Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389

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Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications

Recent advances in nanotechnology have offered new hope for cancer detection, prevention, and treatment. While the enhanced permeability and retention effect has served as a key rationale for using nanoparticles to treat solid tumors, it does not enable uniform delivery of these particles to all regions of tumors in sufficient quantities. This heterogeneous distribution of therapeutics is a result of physiological barriers presented by the abnormal tumor vasculature and interstitial matrix. These barriers are likely to be responsible for the modest survival benefit offered by many FDA-approved nanotherapeutics and must be overcome for the promise of nanomedicine in patients to be realized. Here, we review these barriers to the delivery of cancer therapeutics and summarize strategies that have been developed to overcome these barriers. Finally, we discuss design considerations for optimizing the delivery of nanoparticles to tumors.

https://faculty.washington.edu/mzhang/mse599/NP-drug-Delivering%20nanomedicine%20to%20solid%20tumors-.2010..pdf

Delivering nanomedicine to solid tumors

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Diagnostics and Therapy Guanying Chen,‡,† Indrajit Roy,†,§ Chunhui Yang,*,‡ and Paras N. Prasad*,† †Institute for Lasers, Photonics, and Biophotonics and Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, United States ‡School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China Department of Chemistry, University of Delhi, Delhi 110007, India

Nanochemistry and Nanomedicine for Nanoparticle-based Diagnostics and Therapy

Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today’s strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenom...

Prospects of Nanoscience with Nanocrystals

We report the synthesis of a size series of copper indium selenide quantum dots (QDs) of various stoichiometries exhibiting photoluminescence (PL) from the red to near-infrared (NIR). The synthetic method is modular, and we have extended it to the synthesis of luminescent silver indium diselenide QDs. Previous reports on QDs luminescent in the NIR region have been primarily restricted to binary semiconductor systems, such as InAs, PbS, and CdTe. This work seeks to expand the availability of luminescent QD materials to ternary I−III−VI semiconductor systems.

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Ternary I-III-VI quantum dots luminescent in the red to near-infrared.

We report single-particle photoluminescence (PL) intermittency (blinking) with high on-time fractions in colloidal CdSe quantum dots (QD) with conformal CdS shells of 1.4 nm thickness, equivalent to approximately 4 CdS monolayers. All QDs observed displayed on-time fractions >60% with the majority >80%. The high on-time fraction blinking is accompanied by fluorescence quantum yields (QY) close to unity (up to 98% in an absolute QY measurement) when dispersed in organic solvents and a monoexponential ensemble photoluminescence (PL) decay lifetime. The CdS shell is formed in high synthetic yield using a modified selective ion layer adsorption and reaction (SILAR) technique that employs a silylated sulfur precursor. The CdS shell provides sufficient chemical and electronic passivation of the QD excited state to permit water solubilization with greater than 60% QY via ligand exchange with an imidazole-bearing hydrophilic polymer.

Alternating layer addition approach to CdSe/CdS core/shell quantum dots with near-unity quantum yield and high on-time fractions

We present the synthesis of InAs quantum dots (QDs) with a ZnCdS shell with bright and stable emission in the near-infrared (NIR, 700-900 nm) region for biological imaging applications. We demonstrate how NIR QDs can image tumor vasculature in vivo at significantly deeper penetration depths and with higher contrast than visible emitting CdSe(CdS) QDs. Targeted cellular labeling is also presented and may enable multiplexed and low autofluorescence cellular imaging.

InAs(ZnCdS) quantum dots optimized for biological imaging in the near-infrared.

InAs(ZnCdS) Quantum Dots Optimized for Biological Imaging in the Near-Infrared

This paper examines the molecular mechanism of InP colloidal quantum dot (QD) syntheses. Unlike methods for monodisperse PbSe and CdSe we found that existing InP syntheses result in total depletion of molecular phosphorous species following nucleation, so QD growth is due exclusively to non-molecular ripening. We find that amines inhibit precursor depletion via solvation, and these findings may lead to better synthetic methodology for InP QDs.

Peter M. Allen

Papers

Ternary I-III-VI quantum dots luminescent in the red to near-infrared.

Alternating layer addition approach to CdSe/CdS core/shell quantum dots with near-unity quantum yield and high on-time fractions

InAs(ZnCdS) quantum dots optimized for biological imaging in the near-infrared.

InAs(ZnCdS) Quantum Dots Optimized for Biological Imaging in the Near-Infrared

Mechanistic Insights into the Formation of InP Quantum Dots