scholarly journals Exploring the Effect of the Irradiation Time on Photosensitized Dendrimer-Based Nanoaggregates for Potential Applications in Light-Driven Water Photoreduction

Nanomaterials ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 1316 ◽  
Author(s):  
Martínez ◽  
Inostroza-Rivera ◽  
Durán ◽  
Molero ◽  
Bonardd ◽  
...  

Fourth generation polyamidoamine dendrimer (PAMAM, G4) modified with fluorescein units (F) at the periphery and Pt nanoparticles stabilized by L-ascorbate were prepared. These dendrimers modified with hydrophobic fluorescein were used to achieve self-assembling structures, giving rise to the formation of nanoaggregates in water. The photoactive fluorescein units were mainly used as photosensitizer units in the process of the catalytic photoreduction of water propitiated by light. Complementarily, Pt-ascorbate nanoparticles acted as the active sites to generate H2. Importantly, the study of the functional, optical, surface potential and morphological properties of the photosensitized dendrimer aggregates at different irradiation times allowed for insights to be gained into the behavior of these systems. Thus, the resultant photosensitized PAMAM-fluorescein (G4-F) nanoaggregates (NG) were conveniently applied to light-driven water photoreduction along with sodium L-ascorbate and methyl viologen as the sacrificial reagent and electron relay agent, respectively. Notably, these aggregates exhibited appropriate stability and catalytic activity over time for hydrogen production. Additionally, in order to propose a potential use of these types of systems, the in situ generated H2 was able to reduce a certain amount of methylene blue (MB). Finally, theoretical electronic analyses provided insights into the possible excited states of the fluorescein molecules that could intervene in the global mechanism of H2 generation.

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Mi Xiong ◽  
Zhe Gao ◽  
Peng Zhao ◽  
Guofu Wang ◽  
Wenjun Yan ◽  
...  

Abstract In situ tuning of the electronic structure of active sites is a long-standing challenge. Herein, we propose a strategy by controlling the hydrogen spillover distance to in situ tune the electronic structure. The strategy is demonstrated to be feasible with the assistance of CoOx/Al2O3/Pt catalysts prepared by atomic layer deposition in which CoOx and Pt nanoparticles are separated by hollow Al2O3 nanotubes. The strength of hydrogen spillover from Pt to CoOx can be precisely tailored by varying the Al2O3 thickness. Using CoOx/Al2O3 catalyzed styrene epoxidation as an example, the CoOx/Al2O3/Pt with 7 nm Al2O3 layer exhibits greatly enhanced selectivity (from 74.3% to 94.8%) when H2 is added. The enhanced selectivity is attributed to the introduction of controllable hydrogen spillover, resulting in the reduction of CoOx during the reaction. Our method is also effective for the epoxidation of styrene derivatives. We anticipate this method is a general strategy for other reactions.


Author(s):  
D. Loretto ◽  
J. M. Gibson ◽  
S. M. Yalisove ◽  
R. T. Tung

The cobalt disilicide/silicon system has potential applications as a metal-base and as a permeable-base transistor. Although thin, low defect density, films of CoSi2 on Si(111) have been successfully grown, there are reasons to believe that Si(100)/CoSi2 may be better suited to the transmission of electrons at the silicon/silicide interface than Si(111)/CoSi2. A TEM study of the formation of CoSi2 on Si(100) is therefore being conducted. We have previously reported TEM observations on Si(111)/CoSi2 grown both in situ, in an ultra high vacuum (UHV) TEM and ex situ, in a conventional Molecular Beam Epitaxy system.The procedures used for the MBE growth have been described elsewhere. In situ experiments were performed in a JEOL 200CX electron microscope, extensively modified to give a vacuum of better than 10-9 T in the specimen region and the capacity to do in situ sample heating and deposition. Cobalt was deposited onto clean Si(100) samples by thermal evaporation from cobalt-coated Ta filaments.


