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Three different complexes, TMeQ[6]-TBT, Q[7]-TBT, and Q[8]-TBT are constructed by three different cucurbiturils and synthesized by guest melamine-cored Schiff bases (TBT) through outer-surface interaction and host-guest interactions. TBT forms a TMeQ[6]-TBT complex with TMeQ[6] through outer-surface interaction, while Q[7]-TBT and Q[8]-TBT form complexes with Q[7,8] through host-guest interactions. Among them, Q[7]-TBT is selected as a UV detector for the detection of silver ions (Ag+). This work makes full use of the characteristics of each cucurbituril and melamine-cored Schiff base to construct a series of complexes and these are applied to metal detection.
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Two helical Schiff base compounds (H4TPA and H4TPE) containing a triphenylamine (TPA) or tetraphenylethylene (TPE) scaffold were successfully synthesized and characterized. Both H4TPA and H4TPE exhibited typical aggregation-induced emission characteristics in the mixed solvent of THF/H2O. The two compounds also showed high selectivity and sensitivity for the recognition of Cu2+ over other ions in THF/HEPES (1:4, V/V, pH = 7.4, 2.0 × 10-5 M), and could be used as turn-off fluorescent probes for Cu2+. The stoichiometric ratios and association constants were estimated via Job's plots and UV-vis spectra titration, and the detection limits of H4TPA and H4TPE toward Cu2+ were calculated to be 2.41 × 10-7 M and 1.38 × 10-7 M, respectively. Besides, the crystal structure of the complex obtained from the interaction of H4TPA with Cu2+ well illustrated the binding modes, which helped us understand the Cu2+ recognition mechanism of H4TPA and H4TPE. Moreover, the detection of Cu2+ and spiked recovery experiments were carried out, which indicated that the two probes can be applied to Cu2+ detection in real samples with satisfactory recoveries.
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A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor-seco-cucurbit[10]uril (ns-Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ns-Q[10] assembly, an energy transfer process can occur from the TPEs@ns-Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ns-Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ns-Q[10] assembly and an energy transfer process can take place from the TPEs@ns-Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ns-Q[10]-RB-NiR and TPEs@ns-Q[10]-ESY system, we applied the TPEs@ns-Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ns-Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.
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pH plays a crucial part in numerous chemical and physiological processes. In this work, a new perylene diimide derivative that acts as a pH-sensitive dye with Bay Area Carboxylic Acid functionality. The derivative utilizes the outstanding thermal, chemical and photochemical stability found in PDI materials and has remarkable UV-visible absorption and fluorescence emission qualities. Based on these properties, a fluorescent probe (PCA) was synthesised using a perylene tetracarbodiimide (PDI) backbone for the recognition of alkaline pH. In alkaline environments where the pH values are between 10 and 14, the fluorescence intensity significantly decreases, and a blue shift occurs, which is a standard feature of alkaline pH probes. The probe demonstrates exceptional sensing ability within the pH range of 10.00-14.00, with notable stability and reversibility. Encapsulation of the probe in a thin polymer film material enhances the pH sensing capability of the system. New sensor has been developed to detect basic amino acids by utilizing the probes' pH response characteristics. this sensor has also been applied to detect the concentration of arginine.
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Interaction of the lanthanide nitrates M(NO3)3 (M = Gd, Eu) with methylcucurbit[5]uril (Me10Q[5]) in the presence of transition metal chlorides (ZnCl2 and FeCl3) in acidic media resulted in the isolation of the complexes [Me10Q[5]Gd(H2O)2Cl Gd(H2O)6](ZnCl4)2âClâ8.9H2O (1) and [Me10Q[5]Eu(H2O)3Cl(H3O)](FeCl4)3 (2). The molecular structures of 1 and 2 have been determined by single crystal X-ray crystallography, and reveal discrete complexes which are involved in dense stacking with adjacent Me10Q[5]s linked via H-bonding and/or metal anions resulting in a supramolecular assembly.
