Synthesis, Luminescent Properties, and Biomedical Applications Shili Gai,†,‡ Chunxia Li,† Piaoping Yang,*,‡ and Jun Lin*,† †State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China ‡Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin, 150001, P. R. China

Recent Progress in Rare Earth Micro/Nanocrystals: Soft Chemical Synthesis, Luminescent Properties, and Biomedical Applications

Nanomaterials are finding increasing use for biomedical applications such as imaging, diagnostics, and drug delivery. While it is well understood that nanoparticle (NP) physico-chemical properties can dictate biological responses and interactions, it has been difficult to outline a unifying framework to directly link NP properties to expected in vitro and in vivo outcomes. When introduced to complex biological media containing electrolytes, proteins, lipids, etc., nanoparticles (NPs) are subjected to a range of forces which determine their behavior in this environment. One aspect of NP behavior in biological systems that is often understated or overlooked is aggregation. NP aggregation will significantly alter in vitro behavior (dosimetry, NP uptake, cytotoxicity), as well as in vivo fate (pharmacokinetics, toxicity, biodistribution). Thus, understanding the factors driving NP colloidal stability and aggregation is paramount. Furthermore, studying biological interactions with NPs at the nanoscale level requires an interdisciplinary effort with a robust understanding of multiple characterization techniques. This review examines the factors that determine NP colloidal stability, the various efforts to stabilize NP in biological media, the methods to characterize NP colloidal stability in situ, and provides a discussion regarding NP interactions with cells.

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Nanoparticle colloidal stability in cell culture media and impact on cellular interactions

Carbon dots (C-dots) are a kind of fluorescent nanoparticles that are strongly fluorescent, non-blinking, and can be easily synthesized at low cost. Their emission color can be tuned by varying the excitation wavelength. Their properties make them strong competitors to semiconductor quantum dots. Synthetic approaches for C-dots can be classified into two categories, viz. top-down and bottom-up methods. Surface passivated and functionalized C-dots can be utilized to sense pH values, metal ions and organic molecules. Owing to their low cytotoxicity, biocompatibility and impressive photostability, long-term observations become possible. C-dots also show promise as labels and for bioimaging. This review (with 142 refs.) is divided into several sections. The first covers commonly used methods for preparation of C-dots including laser ablation, arc discharge, electrochemical methods, pyrolytic processes, template based methods, microwave assisted methods, chemical oxidation methods, reverse micelle based methods, etc. The first section also covers methods for surface functionalization and passivation. We continue by discussing the spectroscopic properties and other physical and chemical properties of C-dots (fluorescence, up-conversion fluorescence, methods for enhancing photoluminescence, effects of pH value, cytotoxicity, etc.). Another section covers the characterization including TEM and XRD. Applications in biology are summarized and subdivided into in vitro imaging, in vivo imaging, chemical probe, quantitation of biomacromolecules, but also in drug delivery, photoacoustic imaging and anticancer therapy. We finally discuss current challenges and perspectives in this promising field.

A review on syntheses, properties, characterization and bioanalytical applications of fluorescent carbon dots

Application of nanomaterials for agriculture is relatively new as compared to their use in biomedical and industrial sectors. In order to promote sustainable nanoagriculture, biocompatible silver nanoparticles (AgNPs) have been synthesized through green route using kaffir lime leaf extract for use as nanopriming agent for enhancing seed germination of rice aged seeds. Results of various characterization techniques showed the successful formation of AgNPs which were capped with phytochemicals present in the plant extract. Rice aged seeds primed with phytosynthesized AgNPs at 5 and 10 ppm significantly improved germination performance and seedling vigor compared to unprimed control, AgNO3 priming, and conventional hydropriming. Nanopriming could enhance α-amylase activity, resulting in higher soluble sugar content for supporting seedlings growth. Furthermore, nanopriming stimulated the up-regulation of aquaporin genes in germinating seeds. Meanwhile, more ROS production was observed in germinating seeds of nanopriming treatment compared to unprimed control and other priming treatments, suggesting that both ROS and aquaporins play important roles in enhancing seed germination. Different mechanisms underlying nanopriming-induced seed germination were proposed, including creation of nanopores for enhanced water uptake, rebooting ROS/antioxidant systems in seeds, generation of hydroxyl radicals for cell wall loosening, and nanocatalyst for fastening starch hydrolysis.

