , Estimulação Transcraniana por Corrente Contínua , Extremidade Superior/inervação , Idoso , Avaliação da Deficiência , Método Duplo-Cego , Feminino , Força da Mão , Humanos , Japão , Masculino , Pessoa de Meia-Idade , Paresia/diagnóstico , Paresia/fisiopatologia , Recuperação de Função Fisiológica , Acidente Vascular Cerebral/diagnóstico , Acidente Vascular Cerebral/fisiopatologia , Reabilitação do Acidente Vascular Cerebral/efeitos adversos , Fatores de Tempo , Estimulação Transcraniana por Corrente Contínua/efeitos adversos , Resultado do TratamentoRESUMO
Chlorophyll-a (Chl-a) was extracted from cyanobacterial cells and modified to methyl pyropheophorbide-a. The 3-vinyl-chlorin was transformed to zinc complex of the corresponding 3-acetyl-porphyrin. The zinc porphyrin was oxidized to give cis-7,8- and 17,18-dihydroxy-chlorins as well cis-7,8-cis-17,18-tetrahydroxybacteriochlorin. After zinc-demetallation, the isolated cis-7,8- and 17,18-diols were reduced at the 3-acetyl group and triply dehydrated under acidic conditions to afford two regioisomeric 3-vinyl-porphyrins, methyl divinyl-pyroprotopheophorbide-a possessing the 8-vinyl group and 17-propionate residue (one of the divinyl-protoChl-a derivatives) and methyl pyropheophorbide-c 1 possessing the 8-ethyl group and 17-acrylate residue (one of the Chl-c 1 derivatives), respectively. The resulting 7,8,17,18-tetrol was reduced and then acidically treated, giving five-fold dehydrated free base porphyrin, methyl pyropheophorbide-c 2 possessing the 3,8-divinyl groups and 17-acrylate residue (one of the Chl-c 2 derivatives). The visible absorption and fluorescence emission spectra of the three semi-synthetic 3-vinyl-porphyrins in dichloromethane were compared with those of the corresponding 8-ethyl-porphyrin bearing the 17-propionate residue, methyl pyroprotopheophorbide-a (one of the protoChl-a derivatives). The Soret and Qy absorption maxima were shifted to longer wavelengths with an increase of π-conjugation in a molecule: protoChl-a (8-CH2CH3/17-CH2CH2COOCH3) < divinyl-protoChl-a (8-CH=CH2/17-CH2CH2COOCH3) < Chl-c 1 (8-CH2CH3/17-CH=CHCOOCH3) < Chl-c 2 derivatives (8-CH=CH2/17-CH=CHCOOCH3). The 17(1),17(2)-dehydrogenation broadened the absorption bands. The emission maxima were bathochromically shifted in the same order. The reaction mechanism of the present dehydration indicates that the biosynthetic pathway of Chls-c would include the hydroxylation of the 17-propionate reside at the 17(1)-position and successive dehydration to the 17-acrylate residue.
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Clorofila/biossíntese , Clorofila/metabolismo , Acrilatos/metabolismo , Vias Biossintéticas , Clorofila/análogos & derivados , Clorofila/química , Clorofila A , Fenômenos Ópticos , Espectrometria de FluorescênciaRESUMO
A methyl group at the 2-position of methyl mesopyropheophorbide-a was transformed to the 2-formyl group to give methyl mesopyropheophorbide-f, one of the chlorophyll-f analogs. The 2-formylation moved the redmost electronic absorption band in a solution to a longer wavelength and the bathochromic shift was comparable to that by the 3-formylation. Zinc complex of the synthetic compound in solutions showed similar visible absorption spectra as those of naturally occurring chlorophyll-f.