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OBJECTIVE: To examine maturational changes in expressions of Ophiocordyceps sinensis (O.sinensis) transition and transversion mutation genotypes in Cordyceps sinensis (C.sinensis) stroma. METHODS: MassARRAY single nucleotide polymorphism (SNP) matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrum genotyping was used, and 8 SNP extension primers were designed based on the scattered, multiple point mutations of known sequences for the O.sinensis mutants within their internal transcribed spacer (ITS) segments. Of the extension primers, 5 (not capable of distinguishing between the 2 AT-biased genotypes) located in rDNA ITS1 and ITS2 regions: 067721-211, 067721-240, 067721-477, 067721-531 and 067721-581. The other 3 extension primers located in 5.8S rDNA region: 067740-324, 067740-328 and 067740-360, to distinguish between the 2 AT-biased genotypes. RESULTS: MS chromatograms at the 8 SNP sites showed dynamic alterations of mutant alleles in C.sinensis stroma. The allele for the AT-biased genotypes at 067721-211 site showed higher peak height than its GC-biased counterpart in the premature C.sinensis stroma, but disappeared with C.sinensis maturation. Chromatograms displayed not only the transition mutation alleles, but also transversion mutants. Some of the transversion mutation alleles displayed higher peak heights than those for GC- and AT-biased alleles, but their peak heights and detection rates tended to be decreased with C.sinensis maturation. When distinguishing between the 2 AT-biases, AB067744 and AB067740 genotype alleles co-existed in the premature C.sinensis stroma. The allele peak height for AB067744 genotype was greatly decreased with C.sinensis maturation, while that for AB067740 genotype increased. CONCLUSION: Co-existence of at least 5 transition and transversion mutant genotypes of O.sinensis and the dynamic changes in their expressions in C.sinensis stroma along with C.sinensis maturation may be of extreme importance in C.sinensis stroma germination and maturation, enabling C.sinensis to complete its life cycle.
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Cordyceps/crescimento & desenvolvimento , Cordyceps/genética , DNA Fúngico/genética , Mutação Puntual , Polimorfismo de Nucleotídeo Único , Sequência de Bases , Genótipo , Dados de Sequência Molecular , Análise de Sequência de DNA , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por MatrizRESUMO
OBJECTIVE: To examine the mutants of Ophiocordyceps sinensis (Os) in the stroma of premature Cordyceps sinensis (Cs). METHODS: Used MassARRAY single nucleotide polymorphism (SNP) MALDI-TOF mass spectrum genotyping, designed eight SNP extension primers on the basis of the scattered, multiple point mutations of known Os mutants within their internal transcribed spacer (ITS) segments, and examined the Os mutant genotypes relating to the GC-biased Os genotype (gb #AB067721) in premature Cs stroma. RESULTS: The two AT-biased genotypes and the GC-biased Os were simultaneously detected in premature Cs stroma. SNP genotyping also detected at least two other Os genotypes of unknown sequences. CONCLUSION: Coexistence of the three known Os genotypes indicates the existence of possible transition point mutations within Os genes during germination and early maturation of Cs. Simultaneous detection of at least two unknown genotypes coexisting with those known mutants possibly evidences the transversion mutations within Os genes.
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Cordyceps/genética , Mutação Puntual , Polimorfismo de Nucleotídeo Único , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Sequência de Bases , Primers do DNA/genética , Genótipo , Dados de Sequência Molecular , Reação em Cadeia da Polimerase/métodos , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodosRESUMO
OBJECTIVE: To evaluate the clinical value of ultrasonography detecting the poster urethrovesical angle (PUVA) in diagnosis of stress urinary incontinence (SUI). METHODS: From Jan. 2006 to Dec. 2008, the PUVA in resting phase (PUVA-r) and stress phase (PUVA-s) between 84 patients with SUI and 100 healthy women were measured by color Doppler ultrasound, including 57 cases in SUI degree I, 22 cases in SUI degree II, 5 cases in SUI degree III. RESULTS: (1) The PUVA-r and PUVA-s were (130+/-29) degrees and (158+/-36) degrees in SUI patients, which were significantly higher (113+/-19) degrees and (115+/-23) degrees in control group (P<0.01). (2) Correlation analysis showed that PUVA-s was positively correlated with the severity of SUI (P<0.01). (3) The area under the receiver operating characteristic curves (ROC) of PUVA-s was 0.82 (95% CI: 0.76-0.89) between SUI patients and healthy women. When PUVA-s>or=140 degrees was chosed as the cut-off value, the specificity, accuracy rate and positive predictive value in diagnosis of SUI were 84%, 79%, 81%, which were significantly higher than those when cut-off value of PUVA-s>or=120 degrees (54%, 68%, 62%; P<0.05). CONCLUSION: The PUVA-s in SUI patients are significantly increased and is positively correlated with the severity of SUI, which are indicated that PUVA-s>or=140 degrees should be used as cut-off value in diagnosis of SUI by ultrasonography.