Author(s):  
Z. Liliental-Weber ◽  
C. Nelson ◽  
R. Ludeke ◽  
R. Gronsky ◽  
J. Washburn

The properties of metal/semiconductor interfaces have received considerable attention over the past few years, and the Al/GaAs system is of special interest because of its potential use in high-speed logic integrated optics, and microwave applications. For such materials a detailed knowledge of the geometric and electronic structure of the interface is fundamental to an understanding of the electrical properties of the contact. It is well known that the properties of Schottky contacts are established within a few atomic layers of the deposited metal. Therefore surface contamination can play a significant role. A method for fabricating contamination-free interfaces is absolutely necessary for reproducible properties, and molecularbeam epitaxy (MBE) offers such advantages for in-situ metal deposition under UHV conditions


2020 ◽  
Vol 17 ◽  
Author(s):  
Elham Khodaverdi ◽  
Farhad Eisvand ◽  
Mohammad Sina Nezami ◽  
Seyedeh Nesa Rezaeian Shiadeh ◽  
Hossein Kamali ◽  
...  

Background:: Doxycycline (DOX) is used in treating a bacterial infection, especially for periodontitis treatment. Objective: To reduce irritation of DOX for subgingival administration and increase the chemical stability and against enzy-matic, the complex of α-cyclodextrin with DOX was prepared and loaded into injectable in situ forming implant based on PLGA. Methods:: FTIR, molecular docking studies, X-ray diffraction, and differential scanning calorimetry was performed to char-acterize the DOX/α-cyclodextrin complex. Finally, the in-vitro drug release and modeling, morphological properties, and cellular cytotoxic effects were also evaluated. Results:: The stability of DOX was improved with complex than pure DOX. The main advantage of the complex is the al-most complete release (96.31 ± 2.56 %) of the drug within 14 days of the implant, whereas in the formulation containing the pure DOX and the physical mixture the DOX with α-cyclodextrin release is reached to 70.18 ± 3.61 % and 77.03 ± 3.56 %, respectively. This trend is due to elevate of DOX stability in the DOX/ α-cyclodextrin complex form within PLGA implant that confirmed by the results of stability. Conclusion:: Our results were indicative that the formulation containing DOX/α-cyclodextrin complex was biocompatible and sustained-release with minimum initial burst release.


2020 ◽  
Vol 154 (2) ◽  
pp. 135-153 ◽  
Author(s):  
Gabriel García Caballero ◽  
Donella Beckwith ◽  
Nadezhda V. Shilova ◽  
Adele Gabba ◽  
Tanja J. Kutzner ◽  
...  

Abstract The concept of biomedical significance of the functional pairing between tissue lectins and their glycoconjugate counterreceptors has reached the mainstream of research on the flow of biological information. A major challenge now is to identify the principles of structure–activity relationships that underlie specificity of recognition and the ensuing post-binding processes. Toward this end, we focus on a distinct feature on the side of the lectin, i.e. its architecture to present the carbohydrate recognition domain (CRD). Working with a multifunctional human lectin, i.e. galectin-3, as model, its CRD is used in protein engineering to build variants with different modular assembly. Hereby, it becomes possible to compare activity features of the natural design, i.e. CRD attached to an N-terminal tail, with those of homo- and heterodimers and the tail-free protein. Thermodynamics of binding disaccharides proved full activity of all proteins at very similar affinity. The following glycan array testing revealed maintained preferential contact formation with N-acetyllactosamine oligomers and histo-blood group ABH epitopes irrespective of variant design. The study of carbohydrate-inhibitable binding of the test panel disclosed up to qualitative cell-type-dependent differences in sections of fixed murine epididymis and especially jejunum. By probing topological aspects of binding, the susceptibility to inhibition by a tetravalent glycocluster was markedly different for the wild-type vs the homodimeric variant proteins. The results teach the salient lesson that protein design matters: the type of CRD presentation can have a profound bearing on whether basically suited oligosaccharides, which for example tested positively in an array, will become binding partners in situ. When lectin-glycoconjugate aggregates (lattices) are formed, their structural organization will depend on this parameter. Further testing (ga)lectin variants will thus be instrumental (i) to define the full range of impact of altering protein assembly and (ii) to explain why certain types of design have been favored during the course of evolution, besides opening biomedical perspectives for potential applications of the novel galectin forms.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jing Li ◽  
Xiaoxia Chang ◽  
Haochen Zhang ◽  
Arnav S. Malkani ◽  
Mu-jeng Cheng ◽  
...  

