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1.
Inorg Chem ; 63(2): 1414-1426, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38166391

RESUMO

Reevaluating the composition of the double metal cyanide catalyst (DMC) as a salt of (NC)6Co3- anions with 1:1 Zn2+/(X)Zn+ cations (X = Cl, RO, AcO), we prepared a series of well-defined DMCs, [ClZn+][Zn2+][(NC)6Co3-][ROH], [(RO)Zn+][Zn2+][(NC)6Co3-], [(AcO)Zn+][Zn2+][(NC)6Co3-], [(RO)Zn+]p[ClZn+](1-p)[Zn2+][(NC)6Co3-], [(AcO)Zn+]p[(tBuO)Zn+]q[Zn2+][(NC)6Co3-], and [(AcO)Zn+]p[(tBuO)Zn+]q[ClZn+]r[Zn2+][(NC)6Co3-]. The structure of [(MeOC3H6O)Zn+][Zn2+][(NC)6Co3-] was precisely determined at the atomic level through Rietveld refinement of the synchrotron X-ray powder diffraction data. By evaluating the catalyst's performance in both propylene oxide (PO) polymerization and PO/CO2 copolymerization, a correlation between structure and performance was established on various aspects including activity, dispersity, unsaturation level, and carbonate fraction in the resulting polyols. Ultimately, our study identified highly efficient catalysts that outperformed the state-of-the-art benchmark DMC not only in PO polymerization [DMC-(OAc/OtBu/Cl)(0.59/0.38/0.15)] but also in PO/CO2 copolymerization [DMC-(OAc/OtBu)(0.95/0.08)].

2.
Int J Mol Sci ; 24(8)2023 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-37108832

RESUMO

The efficiency of plasma surface modifications depends on the operating conditions. This study investigated the effect of chamber pressure and plasma exposure time on the surface properties of 3Y-TZP with N2/Ar gas. Plate-shaped zirconia specimens were randomly divided into two categories: vacuum plasma and atmospheric plasma. Each group was subdivided into five subgroups according to the treatment time: 1, 5, 10, 15, and 20 min. Following the plasma treatments, we characterized the surface properties, including wettability, chemical composition, crystal structure, surface morphology, and zeta potential. These were analyzed through various techniques, such as contact angle measurement, XPS, XRD, SEM, FIB, CLSM, and electrokinetic measurements. The atmospheric plasma treatments increased zirconia's electron donation (γ-) capacity, while the vacuum plasma treatments decreased γ- parameter with increasing times. The highest concentration of the basic hydroxyl OH(b) groups was identified after a 5 min exposure to atmospheric plasmas. With longer exposure times, the vacuum plasmas induce electrical damage. Both plasma systems increased the zeta potential of 3Y-TZP, showing positive values in a vacuum. In the atmosphere, the zeta potential rapidly increased after 1 min. Atmospheric plasma treatments would be beneficial for the adsorption of oxygen and nitrogen from ambient air and the generation of various active species on the zirconia surface.


Assuntos
Pressão Atmosférica , Zircônio , Cerâmica/química , Teste de Materiais , Propriedades de Superfície , Molhabilidade , Ítrio , Zircônio/química
3.
Int J Mol Sci ; 24(19)2023 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-37834109

RESUMO

Melanogenesis, the intricate process of melanin synthesis, is central to skin pigmentation and photoprotection and is regulated by various signaling pathways and transcription factors. To develop potential skin-whitening agents, we used B16F1 melanoma cells to investigate the inhibitory effects of anhydrous alum on melanogenesis and its underlying molecular mechanisms. Anhydrous alum (KAl(SO4)2) with high purity (>99%), which is generated through the heat-treatment of hydrated alum (KAl(SO4)2·12H2O) at 400 °C, potentiates a significant reduction in melanin content without cytotoxicity. Anhydrous alum downregulates the master regulator of melanogenesis, microphthalmia-associated transcription factor (MITF), which targets key genes involved in melanogenesis, thereby inhibiting α-melanocyte-stimulating hormone (α-MSH)-induced melanogenesis. Phosphorylation of the cAMP response element-binding protein, which acts as a co-activator of MITF gene expression, is attenuated by anhydrous alum, resulting in compromised MITF transcription. Notably, anhydrous alum promoted extracellular signal-regulated kinase phosphorylation, leading to the impaired nuclear localization of MITF. Overall, these results demonstrated the generation and mode of action of anhydrous alum in B16F1 cells, which constitutes a promising option for cosmetic or therapeutic use.