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Ultrassonografia Doppler em Cores , Uretra/diagnóstico por imagem , Bexiga Urinária/diagnóstico por imagem , Incontinência Urinária por Estresse/diagnóstico por imagem , Idoso , Feminino , Humanos , Pessoa de Meia-Idade , Curva ROC , Sensibilidade e Especificidade , Índice de Gravidade de Doença , Uretra/patologia , Bexiga Urinária/patologia , Incontinência Urinária por Estresse/patologiaRESUMO
OBJECTIVE: To investigate the roles of matrix metalloproteinase-9, -2 (MMP-9, 2), and tissue inhibitors of metalloproteinase-1, 2 (TIMP-1, 2) in pathogenesis of the accretio placenta. METHODS: The women with the placenta accrete were recruited and the placenta (23) and deciduas tissues (9) after labor were obtained, and the placenta (28) and deciduas (11) from women without the placenta accreta were obtained as control to get, too. The expressions of MMP-9, -2, TIMP-1, 2 in the placental and decidual tissues were analyzed by real-time PCR. RESULTS: mRNA expression of MMP-9 in the placenta accreta was (3.21 +/- 0.76) copies/microg total RNA, significantly higher (P < 0.05) than that of normal placenta [(3.84 +/- 0.24) copies/microg total RNA)]. MMP-9 transcription in the decidua accreta was (2.50 +/- 0.49) copies/microg total RNA, significantly higher (P < 0.05) than that of normal decidua [(3.81 +/- 0.66) copies/microg total RNA]. mRNA expression of TIMP-1 in normal placenta and placenta accreta was (5.91 +/- 0.56) and (5.92 +/- 0.46) copies/microg total RNA, respectively, with no significant difference between the two groups. mRNA expression of TIMP-1 in the accrete deciduas was (6.63 +/- 0.51) copies/microg total RNA, significantly lower (P < 0.05) than that of normal decidua (7.09 +/- 0.55) copies/microg. mRNA expression of MMP-2 in the accrete placenta was (4.55 +/- 1.13) copies/microg total RNA, significantly higher (P < 0.05) than that of normal placenta (5.53 +/- 0.59) copies/microg. mRNA expression of MMP-2 in the accrete decidua and normal decidua was (6.07 +/- 0.83) and (5.97 +/- 0.76) copies/microg total RNA, respectively, with no significant difference between the two groups. mRNA expression of TIMP-2 in the accrete placenta was (4.69 +/- 0.60) copies/microg total RNA, significantly higher (P < 0.05) than that of normal placenta (3.79 +/- 1.06) copies/microg. mRNA expression of TIMP-2 in the accrete decidua was (5.06 +/- 0.33) copies/microg total RNA, higher significantly (P < 0.05) than that of normal decidua (3.98 +/- 0.60) copies/microg. CONCLUSIONS: The upregulation of MMP-9, MMP-2 in placenta and downregulation of TIMP-1 in decidua were involved in occurrence of the placental accreta, and the roles of TIMP-2 in occurrence of the placental accreta need to elucidated.
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Metaloproteinases da Matriz/genética , Placenta Acreta/genética , Placenta/metabolismo , Inibidores Teciduais de Metaloproteinases/genética , Adulto , Decídua/metabolismo , Decídua/patologia , Feminino , Expressão Gênica , Humanos , Metaloproteinase 2 da Matriz/genética , Metaloproteinase 9 da Matriz/genética , Placenta/patologia , Reação em Cadeia da Polimerase/métodos , Gravidez , RNA Mensageiro/biossíntese , RNA Mensageiro/genética , Inibidor Tecidual de Metaloproteinase-1/genética , Inibidor Tecidual de Metaloproteinase-2/genéticaRESUMO
OBJECTIVE: To investigate the mechanisms underlying the effect of selenium dioxide (SeO(2)) on the proliferation, apoptosis, and apoptosis-related gene expressions of Bcl-2 and p53 in 3 leukemia cell lines NB4, K562 and HL-60. METHODS: The three leukemia cell lines were treated with 3, 10 and 30 mmol/L SeO(2) and apoptosis detected by flow cytometry and analysis of p53 and Bcl-2 expressions. RESULTS: SeO(2) at 10 and 30 mmol/L could inhibit the proliferation of three leukemia cell lines. SeO(2) treatment at 30 mmol/L for 48 h induced an apoptosis rate of 54.0 %, 46.5 %, 49.6 % in NB4, K562, and HL-60 cells respectively, and down-regulated Bcl-2 expression in NB4 and K562 but not in HL-60 cells. CONCLUSION: SeO(2) can induce apoptosis in NB4, K562 and HL-60 leukemia cells, involving the down-regulation of Bcl-2 and up-regulation of p53.
