Catalytic mechanism of TiO2 quantum dots on the de/re-hydrogenation characteristics of magnesium hydride

Abstract Owing to their low cost, high catalytic efficiency and biocompatibility, carbon-based metalfree catalysts (C-MFCs) have attracted intense interest for various applications, ranging from energy through environmental to biomedical technologies. While considerable efforts and progress have been made in mechanistic understanding of C-MFCs for non-biomedical applications, their catalytic mechanism for therapeutic effects has rarely been investigated. In this study, defect-rich graphene quantum dots (GQDs) were developed as C-MFCs for efficient ROS generation, specifically in the H2O2 -rich tumor microenvironment to cause multi-level damage of subcellular components (even in nuclei). While a desirable anti-cancer performance was achieved, the catalytic performance was found to strongly depend on the defect density. It is for the first time that the defect-induced catalytic generation of ROS by C-MFCs in the tumor microenvironment was demonstrated and the associated catalytic mechanism was elucidated. This work opens a new avenue for the development of safe and efficient catalytic nanomedicine.

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Enhanced Peroxidase-Like Activity of MoS2 Quantum Dots Functionalized g-C3N4 Nanosheets towards Colorimetric Detection of H2O2

Nanomaterials ◽

10.3390/nano8120976 ◽

2018 ◽

Vol 8 (12) ◽

pp. 976 ◽

Cited By ~ 8

Author(s):

Peng Ju ◽

Yunhong He ◽

Min Wang ◽

Xiuxun Han ◽

Fenghua Jiang ◽

...

Keyword(s):

Quantum Dots ◽

Catalytic Mechanism ◽

Close Contact ◽

Colorimetric Detection ◽

Active Species ◽

Biomedical Analysis ◽

Exchange Method ◽

Visual Assay ◽

Loading Amount

MoS2 quantum dots (QDs) functionalized g-C3N4 nanosheets (MoS2@CNNS) were prepared through a protonation-assisted ion exchange method, which were developed as a highly efficient biomimetic catalyst. Structural analysis revealed that uniformly-dispersed MoS2 QDs with controllable size and different loading amount grew in-situ on the surface of CNNS, forming close-contact MoS2@CNNS nanostructures and exhibiting distinct surface properties. Compared to MoS2 QDs and CNNS, the MoS2@CNNS nanocomposites exhibited a more than four times stronger peroxidase-like catalytic activity, which could catalyze the oxidation of 3,3’,5,5’-tetramethylbenzidine (TMB) in the presence of H2O2 to generate a blue oxide. Among the MoS2@CNNS nanocomposites, MoS2@CNNS(30) was verified to present the best intrinsic peroxidase-like performance, which could be attributed to the more negative potential and larger specific surface area. A simple, rapid and ultrasensitive system for colorimetric detection of H2O2 was thus successfully established based on MoS2@CNNS, displaying nice selectivity, reusability, and stability. The detection limit of H2O2 could reach as low as 0.02 μM. Furthermore, the kinetic and active species trapping experiments indicated the peroxidase-like catalytic mechanism of MoS2@CNNS. This work develops a novel, rapid, and ultrasensitive approach for visual assay of H2O2, which has a potential application prospect on clinical diagnosis and biomedical analysis.

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Understanding of catalytic ROS generation from defect-rich graphene quantum-dots for therapeutic effects in tumor microenvironment

Journal of Nanobiotechnology ◽

10.1186/s12951-021-01053-6 ◽

2021 ◽

Vol 19 (1) ◽

Author(s):

Xichu Wang ◽

Chuangang Hu ◽

Zi Gu ◽

Liming Dai

Keyword(s):

Quantum Dots ◽

Tumor Microenvironment ◽

Catalytic Mechanism ◽

Defect Density ◽

Low Cost ◽

Graphene Quantum Dots ◽

Catalytic Efficiency ◽

Catalytic Performance ◽

Ros Generation ◽

Therapeutic Effects

AbstractOwing to their low cost, high catalytic efficiency and biocompatibility, carbon-based metal-free catalysts (C-MFCs) have attracted intense interest for various applications, ranging from energy through environmental to biomedical technologies. While considerable effort and progress have been made in mechanistic understanding of C-MFCs for non-biomedical applications, their catalytic mechanism for therapeutic effects has rarely been investigated. In this study, defect-rich graphene quantum dots (GQDs) were developed as C-MFCs for efficient ROS generation, specifically in the H2O2-rich tumor microenvironment to cause multi-level damages of subcellular components (even in nuclei). While a desirable anti-cancer performance was achieved, the catalytic performance was found to strongly depend on the defect density. It is for the first time that the defect-induced catalytic generation of ROS by C-MFCs in the tumor microenvironment was demonstrated and the associated catalytic mechanism was elucidated. This work opens a new avenue for the development of safe and efficient catalytic nanomedicine.

