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1.
Nat Mater ; 23(1): 52-57, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-38052935

RESUMEN

Although metallic nanostructures have been attracting tremendous research interest in nanoscience and nanotechnologies, it is known that environmental attacks, such as surface oxidation, can easily initiate cracking on the surface of metals, thus deteriorating their overall functional/structural properties1-3. In sharp contrast, here we report that severely oxidized metallic glass nanotubes can attain an ultrahigh recoverable elastic strain of up to ~14% at room temperature, which outperform bulk metallic glasses, metallic glass nanowires and many other superelastic metals hitherto reported. Through in situ experiments and atomistic simulations, we reveal that the physical mechanisms underpinning the observed superelasticity can be attributed to the formation of a percolating oxide network in metallic glass nanotubes, which not only restricts atomic-scale plastic events during loading but also leads to the recovery of elastic rigidity on unloading. Our discovery implies that oxidation in low-dimensional metallic glasses can result in unique properties for applications in nanodevices.

2.
Biochem Biophys Res Commun ; 503(1): 195-201, 2018 09 03.
Artículo en Inglés | MEDLINE | ID: mdl-29864427

RESUMEN

Archaeal/fungal Rib7 and eubacterial RibG possess a reductase domain for ribosyl reduction in the second and third steps, respectively, of riboflavin biosynthesis. These enzymes are specific for an amino and a carbonyl group of the pyrimidine ring, respectively. Here, several crystal structures of Methanosarcina mazei Rib7 are reported at 2.27-1.95 Šresolution, which are the first archaeal dimeric Rib7 structures. Mutational analysis displayed that no detectable activity was observed for the Bacillus subtilis RibG K151A, K151D, and K151E mutants, and the M. mazei Rib7 D33N, D33K, and E156Q variants, while 0.1-0.6% of the activity was detected for the M. mazei Rib7 N9A, S29A, D33A, and D57N variants. Our results suggest that Lys151 in B. subtilis RibG, while Asp33 together with Arg36 in M. mazei Rib7, ensure the specific substrate recognition. Unexpectedly, an endogenous NADPH cofactor is observed in M. mazei Rib7, in which the 2'-phosphate group interacts with Ser88, and Arg91. Replacement of Ser88 with glutamate eliminates the endogenous NADPH binding and switches preference to NADH. The lower melting temperature of ∼10 °C for the S88E and R91A mutants suggests that nature had evolved a tightly bound NADPH to greatly enhance the structural stability of archaeal Rib7.


Asunto(s)
Proteínas Arqueales/metabolismo , Proteínas Bacterianas/metabolismo , Nucleótido Desaminasas/metabolismo , Oxidorreductasas/metabolismo , Riboflavina/biosíntesis , Deshidrogenasas del Alcohol de Azúcar/metabolismo , Secuencia de Aminoácidos , Sustitución de Aminoácidos , Proteínas Arqueales/química , Proteínas Arqueales/genética , Bacillus subtilis/enzimología , Bacillus subtilis/genética , Proteínas Bacterianas/química , Proteínas Bacterianas/genética , Dominio Catalítico/genética , Cristalografía por Rayos X , Estabilidad de Enzimas , Evolución Molecular , Methanosarcina/enzimología , Methanosarcina/genética , Modelos Moleculares , Mutagénesis Sitio-Dirigida , NAD/metabolismo , NADP/metabolismo , Nucleótido Desaminasas/química , Nucleótido Desaminasas/genética , Oxidorreductasas/química , Oxidorreductasas/genética , Estructura Cuaternaria de Proteína , Homología de Secuencia de Aminoácido , Electricidad Estática , Especificidad por Sustrato , Deshidrogenasas del Alcohol de Azúcar/química , Deshidrogenasas del Alcohol de Azúcar/genética
3.
Anal Chim Acta ; 1039: 65-73, 2018 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-30322554

RESUMEN

High-throughput screening of plastic products in children's living environment is necessary to identify phthalate-containing objects for the concern of public health and safety. A novel strategy of probe collecting technique combined with ambient mass spectrometry was developed to carry out the large-scale sample analysis. Analytes from the surface of approximately 500 objects each in two kindergartens in Taiwan were collected using the same number of the metallic probes. After being delivered to laboratory, the analytes on the probes were analyzed with thermal desorption-electrospray ionization/mass spectrometry (TD-ESI/MS). As sample pretreatment was unnecessary, the analysis of phthalates on a probe was completed within 30 s enabling high-throughput screening of a large number of objects. All procedure including sampling and TD-ESI/MS analysis together with report writing for a kindergarten was completed in one day. A reasonable relative standard deviation (<15.6%) was obtained from replicate analyses of phthalate standards. Single-point calibration was used to perform semi-quantitative analysis, and results were validated by liquid chromatography/mass spectrometry (LC/MS). It was found that 20-40% of the objects in two kindergartens contained greater than low-level (>2 ng) of phthalates and 40-60% of the objects in the kindergartens contained more than one kind of phthalate.


Asunto(s)
Ensayos Analíticos de Alto Rendimiento/métodos , Espectrometría de Masas/métodos , Ácidos Ftálicos/análisis , Preescolar , Humanos , Instituciones Académicas , Taiwán
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