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Apoptose/efeitos dos fármacos , Leucemia/patologia , Proteínas Proto-Oncogênicas c-bcl-2/biossíntese , Compostos de Selênio/farmacologia , Proteína Supressora de Tumor p53/biossíntese , Antineoplásicos/farmacologia , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Células HL-60 , Humanos , Células K562 , Leucemia Promielocítica Aguda/patologia , Proteínas Proto-Oncogênicas c-bcl-2/genética , Óxidos de Selênio , Células Tumorais Cultivadas , Proteína Supressora de Tumor p53/genéticaRESUMO
OBJECTIVES/HYPOTHESIS: To investigate how quickly an allergic rhinitis (AR) patients' symptoms will improve with sublingual immunotherapy (SLIT). STUDY DESIGN: Double-blind placebo study. METHODS: This is a multicenter, randomized, double-blind, placebo-controlled study of SLIT used to treat house dust mite-induced AR. A total of 120 AR patients, aged 4 to 60 years, were treated for 6 months and randomized into two groups: 1) SLIT with Dermatophagoides pteronyssinus (D.p.) and Dermatophagoides farina (D.f.) extract (n = 60) ; and 2) matched placebo controls (n = 60). Symptom, medications received, and a visual analog scale score were recorded during the whole study. Serum-specific IgE and IgG4 to D. p. and D. f. were assessed before and after the treatment. RESULTS: Eighty-five patients (70.8%) completed the study. Twelve patients (20%) chose to withdraw from the SLIT group, but none because of serious adverse effects. The total symptom and visual analog scores VAS in the SLIT group decreased significantly when compared to the placebo controls (P <0.05) after week 14, as well as for the significant (P <0.05) improvement of all individual AR symptoms in the SLIT group (e.g., sneezing, nasal discharge, itching, and nasal obstruction) after week 22. There was a significant (P <0.05) increase of IgG4 to both D.f. and D.p. in the SLIT, but not in the placebo group after treatment. CONCLUSION: SLIT with a mixture of D.f. and D.p. extract is an effective and safe treatment for patients with house dust mite-induced AR. Its onset of action can be observed as early as 14 weeks after treatment.
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Alérgenos/administração & dosagem , Antígenos de Dermatophagoides/administração & dosagem , Dermatophagoides farinae/imunologia , Dermatophagoides pteronyssinus/imunologia , Dessensibilização Imunológica/métodos , Rinite Alérgica Perene/terapia , Administração Sublingual , Adolescente , Adulto , Alérgenos/uso terapêutico , Animais , Anticorpos Anti-Idiotípicos/sangue , Anticorpos Anti-Idiotípicos/imunologia , Antígenos de Dermatophagoides/uso terapêutico , Criança , Pré-Escolar , Relação Dose-Resposta a Droga , Método Duplo-Cego , Feminino , Humanos , Imunoglobulina A/imunologia , Imunoglobulina E/imunologia , Masculino , Pessoa de Meia-Idade , Rinite Alérgica , Rinite Alérgica Perene/sangue , Rinite Alérgica Perene/imunologia , Fatores de Tempo , Resultado do Tratamento , Adulto JovemRESUMO
OBJECTIVE: To investigate the clinical efficacy of subcutaneous immunotherapy (SCIT) and sublingual immunotherapy (SLIT) with standardized house dust mite (HDM) extract for persistent allergic rhinitis (PER). METHODS: Ninety-eight patients with moderate to severe PER caused by HDM and who completed SCIT (Alutard SQ, ALK-Abell¨®) or SLIT (Chanllergen-Df drops, Wolwo Pharma) regimen for two years were enrolled in this open-label controlled study. The patients were divided into two groups: SCIT group consisted of 40 patients aged 7 to 57 years old [(19.0 ± 2.7) years, x(-) ± s], and SLIT group consisted of 58 patients aged 6 to 50 years old [(17.7 ± 3.2) years]. The nasal symptoms (sneezing, rhinorrhea, nasal obstruction and pruritus) were evaluated using a four-point rating scale (from 0 = absent to 3 = severe) as well as 10 cm-visual analogue scale (VAS). Efficacy of SCIT and SLIT was assessed as the mean change from baseline in nasal symptom scores after 2-year course of immunotherapy, and the results were compared. SAS software version 9.1.3 was applied for statistical analysis. RESULTS: Both SCIT and SLIT significantly reduced the individual symptom score of sneezing, rhinorrhea, nasal obstruction and pruritus, and the total nasal symptom scores (including 4-point scale and