AbstractRigorous electrokinetic results are key to understanding the reaction mechanisms in the electrochemical CO reduction reaction (CORR), however, most reported results are compromised by the CO mass transport limitation. In this work, we determined mass transport-free CORR kinetics by employing a gas-diffusion type electrode and identified dependence of catalyst surface speciation on the electrolyte pH using in-situ surface enhanced vibrational spectroscopies. Based on the measured Tafel slopes and reaction orders, we demonstrate that the formation rates of C2+ products are most likely limited by the dimerization of CO adsorbate. CH4 production is limited by the CO hydrogenation step via a proton coupled electron transfer and a chemical hydrogenation step of CO by adsorbed hydrogen atom in weakly (7 < pH < 11) and strongly (pH > 11) alkaline electrolytes, respectively. Further, CH4 and C2+ products are likely formed on distinct types of active sites.


Water ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1409
Author(s):  
Hamdhani Hamdhani ◽  
Drew E. Eppehimer ◽  
David Walker ◽  
Michael T. Bogan

Chlorophyll-a measurements are an important factor in the water quality monitoring of surface waters, especially for determining the trophic status and ecosystem management. However, a collection of field samples for extractive analysis in a laboratory may not fully represent the field conditions. Handheld fluorometers that can measure chlorophyll-a in situ are available, but their performance in waters with a variety of potential light-interfering substances has not yet been tested. We tested a handheld fluorometer for sensitivity to ambient light and turbidity and compared these findings with EPA Method 445.0 using water samples obtained from two urban lakes in Tucson, Arizona, USA. Our results suggested that the probe was not sensitive to ambient light and performed well at low chlorophyll-a concentrations (<25 µg/L) across a range of turbidity levels (50–70 NTU). However, the performance was lower when the chlorophyll-a concentrations were >25 µg/L and turbidity levels were <50 NTU. To account for this discrepancy, we developed a calibration equation to use for this handheld fluorometer when field monitoring for potential harmful algal blooms in water bodies.


Chemosensors ◽  
2021 ◽  
Vol 9 (6) ◽  
pp. 140
Author(s):  
Jing Li ◽  
Keying Xu ◽  
Yang Chen ◽  
Jie Zhao ◽  
Peiyao Du ◽  
...  

Dopamine (DA) is an important catecholamine neurotransmitter that plays a highly relevant role in regulating the central nervous system, and abnormal DA content can cause many immune-related diseases. Hence, it is of significance to sensitively and specifically identify DA for clinical medicine. In this work, Pt/NH2-MIL-101 hybrid nanozymes with bimetallic catalytic centers were fabricated by forming coordinate bonds between Pt nanoparticles (Pt NPs) and –NH2 on metal–organic frameworks (MOF). The catalytic activity of Pt/NH2-MIL-101 was increased by 1.5 times via enlarging the exposure of more active sites and improving the activity of the active sites through the strategy of forming bimetallic catalytic centers. In the presence of DA, competing with 3, 3′, 5, 5′-tetramethylbenzidine (TMB) for the generated hydroxyl radicals (•OH), the blue oxidation state TMB (Ox-TMB) is reduced to colorless TMB, showing dramatic color changes. The Pt/NH2-MIL-101-based colorimetric assay enables the sensitive and robust detection of DA molecules with a detection limit of only 0.42 μM and has an observable potential in clinical applications.


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