Assuntos
Melaninas , alfa-MSH , Melaninas/metabolismo , alfa-MSH/metabolismo , Monofenol Mono-Oxigenase/metabolismo , Fator de Transcrição Associado à Microftalmia/genética , Fator de Transcrição Associado à Microftalmia/metabolismo , Linhagem Celular Tumoral
4.
Int J Mol Sci ; 23(6)2022 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-35328427

RESUMO

Plasma surface treatment can be an attractive strategy for modifying the chemically inert nature of zirconia to improve its clinical performance. This study aimed to clarify the effect of plasma gas compositions on the physicochemical surface modifications of 3 mol% yttria-stabilized zirconia (3Y-TZP). The cold, atmospheric plasma discharges were carried out by using four different plasma gases, which are He/O2, N2/Ar, N2, and Ar from an application distance of 10 mm for 60 s. Static contact angles were measured to define the surface free energy. Changes in elemental composition, surface crystallinity, and surface topography were assessed with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), confocal laser scanning microscopy (CLSM), and scanning electron microscopy (SEM), respectively. A significant decrease in water contact angle was observed in all plasma groups with the lowest value of 69° in the N2/Ar group. CLSM and SEM investigations exhibited no morphological changes in all plasma groups. XPS revealed that a reduction in the surface C content along with an increase in O content was pronounced in the case of N2/Ar compared to others, which was responsible for high hydrophilicity of the surface. XRD showed that the changes in crystallite size and microstrain due to oxygen atom displacements were observed in the N2/Ar group. The N2/Ar plasma treatment may contribute to enhancing the bioactivity as well as the bonding performance of 3Y-TZP by controlling the plasma-generated nitrogen functionalities.


Assuntos
Gases em Plasma , Ítrio , Cerâmica/química , Teste de Materiais , Microscopia Eletrônica de Varredura , Propriedades de Superfície , Difração de Raios X , Ítrio/química , Zircônio/química
5.
Phys Chem Chem Phys ; 21(4): 1737-1749, 2019 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-30623958

RESUMO

Self-emitting blue and red EuOX (X = F, Cl, Br, and I) were successfully synthesized and characterized. Far-infrared and Raman measurements revealed that the vibration modes prominently reflected the Eu-O and Eu-X bond characters of these materials. X-ray photoelectron spectroscopy (XPS) of the red-emitting EuOX compounds showed that Eu exclusively existed as Eu3+, while in the blue-emitting EuOX, a mixed Eu3+/Eu2+ state was observed. For the red-emitting EuOX (X = F, Cl, and Br), the maximum wavelengths of the charge-transfer (CT) bands were red-shifted: F → Cl → Br (282, 320, and 330 nm for F, Cl, and Br, respectively). Using one-electron spin-polarized band structure calculations, it was verified that the red-shift of the CT energy from F to Br in EuOX was mainly due to the relative positions of the halogen orbital energies being gradually increased, following the trend in their electronegativity. For the blue-emitting EuOX (X = Cl, Br, and I), the emission band maxima were red-shifted from Cl to I (409, 414, and 432 nm for Cl, Br, and I, respectively), which was quite opposite to the trend predicted based on the spectrochemical series in crystal field theory, which was in good agreement with the previous results of the calculated 5d → 4f transition energies of the Eu2+ activator based on the crystal field theory. Through photoluminescence, UV-visible absorbance, and XPS, it was elucidated that the red emission due to Eu3+ was strongly masked by the intensified blue emission associated with the small amount of Eu2+ in the blue-emitting EuOX (X = Cl, Br, and I). These materials may provide a platform for modeling new phosphors for application in solid-state lighting.