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Electrochemical nucleation and growth of copper on iron and aluminum: A TEM study of industrial copper cementation

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100109410 ◽

1978 ◽

Vol 36 (1) ◽

pp. 454-455

Author(s):

L.E. Murr ◽

V. Annamalai

Keyword(s):

Metal Surface ◽

Copper Deposit ◽

Nucleation And Growth ◽

16Th Century ◽

Electrochemical Reactions ◽

Mine Shaft ◽

De Re ◽

Copper Precipitation ◽

Electrochemical Nucleation ◽

Interesting System

Georgius Agricola in 1556 in his classical book, “De Re Metallica”, mentioned a strange water drawn from a mine shaft near Schmölnitz in Hungary that eroded iron and turned it into copper. This precipitation (or cementation) of copper on iron was employed as a commercial technique for producing copper at the Rio Tinto Mines in Spain in the 16th Century, and it continues today to account for as much as 15 percent of the copper produced by several U.S. copper companies.In addition to the Cu/Fe system, many other similar heterogeneous, electrochemical reactions can occur where ions from solution are reduced to metal on a more electropositive metal surface. In the case of copper precipitation from solution, aluminum is also an interesting system because of economic, environmental (ecological) and energy considerations. In studies of copper cementation on aluminum as an alternative to the historical Cu/Fe system, it was noticed that the two systems (Cu/Fe and Cu/Al) were kinetically very different, and that this difference was due in large part to differences in the structure of the residual, cement-copper deposit.

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Nanostructure of semiconductor quantum dots in a borosilicate glass matrix by complementary use of HREM and AEM

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100176770 ◽

1990 ◽

Vol 48 (4) ◽

pp. 728-729

Author(s):

M.J. Kim ◽

L.C. Liu ◽

S.H. Risbud ◽

R.W. Carpenter

Keyword(s):

Quantum Dots ◽

Borosilicate Glass ◽

Glass Matrix ◽

Optical Switching ◽

Response Times ◽

Fast Response ◽

Processing Technique ◽

Internal Stresses ◽

Electron Hole ◽

Spatial Dimensions

When the size of a semiconductor is reduced by an appropriate materials processing technique to a dimension less than about twice the radius of an exciton in the bulk crystal, the band like structure of the semiconductor gives way to discrete molecular orbital electronic states. Clusters of semiconductors in a size regime lower than 2R {where R is the exciton Bohr radius; e.g. 3 nm for CdS and 7.3 nm for CdTe) are called Quantum Dots (QD) because they confine optically excited electron- hole pairs (excitons) in all three spatial dimensions. Structures based on QD are of great interest because of fast response times and non-linearity in optical switching applications.In this paper we report the first HREM analysis of the size and structure of CdTe and CdS QD formed by precipitation from a modified borosilicate glass matrix. The glass melts were quenched by pouring on brass plates, and then annealed to relieve internal stresses. QD precipitate particles were formed during subsequent "striking" heat treatments above the glass crystallization temperature, which was determined by differential thermal analysis.

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Semiconductor Quantum Dots

10.1039/9781782628354 ◽

2014 ◽

Keyword(s):

Quantum Dots ◽

Semiconductor Quantum Dots

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Structures of c-di-GMP/cGAMP degrading phosphodiesterase VcEAL: identification of a novel conformational switch and its implication

Biochemical Journal ◽

10.1042/bcj20190399 ◽

2019 ◽

Vol 476 (21) ◽

pp. 3333-3353 ◽

Cited By ~ 3

Author(s):

Malti Yadav ◽

Kamalendu Pal ◽

Udayaditya Sen

Keyword(s):

Active Site ◽

Metal Binding ◽

Metal Ion ◽

Triosephosphate Isomerase ◽

Catalytic Mechanism ◽

Degradation Mechanism ◽

Structural Basis ◽

Conserved Residues ◽

Phosphodiester Bond ◽

Cyclic Dinucleotides

Cyclic dinucleotides (CDNs) have emerged as the central molecules that aid bacteria to adapt and thrive in changing environmental conditions. Therefore, tight regulation of intracellular CDN concentration by counteracting the action of dinucleotide cyclases and phosphodiesterases (PDEs) is critical. Here, we demonstrate that a putative stand-alone EAL domain PDE from Vibrio cholerae (VcEAL) is capable to degrade both the second messenger c-di-GMP and hybrid 3′3′-cyclic GMP–AMP (cGAMP). To unveil their degradation mechanism, we have determined high-resolution crystal structures of VcEAL with Ca2+, c-di-GMP-Ca2+, 5′-pGpG-Ca2+ and cGAMP-Ca2+, the latter provides the first structural basis of cGAMP hydrolysis. Structural studies reveal a typical triosephosphate isomerase barrel-fold with substrate c-di-GMP/cGAMP bound in an extended conformation. Highly conserved residues specifically bind the guanine base of c-di-GMP/cGAMP in the G2 site while the semi-conserved nature of residues at the G1 site could act as a specificity determinant. Two metal ions, co-ordinated with six stubbornly conserved residues and two non-bridging scissile phosphate oxygens of c-di-GMP/cGAMP, activate a water molecule for an in-line attack on the phosphodiester bond, supporting two-metal ion-based catalytic mechanism. PDE activity and biofilm assays of several prudently designed mutants collectively demonstrate that VcEAL active site is charge and size optimized. Intriguingly, in VcEAL-5′-pGpG-Ca2+ structure, β5–α5 loop adopts a novel conformation that along with conserved E131 creates a new metal-binding site. This novel conformation along with several subtle changes in the active site designate VcEAL-5′-pGpG-Ca2+ structure quite different from other 5′-pGpG bound structures reported earlier.

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