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Nanopriming technology for enhancing germination and starch metabolism of aged rice seeds using phytosynthesized silver nanoparticles

Recent advances in bioapplications of C-dots

Hydrophilic functionalization of nanoparticle surface is essential for their biomedical applications. Herein, we report a facile one-step reverse precipitation method to synthesize water-dispersible, biocompatible, and carboxylate-functionalized superparamagnetic magnetite (Fe3O4) nanoparticles with the help of biocompatible sodium citrate salt. Transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), zeta potential measurement, dynamic light scattering (DLS), and superconducting quantum interference device (SQUID) were used to characterize the as-prepared magnetite nanoparticles. The size of the as-prepared magnetite nanoparticles was tuned from 27 ± 3.8 to 4.8 ± 1.9 nm by changing the sodium citrate concentration from 25 to 125 mM. The sodium citrate concentration also influenced the water-dispersible stability of the as-prepared magnetite nanoparticles, which was due to the electrostatic repulsion.

One-step reverse precipitation synthesis of water-dispersible superparamagnetic magnetite nanoparticles

Economic and environmentally benign technology to remove organic pollutants is highly desired for the sustainable water management to meet the growing clean water demand. This review focuses on the progress of nitrogen-containing organic compounds removal in wastewater by TiO 2 photocatalytic degradation during the past 15 years and summarizes the important factors affecting the relevant photocatalytic activity. Photodegradation performance of nitrogen-containing organic compounds with different natures is the result of a strong interaction among pollutant structures, TiO 2 properties and photocatalytic reaction conditions. However, the specific function and influence of a given feature for the photodegradation of nitrogen-containing organic compound is difficult to be characterized accurately because some of the above-mentioned parameters are often strongly coupled. It is also clear that for each organic pollutant, a unique set of conditions may be needed for the optimal performance. We also point out some weak points and the further efforts needed in the field.

Photocatalytic degradation of nitrogen-containing organic compounds over TiO2

Colloidal platinum nanoparticles with 2.2 nm were immobilized on γ-iron oxide (γ-Fe 2 O 3 ) powder to make a supported catalyst (Pt/γ-Fe 2 O 3 ) with controlled Pt nanoparticle size and size distribution. This catalyst was used to catalyze the selective hydrogenation of o -chlorobenzene to o -chloroaniline without using any solvent; 99.9% selectivity at 99.95% conversion was achieved.

Selective hydrogenation of o-chloronitrobenzene using supported platinum nanoparticles without solvent

Pulverized semi-coke was employed as raw material to prepare activated carbon via steam activation and evaluated as a CO2 adsorbent. The effects of the preparation parameters including demineralization, activation temperature, activation time and steam flow on the structure and performance of the synthesized activated carbon were investigated. It was found that the microporous structure of activated carbon was greatly influenced by demineralization order and activation conditions. Demineralization before activation significantly increased the microporous structure of the activated carbon, which was ascribed to the removal of the inorganic fraction. Compared to the commercial activated carbon, activated carbon obtained by employing 150 mL/min steam to treat the demineralized pulverized semi-coke at 700 °C for 70 min possessed a higher CO2/N2 selectivity of 34.4 and good cyclic performance, which was due to its narrow microporosity of 0.55 nm. Furthermore, it was proved that a pore size of smaller than 1 nm is favorable for CO2 sorption.

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CO2 Capture over Activated Carbon Derived from Pulverized Semi-Coke

Jet fuel rich in hydroaromatics and cycloalkanes could be derived from direct coal liquefaction oil via the hydrogenation saturation process. Developing an efficient catalyst to transform naphthalene hydrocarbons to hydroaromatics and cycloalkanes with high selectivity plays a significant role in realizing the above hydrogenation saturation process. In this work, Ni2P/Al2O3 catalysts were prepared at different reduction temperatures via the thermal decomposition of hypophosphite. We investigated the influence of reduction temperature and the results showed that reduction temperature had an important impact on the properties of Ni2P/Al2O3 catalysts. When the reduction temperature was 400 °C, the Ni2P particle size of the Ni2P/Al2O3 catalyst was 3.8 nm and its specific surface area was 170 m2/g. Furthermore, the Ni2P/Al2O3 catalyst reduced at 400 °C obtained 98% naphthalene conversion and 98% decalin selectivity. The superior catalytic activity was attributed to the smaller Ni2P particle size, higher specific surface area and suitable acidity, which enhanced the adsorption of naphthalene on Ni2P/Al2O3 catalyst.

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Jieying Jing

Papers

One-step reverse precipitation synthesis of water-dispersible superparamagnetic magnetite nanoparticles

Photocatalytic degradation of nitrogen-containing organic compounds over TiO2

Selective hydrogenation of o-chloronitrobenzene using supported platinum nanoparticles without solvent

CO2 Capture over Activated Carbon Derived from Pulverized Semi-Coke

Influence of Reduction Temperature on the Structure and Naphthalene Hydrogenation Saturation Performance of Ni2P/Al2O3 Catalysts