6.
Inorg Chem ; 56(20): 12116-12128, 2017 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-28949134

RESUMO

Blue-emitting Ca2-xMgxSiO4:Ce (0.0 ≤ x ≤ 1.0) phosphors were successfully synthesized and characterized. Rietveld refinement revealed that four main phases exist within the solid-solution range of CaO-MgO-SiO2, namely, ß-Ca2SiO4 (Mg (x) = 0.0), Ca14Mg2(SiO4)8 (Mg (x) = 0.25), Ca3Mg(SiO4)2 (Mg (x) = 0.5), and CaMgSiO4 (Mg (x) = 1.0). The variation of the IR modes was more prominent with increasing Mg2+ content in the Ca2-xMgxSiO4 materials. The sharing of O atoms of the SiO4-tetrahedra by the MgO6-octahedra induced weakening of the Si-O bonds, which resulted in the red shift of the [SiO4] internal modes and appearance of a Mg-O stretching vibration at ∼418 cm-1. Raman measurement revealed that the change of the Ca-O bond lengths because of the Mg2+-substitution directly reflected the frequency shift of the Si-O stretching-Raman modes. Notably, the thermal stability of Ca2-xMgxSiO4:Ce (Mg (x) > 0.0) phosphors was superior to that of ß-Ca2SiO4:Ce (Mg (x) = 0.0) as confirmed by temperature-dependent photoluminescence (PL) measurements. This indicated that Mg2+ ions play an important role in enhancement of the thermal stability. In combination with the results from PL and electroluminescence (EL), it was elucidated that the luminous efficiency of Ca2-xMgxSiO4:Ce (Mg (x) = 0.1) was approximately twice as much as ß-Ca2SiO4:Ce (Mg (x) = 0.00), directly indicating a "Mg2+-substitution effect". The large enhancements of PL, EL, and thermal stability because of Mg2+-substitution may provide a platform in the discovery of more efficient phosphors for NUV-LEDs.

7.
Proc Natl Acad Sci U S A ; 111(2): 599-604, 2014 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-24379365

RESUMO

Sodium ion batteries offer promising opportunities in emerging utility grid applications because of the low cost of raw materials, yet low energy density and limited cycle life remain critical drawbacks in their electrochemical operations. Herein, we report a vanadium-based ortho-diphosphate, Na7V4(P2O7)4PO4, or VODP, that significantly reduces all these drawbacks. Indeed, VODP exhibits single-valued voltage plateaus at 3.88 V vs. Na/Na(+) while retaining substantial capacity (>78%) over 1,000 cycles. Electronic structure calculations reveal that the remarkable single plateau and cycle life originate from an intermediate phase (a very shallow voltage step) that is similar both in the energy level and lattice parameters to those of fully intercalated and deintercalated states. We propose a theoretical scheme in which the reaction barrier that arises from lattice mismatches can be evaluated by using a simple energetic consideration, suggesting that the presence of intermediate phases is beneficial for cell kinetics by buffering the differences in lattice parameters between initial and final phases. We expect these insights into the role of intermediate phases found for VODP hold in general and thus provide a helpful guideline in the further understanding and design of battery materials.