VAS) after 2-year treatment when compared with the baseline (Z value were -3.14, -3.76, -3.09, -3.48, -4.13; -3.63, -3.21, -2.48, -3.56, -3.98, respectively, all P < 0.05). There was no significant difference in decreased mean score of the individual and total nasal symptoms (4-point scale) between SCIT and SLIT groups (Z value were -0.97, -0.67, -0.36, -0.04, -0.67, respectively, all P > 0.05). However, a significant reduction of VAS score of nasal obstruction was found in SCIT group after 2-year treatment, compared with SLIT group (t = -2.21, P = 0.032). There was no significant difference in decreased VAS score of three other nasal symptoms as well as global rhinitis severity between two immunotherapy groups (t value were -0.57, -1.93, -1.73, -0.99, respectively, all P > 0.05). CONCLUSIONS: Both SCIT and SLIT demonstrated clinical improvement in moderate to severe PER patients sensitized to HDM after two years treatment. It is suggested that SCIT may relieve nasal obstruction significantly; however, the overall clinical efficacy is consistent with SCIT and SLIT.
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Imunoterapia/métodos , Rinite Alérgica Perene/terapia , Administração Sublingual , Adolescente , Adulto , Alérgenos/imunologia , Animais , Criança , Feminino , Humanos , Injeções Subcutâneas , Masculino , Pessoa de Meia-Idade , Pyroglyphidae/imunologia , Resultado do Tratamento , Adulto JovemRESUMO
OBJECTIVE: To investigate the safety profile of subcutaneous immunotherapy (SCIT) versus sublingual immunotherapy (SLIT) in patients with allergic rhinitis (AR) caused by house dust mites. The treatment compliance and related factors were also evaluated. METHODS: A total of 160 patients with AR were enrolled in this study and received either SCIT (Alutard SQ, ALK-Abelló) or SLIT (Chanllergen-Df drops, Wolwo Pharma). All subjects were divided into two groups: SCIT group consisted of 81 patients aged 7 to 62 years [(21.5 ± 14.6) years, x ± s], and SLIT group consisted of 79 patients aged 6 to 53 years [(15.1 ± 10.3) years]. The selected patients were persistent and moderate to severe AR sensitized to Dermatophagoides pteronyssinus and Dermatophagoides farinae. Local and systemic reactions, as well as patient's adherence to the treatment, were carefully recorded and analyzed during the immunotherapy schedules (followed up for 6 months to 2 years). Statistical analysis was performed using a SPSS13.0 software. RESULTS: Local swelling commonly occurred following injections throughout the treatment duration (62.9% of overall injections) in the SCIT group. Oral itching associated with drop intakes was reported by 4 subjects (5.1%) in the SLIT group. All local reactions were mild, well tolerated and self-limiting in both groups. A total of 11 patients (13.6%) with 18 injections (0.9%) experienced systemic reactions in the SCIT group, involving respiratory distress, asthmatic attacks, and urticaria. These adverse effects were mostly immediate reactions, and occurred more frequently in patients during the maintenance phase of treatment. There were also 11 patients (13.9%) who experienced systemic reactions in the SLIT group, including gastrointestinal symptoms, urticaria, and rhinitis exacerbations. However, systemic reactions to SLIT were mainly observed in patients during the up-dosing phase of treatment. No significant difference in the overall incidence of systemic adverse effects was found between the SCIT and SLIT groups (13.6% and 13.9% respectively, χ(2) = 0.004, P > 0.05). There was only one case of non-life-threatening systemic reaction (severe asthma) in the SCIT group. Others were mild or moderate and no anaphylactic shock occurred in any group. No significant difference in treatment compliance was found between the SCIT and SLIT groups (86.4% and 79.7% respectively, χ(2) = 0.84, P > 0.05), with an overall rate of compliance (83.1%) among 160 patients. The most common cause for treatment withdrawal was insufficient ineffectiveness, in both groups of SCIT (6.2%) and SLIT (10.1%). CONCLUSION: The results suggest that the frequency of systemic adverse effects of SCIT is not significantly different from SLIT in mite-sensitized patients with AR, and both treatments are well tolerated and had favorable compliance during the study period.