Room-temperature borane-catalyzed functionalization of hydride-terminated silicon nanocrystals (H-SiNCs) with alkenes/alkynes is reported. This new methodology affords formation of alkyl and alkynyl surface monolayers of varied chain lengths (i.e., C5-C12). The present study also indicates alkynes react more readily with H-SiNC surfaces than equivalent alkenes. Unlike other toxic transition-metal catalysts, borane or related byproducts can be readily removed from the functionalized SiNCs. The new method affords stable luminescent alkyl/alkenyl-functionalized SiNCs.

Silicon nanocrystals exhibit size-dependent optical and electronic properties that may be exploited for applications ranging from sensors to photovoltaics. In addition, they can be utilized in biological and environmental systems thanks to the nontoxicity of silicon. Synthesis of silicon nanocrystals has been accomplished using a variety of methods. However, creating near monodisperse systems of high purity has been a challenge. The high temperature processing of hydrogen silsesquioxane method of particle synthesis reproducibly provides pure, near monodisperse particles in scalable quantities. These particles can then be liberated using HF etching and functionalized using a variety of methods. This paper outlines our lab procedures for creating silicon nanocrystals, the various functionalization methods and the most commonly used characterization techniques.

Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

Luminescent silicon nanocrystals (Si-NCs) surface functionalized with dodecyl groups were exposed to solutions of nitroaromatic compounds including nitrobenzene, nitrotoluene, and dinitrotoluene. It was found that Si-NC luminescence was quenched upon exposure to nitroaromatics via an electron transfer mechanism as indicated by Stern-Volmer analysis. This quenching was exploited and a straightforward paper-based Si-NC sensor was developed. This paper motif was found to be sensitive to solution, vapor, and solid phase nitroaromatics, as well as solution borne RDX and PETN.

Nanomaterials are of particular interest in environmental chemistry due to their unknown toxicity to living organisms. Reports indicate that nanoparticles (NPs) affect seed germination, but the uptake and biotransformation of metal nanoparticles is not well understood. The present study investigated the toxicity and biotransformation of Ni(OH)2 NPs by mesquite plants (Prosopis sp.). Three sets of plants were treated for four weeks with 0.01, 0.05, or 0.10 g of either uncoated or sodium citrate coated NPs before and after synthesis. Nickel concentrations in plants were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and the form and oxidation state of Ni was determined using X-ray absorption spectroscopy (XAS). Results showed that uncoated NPs had an average size of 8.7 nm, whereas coated NPs before and after synthesis had an average of 2.5 and 0.9 nm, respectively. The ICP-OES results showed that plants treated with 0.10 g of uncoated and coated NPs before and after synthesis had 803, 764, and 400 mg Ni kg dry weight, in the leaves, respectively. The XAS analyses showed Ni NPs in roots and shoots of plants treated with uncoated NPs, whereas leaves showed a Ni(II)-organic acid type complex. However, plants treated with coated NPs before or after synthesis showed Ni NPs only in roots and a Ni(II)-organic acid complex in shoots and leaves. Results also showed that none of the treatments reduced plant size or chlorophyll production. To the authors' knowledge, this is the first time that the biotransformation of nanoparticles by a plant system is reported.