Assuntos
Difosfatos/química , Fontes de Energia Elétrica , Compostos de Vanádio/química , Cristalografia , Eletroquímica , Cinética , Modelos Teóricos , Difração de Raios X
8.
Inorg Chem ; 55(17): 8359-70, 2016 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-27494550

RESUMO

Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

9.
Ann Surg Oncol ; 22(3): 765-71, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-25201506

RESUMO

BACKGROUND: In TNM staging system, lymph node staging is based on the number of metastatic lymph nodes in gastric cancer and micrometastasis is not considered. Several reports proposed the importance of lymph node micrometastasis as the causative factor for recurrence and poor survival, but it remains controversial among researchers. METHODS: A total of 482 gastric cancer patients who underwent curative resection from 2004 to 2010 at Korea University Medical Center Ansan Hospital, South Korea were prospectively enrolled. For detecting lymph node micrometastasis, immunohistochemical staining with anti-cytokeratin antibody (CAM 5.2) was performed on negative lymph nodes by hematoxylin-eosin (H-E) staining. Survival differences were compared between conventional node staging and new node staging that took micrometastasis into consideration. Also, the prognostic value of lymph node micrometastasis was investigated in multivariate analysis. RESULTS: A total of 156 patients (32.4%) showed lymph node micrometastasis. Overall, the micrometastatic group had more advanced tumor and lymph node stage, lymphovascular cancer cell invasion, a higher rate of recurrence, and poor survival. Furthermore, when the cumulative numbers of macro- and micrometastatic lymph nodes were calculated together, the discriminative power of survival difference between each node stage became more stratified. Also, multivariate analysis using Cox's proportional hazards model demonstrated perineural invasion, pathologic T stage, dissected lymph nodes, macro- and micrometastatic lymph nodes are independent prognostic factors. CONCLUSIONS: Lymph node micrometastasis was clinically significant as a risk factor for recurrent gastric cancer. Lymph node micrometastasis should be considered when estimating TNM stage for determining prognosis and the best treatment strategy.


Assuntos
Adenocarcinoma Mucinoso/secundário , Adenocarcinoma/secundário , Carcinoma Papilar/secundário , Carcinoma de Células em Anel de Sinete/secundário , Linfonodos/patologia , Recidiva Local de Neoplasia/patologia , Neoplasias Gástricas/patologia , Adenocarcinoma/mortalidade , Adenocarcinoma/cirurgia , Adenocarcinoma Mucinoso/mortalidade , Adenocarcinoma Mucinoso/cirurgia , Adulto , Idoso , Idoso de 80 Anos ou mais , Carcinoma Papilar/mortalidade , Carcinoma Papilar/cirurgia , Carcinoma de Células em Anel de Sinete/mortalidade , Carcinoma de Células em Anel de Sinete/cirurgia , Feminino , Seguimentos , Humanos , Linfonodos/cirurgia , Metástase Linfática , Masculino , Pessoa de Meia-Idade , Invasividade Neoplásica , Micrometástase de Neoplasia , Recidiva Local de Neoplasia/mortalidade , Recidiva Local de Neoplasia/cirurgia , Estadiamento de Neoplasias , Prognóstico , Estudos Prospectivos , Fatores de Risco , Neoplasias Gástricas/mortalidade , Neoplasias Gástricas/cirurgia , Taxa de Sobrevida
10.
Inorg Chem ; 54(4): 1325-36, 2015 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-25581600

RESUMO

Novel LiCe9(SiO4)6O2 and LiTb9(SiO4)6O2 compounds have been successfully synthesized, and the site selectivity and occupancy of activator ions have been estimated including LiEu9(SiO4)6O2 compound. The rare earth (RE) fully occupied compounds, as well as the RE partially occupied congeners are required for the assessment of site selectivity of RE (activator) ions in apatite-type compounds. The splitting energies of the 6H and 4F Wycoff positions of LiRE9(SiO4)6O2 (RE = Ce, Eu, and Tb) compounds are calculated based on crystal field theory: ΔECe(6H) = 3849.3 cm(-1), ΔECe(4F) = 4228.1 cm(-1), ΔEEu(6H) = 3870.0 cm(-1), ΔEEu(4F) = 4092.8 cm(-1), ΔETb(6H) = 3637.6 cm(-1), ΔETb(4F) = 4396.1 cm(-1), indicating that the splitting energy for the 4F site is larger than that for the 6H site in all compounds; thus the absorption energy is higher for the 6H site. In apatite-type LiRE9(SiO4)6O2 (RE = Ce, Eu, and Tb) compounds, the Ce(3+) ions predominantly occupy the 4F site associated with the absorption band around 300 nm at lower Ce(3+) concentration, and then enter the 6H site associated the absorption band around 245 nm. For the Eu(3+)-doped compounds, the 4F site and 6H site are mixed within the charge transfer band (CTB) between 220 and 350 nm. Eu(3+) ions initially preferentially occupy the 6H site (around 290 nm) at lower Eu(3+) concentration and subsequently enter the 4F site (around 320 nm) with increasing Eu(3+) concentration. For the Tb(3+)-doped compounds, the absorption due to the two different sites is mixed within f-d absorption band between 200 and 300 nm. At lower Tb(3+) concentration, the Tb(3+) ions enter favorably 6H site around 240 nm and then enter 4F site around 270 nm. These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

