International Institute for Nanotechnology

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTTemplated Techniques for the Synthesis and Assembly of Plasmonic NanostructuresMatthew R. Jones†§, Kyle D. Osberg†§, Robert J. Macfarlane‡§, Mark R. Langille‡§, and Chad A. Mirkin*†‡§View Author Information† ‡ § †Department of Materials Science and Engineering, ‡Department of Chemistry, and §International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States*Fax: (847) 467-5123. E-mail: [email protected]Cite this: Chem. Rev. 2011, 111, 6, 3736–3827Publication Date (Web):June 8, 2011Publication History Received21 December 2010Published online8 June 2011Published inissue 8 June 2011https://pubs.acs.org/doi/10.1021/cr1004452https://doi.org/10.1021/cr1004452review-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views47264Altmetric-Citations1050LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Genetics,Gold,Metal nanoparticles,Metals,Nanoparticles Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTNanoparticle Probes for the Detection of Cancer Biomarkers, Cells, and Tissues by FluorescenceAlyssa B. Chinen†∥, Chenxia M. Guan‡∥, Jennifer R. Ferrer§∥, Stacey N. Barnaby†∥, Timothy J. Merkel†∥, and Chad A. Mirkin*†∥View Author Information† ∥ †Department of Chemistry, ