Multimodal stimuli-responsive heterotelechelic poly(2-isopropyl-2-oxazoline) (TPE-PiPrOx-R6G) bearing tetraphenylethene (TPE) and rhodamine 6G (R6G) at the α and ω terminals, respectively, was synthesized. TPE-PiPrOx-R6G formed supramolecular polymeric micelles in aqueous solution with a critical micelle concentration of 0.19 g·L–1. Upon excitation at 310 nm, an aqueous solution of TPE-PiPrOx-R6G (1.00 g·L–1) exhibited a strong fluorescence emission at approximately 480 and 550 nm, which originated from the aggregation-induced emission of the TPE units and Förster resonance energy transfer from TPE to R6G, respectively. The aforementioned solution showed a phase transition behavior at 30 °C, and its fluorescence emission changed upon heating due to the phase transition of TPE-PiPrOx-R6G. Upon addition of γ-cyclodextrin (γ-CD), the cloud point temperature increased to 40 °C. Furthermore, the fluorescence emission of TPE-PiPrOx-R6G decreased due to the dissociation of the TPE units following their inclusion into γ-CD.
Background and Objectives The purpose of this study was to review the clinical characteristics and treatment outcomes of benign and malignant nasal septal tumors. Subjects and Method A total of 34 patients who underwent the treatment for nasal septal tumor between 2004 and 2015 were included in this study. Demographic characteristics, sinonasal chief complaints, size and localization of nasal septal tumor, imaging findings, surgical method, histopathologic results, treatment outcomes, and postoperative complications were reviewed. Results Of the 34 patients with nasal septal tumor used in this study, 22 (64.7%) had benign tumors and 12 (35.3%) had malignant tumors. The most common sinonasal complaint of both benign and malignant nasal septal tumors was nasal obstruction. The most common benign tumor was inverted papilloma (n=7), whereas the most common malignant tumors were malignant melanoma (n=2), plasmacytoma (n=2), and metastatic carcinoma (n=2). All patients except two cases underwent endoscopic tumor removal. There were 4 recurrences in malignant nasal septal tumors. There was no recurrence in benign tumors. No major complications resulting from surgical intervention were found. Conclusion Endoscopic surgery with complete excision is a safe and effective procedure for benign nasal septal tumors. Recurrence is more common in malignant nasal septal tumor. Therefore, long term follow-ups with regular radiologic and endoscopic examinations are necessary for patients with malignant nasal septal tumor. Key words: Neoplasms ã Transnasal endoscopic surgery ã Nasal septum ã Radiotherapy
A 25-year-old primigravida at 12 weeks gestation was referred for evaluation of edematous changes in one of two fetuses. The ultrasonographic findings included increased nuchal translucency (NT; 0.91 cm) with ascites and a pleural effusion, which were consistent with fetal hydrops. There was a single monochorionic diamniotic placenta. The results of an amniocentesis were 46, XY (normal karyotype) and 45, XO (Turner syndrome). On ultrasonography after the amniocentesis, the fetuses were shown to be of different genders. At 20 weeks 3 days, the hydropic changes had progressed, including the ascites, pleural effusion, and skin edema. After a thorough discussion of the condition of the fetus with the parents, the decision was made to discontinue the pregnancy. A 400 g non-viable male and a 670 g non-viable female were delivered. The male had no gross abnormalities, but the female showed severe hydropic changes. On pathologic examination, a monochorionic diamniotic placenta was confirmed. There have been reports that due to genetic defects in the embryo itself or embryo manipulation by assisted reproductive technology, twins have been diagnosed with a monochorionic placenta, but of different gender on prenatal ultrasonography. We managed twins who had been diagnosed prenatally as monochorionic, but were of different gender, which we report with a brief review of the literature.
Developing nonaggregated photosensitizers (PSs) for efficient photodynamic therapy (PDT) using polymeric micelles (PMs) has been challenging. In this study, axially substituted nonaggregated silicon tetrapyrazinoporphyrazine (SiTPyzPz) derivatives in carbohydrate-based block glycopolymer-based PMs were designed and used as PSs for PDT. To achieve the nonaggregated PSs, SiTPyzPz was axially substituted with trihexylsiloxy (THS) groups to form SiTPyzPz-THS, which exhibited highly monomeric behaviors in organic solvents. Moreover, three block copolymers were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization. Each copolymer comprised hydrophobic polystyrene blocks and loadable SiTPyzPz-THS, and one or two consisted of two possible hydrophilic blocks, polyethylene glycol or poly(glucosylethyl methacrylate). The self-assembly of SiTPyzPz-THS and the block copolymers in aqueous solvents induced the formation of spherical PMs with core–shell or core–shell–corona structures. The SiTPyzPz-THS in the PMs exhibited monomeric state, intense fluorescence emission, and outstanding singlet oxygen generation; moreover, it did not form aggregates. During the in vitro test, which was performed to investigate the PDT efficiency, the PMs, which consisted of poly(glucosylethyl methacrylate) shells, exhibited high photocytotoxicity and cellular internalization ability. Consequently, the PM systems of nonaggregated PSs and carbohydrate-based block copolymers could become very promising materials for PDT owing to their photophysicochemical properties and considerable selectivity against cancer cells.
Porphyrin derivatives are ubiquitous in nature and have important biological roles, such as in light harvesting, oxygen transport, and catalysis. Owing to their intrinsic π-conjugated structure, porphyrin derivatives exhibit characteristic photophysical and electrochemical properties. In biological systems, porphyrin derivatives are associated with various protein molecules through noncovalent interactions. For example, hemoglobin, which is responsible for oxygen transport in most vertebrates, consists of four subunits of a globular protein with an iron porphyrin derivative prosthetic group. Furthermore, noncovalently arranged porphyrin derivatives are the fundamental chromophores in light-harvesting systems for photosynthesis in plants and algae. These biologically important roles originate from the functional versatility of porphyrin derivatives. Specifically, porphyrins are excellent host compounds, forming coordination complexes with various metal ions that adds functionality to the porphyrin unit, such as redox activity and additional ligand binding at the central metal ion. In addition, porphyrins are useful building blocks for functional supramolecular assemblies because of their flat and symmetrical molecular architectures, and their excellent photophysical properties are typically utilized for the fabrication of bioactive functional materials. In this Account, we summarize our endeavors over the past decade to develop functional materials based on porphyrin derivatives using bioinspired approaches. In the first section, we discuss several synthetic receptors that act as artificial allosteric host systems and can be used for the selective detection of various chemicals, such as cyanide, chloride, and amino acids. In the second section, we introduce multiporphyrin arrays as mimics of natural light-harvesting complexes. The active control of energy transfer processes by additional guest binding and the fabrication of organic photovoltaic devices using porphyrin derivatives are also introduced. In the third section, we introduce several types of porphyrin-based supramolecular assemblies. Through noncovalent interactions such as metal-ligand interaction, hydrogen bonding, and π-π interaction, porphyrin derivatives were constructed as supramolecular polymers with formation of fiber or toroidal assembly. In the last section, the application of porphyrin derivatives for biomedical nanodevice fabrication is introduced. Even though porphyrins were good candidates as photosensitizers for photodynamic therapy, they have limitations for biomedical application owing to aggregation in aqueous media. We suggested ionic dendrimer porphyrins and they showed excellent photodynamic therapy (PDT) efficacy.
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