11.
ScientificWorldJournal ; 2014: 936319, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25374943

RESUMO

There has been an explosive increase in the population of the OSN (online social network) in recent years. The OSN provides users with many opportunities to communicate among friends and family. Further, it facilitates developing new relationships with previously unknown people having similar beliefs or interests. However, the OSN can expose users to adverse effects such as privacy breaches, the disclosing of uncontrolled material, and the disseminating of false information. Traditional access control models such as MAC, DAC, and RBAC are applied to the OSN to address these problems. However, these models are not suitable for the dynamic OSN environment because user behavior in the OSN is unpredictable and static access control imposes a burden on the users to change the access control rules individually. We propose a dynamic trust-based access control for the OSN to address the problems of the traditional static access control. Moreover, we provide novel criteria to evaluate trust factors such as sociological approach and evaluate a method to calculate the dynamic trust values. The proposed method can monitor negative behavior and modify access permission levels dynamically to prevent the indiscriminate disclosure of information.


Assuntos
Redes Comunitárias/estatística & dados numéricos , Segurança Computacional , Modelos Estatísticos , Apoio Social , Confiança , Redes Comunitárias/ética , Amigos , Humanos , Privacidade
12.
Int J Antimicrob Agents ; 64(2): 107216, 2024 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-38795926

RESUMO

The emergence of multidrug-resistant pathogens has outpaced the development of new antibiotics, leading to renewed interest in endolysins. Endolysins have been investigated as novel biocontrol agents for Gram-positive bacteria. However, their efficacy against Gram-negative species is limited by the barrier presented by their outer membrane, which prevents endolysin access to the peptidoglycan substrate. Here, we used the translocation domain of botulinum neurotoxin to deliver endolysin across the outer membrane of Gram-negative bacteria. The translocation domain selectively interacts with and penetrates membranes composed of anionic lipids, which have been used in nature to deliver various proteins into animal cells. In addition to the botulinum neurotoxin translocation domain, we have fused bacteriophage-derived receptor binding protein to endolysins. This allows the attached protein to efficiently bind to a broad spectrum of Gram-negative bacteria. By attaching these target-binding and translocation machineries to endolysins, we aimed to develop an engineered endolysin with broad-spectrum targeting and enhanced antibacterial activity against Gram-negative species. To validate our strategy, we designed engineered endolysins using two well-known endolysins, T5 and LysPA26, and tested them against 23 strains from six species of Gram-negative bacteria, confirming that our machinery can act broadly. In particular, we observed a 2.32 log reduction in 30 min with only 0.5 µM against an Acinetobacter baumannii isolate. We also used the SpyTag/SpyCatcher system to easily attach target-binding proteins, thereby improving its target-binding ability. Overall, our newly developed endolysin engineering strategy may be a promising approach to control multidrug-resistant Gram-negative bacterial strains.

13.
J Nanosci Nanotechnol ; 13(4): 2814-8, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23763165

RESUMO

KMn8O16 nanorods were prepared through a facile hydrothermal method by using KMnO4 and MnSO4 as reactants. The KMn8O16 samples synthesized at different temperatures (100-160 degrees C) were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and its electrochemical properties were tested by galvanostatic charge/discharge system. The effect of reaction temperature on the morphology and electrochemical properties was investigated. As electrode materials for the lithium ion battery cycled between 1.5 and 4.2 V, the KMn8O16 nanorods synthesized at 160 degrees C show the highest reversible discharge capacity (160.1 mA h/g even after 50 cycles at current density of 50 mA/g) and the best cycling stability. These results indicate that the KMn8O16 nanorods could be a promising cathode material for lithium ion batteries.

14.
Acta Crystallogr Sect E Struct Rep Online ; 69(Pt 6): i34, 2013 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-23794965

RESUMO

Polycrystalline tris-odium vanadium(III) nitridotriphosphate, Na3V(PO3)3N, was prepared by thermal nitridation of a mixture of NaPO3 and V2O5. The title compound is isotypic with Na3Al(PO3)3N. In the crystal, the P-atom and the three O-atom sites are on general positions, whereas the Na-, V- and N-atom sites are located on threefold rotation axes. The P atom is coordinated by three O atoms and one N atom in form of a slightly distorted tetra-hedron. Three PO3N tetra-hedra build up a nitridotriphosphate group, (PO3)3N, by sharing a common N atom. The V atom is coordinated by six O atoms in form of a slightly distorted octa-hedron. The Na(+) ions occupy three crystallographically distinct sites. One Na(+) ion is situated in an irregular polyhedral coordination environment composed of six O atoms and one N atom, while the other two Na(+) cations are surrounded by six and nine O atoms, respectively.

15.
J Surg Oncol ; 106(4): 456-61, 2012 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-22422271

RESUMO

BACKGROUNDS AND OBJECTIVES: The male predominance of gastric cancer suggests that female sex hormones may have a protective effect against gastric cancer. We evaluated the expression of estrogen receptors in gastric cancer tissue and cells and the clinical significance of ER-ß expression in gastric cancer. METHOD: ER-α, ER-ß proteins extracted from normal stomach, gastric cancer tissues, and cultured gastric cancer cells (KATO-III, mkn28, mkn45, and mkn74) were assessed by Western blot analysis. The clinical significance of ER-ß was explored using tissue microarray methods and immunohistochemical staining of specimens from 148 gastric cancers. RESULTS: Both ER-α and ß protein expression were noted in normal and gastric cancer tissues. However, in cultured gastric cells, only ER-ß was noted in mkn28 and mkn74. Of 148 gastric cancers, 67 (45.3%) were ER-ß positive. The ER-ß positive group was associated with lower tumor stage, Lauren's intestinal type, negative perineural invasion, and free of recurrence. The ER-ß positive group had a better 3-year survival compared with the negative group in survival analysis. CONCLUSION: Our results suggest that the presence of ER-ß in gastric cancer could have a protective effect against invasiveness of gastric cancer. Further studies are needed to clarify the role of ER-ß in gastric cancers.


Assuntos
Receptor beta de Estrogênio/análise , Neoplasias Gástricas/química , Adulto , Idoso , Western Blotting , Linhagem Celular Tumoral , Receptor alfa de Estrogênio/análise , Receptor beta de Estrogênio/fisiologia , Feminino , Humanos , Imuno-Histoquímica , Masculino , Pessoa de Meia-Idade , Recidiva Local de Neoplasia , Prognóstico , Neoplasias Gástricas/patologia , Análise Serial de Tecidos
16.
Inorg Chem ; 51(19): 10222-32, 2012 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-22963192

RESUMO

The thermal behavior of gadolinium hydroxychloride (Gd(2)(OH)(5)Cl·nH(2)O, LGdH) has been closely studied to provide the important factors that should be considered for its high temperature applications. Combined analyses of thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS) showed that, under atmospheric air with a considerable amount of water, the decomposition of LGdH to Gd(2)O(3) is completed at 1050 °C. However, in either dry air or Ar gas, the transformation continued up to around 1300 °C. Thus, the thermal decomposition of LGdH was more influenced by H(2)O than by O(2). FT-IR spectra and X-ray diffraction (XRD) patterns were used to study LGdHs calcined at high temperatures (up to at least 600 °C). Calcined LGdH's ability to intercalate anions into the interlayer space could be recovered by the reconstruction of intralayer structure through rehydration and rehydroxylation. These processes were significantly accelerated at elevated temperatures. The recovery behavior of LGdH was examined in different anionic solutions at different temperatures.

17.
J Microbiol Biotechnol ; 32(11): 1471-1478, 2022 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-36437520

RESUMO

2'-Fucosyllactose (2'-FL), the most abundant fucosylated oligosaccharide in human milk, has multiple beneficial effects on human health. However, its biosynthesis by metabolically engineered Escherichia coli is often hampered owing to the insolubility and instability of α-1,2-fucosyltransferase (the rate-limiting enzyme). In this study, we aimed to enhance 2'-FL production by increasing the expression of soluble α-1,2-fucosyltransferase from Helicobacter pylori (FucT2). Because structural information regarding FucT2 has not been unveiled, we decided to improve the expression of soluble FucT2 in E. coli via directed evolution using a protein solubility biosensor that links protein solubility to antimicrobial resistance. For such a system to be viable, the activity of kanamycin resistance protein (KanR) should be dependent on FucT2 solubility. KanR was fused to the C-terminus of mutant libraries of FucT2, which were generated using a combination of error-prone PCR and DNA shuffling. Notably, one round of the directed evolution process, which consisted of mutant library generation and selection based on kanamycin resistance, resulted in a significant increase in the expression level of soluble FucT2. As a result, a batch fermentation with the ΔL M15 pBCGW strain, expressing the FucT2 mutant (F#1-5) isolated from the first round of the directed evolution process, resulted in the production of 0.31 g/l 2'-FL with a yield of 0.22 g 2'-FL/g lactose, showing 1.72- and 1.51-fold increase in the titer and yield, respectively, compared to those of the control strain. The simple and powerful method developed in this study could be applied to enhance the solubility of other unstable enzymes.


Assuntos
Escherichia coli , Fucosiltransferases , Humanos , Fucosiltransferases/genética , Resistência a Canamicina , Escherichia coli/genética , Trissacarídeos
18.
Materials (Basel) ; 15(24)2022 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-36556732

RESUMO

Residual oxygen in wurtzite-type aluminum nitride (AlN) crystal, which significantly affects phonon transport and crystal growth, is crucial to thermal conductivity and the crystal quality of AlN ceramics. In this study, the effect of residual oxygen on the lattice of AlN was examined for as-synthesized and sintered samples. By controlling reaction time in the carbothermal reduction nitridation (CRN) procedure, AlN powder was successfully synthesized, and the amount of residual oxygen was systematically controlled. The evolution of lattice parameters of AlN with respect to oxygen conc. was carefully investigated via X-ray diffraction analysis. With increasing amounts of residual oxygen in the as-synthesized AlN, lattice expansion in the ab plane was induced without a significant change in the c-axis lattice parameter. The lattice expansion in the ab plane owing to the residual oxygen was also confirmed with high-resolution transmission electron microscopy, in contrast to the invariant lattice parameter of the sintered AlN phase. Micro-strain values from XRD peak broadening confirm that stress, induced by residual oxygen, expands the AlN lattice. In this work, the lattice expansion of AlN with increasing residual oxygen was elucidated via X-ray diffraction and HR-TEM, which is useful to estimate and control the lattice oxygen in AlN ceramics.

19.
Enzyme Microb Technol ; 153: 109914, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34670187

RESUMO

Directed evolution is widely used to optimize protein folding and solubility in cells. Although the screening and selection of desired mutants is an essential step in directed evolution, it generally requires laborious optimization and/or specialized equipment. With a view toward designing a more practical procedure, we previously developed an inducible plasmid display system, in which the intein (auto-processing) and Oct-1 DNA-binding (DBD) domains were used as the protein trans-splicing domain and DNA-binding module, respectively. Specifically, the N-terminal (CfaN) and C-terminal (CfaC) domains of intein were fused to the C-terminal end of the His-tag and the N-terminal end of Oct-1 DBD to generate His6-CfaN and CfaC-Oct-1, respectively. For such a system to be viable, the efficiency of protein trans-splicing without the protein of interest (POI) should be maximized, such that the probability of occurrence is solely dependent on the solubility of the POI. To this end, we initially prevented the degradation of l-arabinose (the inducer of the PBAD promoter) by employing an Escherichia coli host strain deficient in the metabolism of l-arabinose. Given that a low expression of His6-CfaN, compared with that of CfaC-Oct-1, was found to be conducive to the generation to a soluble product of the protein trans-splicing event, we designed the expression of His6-CfaN and CfaC-Oct-1 to be inducible from the PBAD and PT7 promoters, respectively. The optimized system thus obtained enabled in vitro selection of the plasmid-protein complex with high yield. We believe that the inducible plasmid display system developed in this study would be applicable to high-throughput screening and/or selection of protein variants with enhanced solubility.


Assuntos
Ensaios de Triagem em Larga Escala , Trans-Splicing , Plasmídeos/genética
20.
J Surg Res ; 171(2): 657-62, 2011 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-20934721

RESUMO

BACKGROUND: The objective of this study was to compare the chemosensitivity of primary tumor and metastasized lymph node from patient with gastric adenocarcinoma. MATERIALS AND METHODS: We studied 26 gastric cancer patients with lymph node metastasis who underwent gastric resection at the Korea University Guro Hospital from Feb 2007 to July 2008. The chemosensitivity of primary tumor and metastatic lymph node were studied using an adenosine triphosphate-based chemotherapy response assay (ATP-CRA). RESULTS: The concordance rate of the ATP-CRA test was 30.8% (8/26). The concordance rate between primary tumor and metastatic N2 group lymph node was only 9.1% (1/11). The metastatic tumor inhibition rates with 5-fluorouracil, cisplatin, doxorubicin, and oxaliplatin were higher than the inhibition rates for primary tumor. Tumor inhibition rates was significantly different between primary tumor and metastatic tumor after doxorubicin treatment (27.734±20.95 versus 38.403±26.87, P=0.021). We detected simple correlations of tumor inhibition rates between primary and metastatic tumors with cisplatin (r=0.661, P<0.001) and doxorubicin (r=0.475, P=0.031). CONCLUSIONS: We observed differences between first choice chemotherapeutic agents based on ATPCRA tests of primary tumor and metastatic tumor in lymph node. Therefore, chemotherapeutic agents should be carefully selected for adjuvant chemotherapy using a chemosensitivity test.


Assuntos
Adenocarcinoma/tratamento farmacológico , Adenocarcinoma/secundário , Quimioterapia Adjuvante/métodos , Neoplasias Gástricas/tratamento farmacológico , Neoplasias Gástricas/patologia , Adenocarcinoma/cirurgia , Adenocarcinoma Mucinoso/tratamento farmacológico , Adenocarcinoma Mucinoso/secundário , Adenocarcinoma Mucinoso/cirurgia , Trifosfato de Adenosina/farmacologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Antibióticos Antineoplásicos/farmacologia , Antimetabólitos Antineoplásicos/farmacologia , Carcinoma de Células em Anel de Sinete/tratamento farmacológico , Carcinoma de Células em Anel de Sinete/secundário , Carcinoma de Células em Anel de Sinete/cirurgia , Cisplatino/farmacologia , Doxorrubicina/farmacologia , Feminino , Fluoruracila/farmacologia , Humanos , Técnicas In Vitro , Metástase Linfática , Masculino , Pessoa de Meia-Idade , Compostos Organoplatínicos/farmacologia , Oxaliplatina , Neoplasias Gástricas/cirurgia
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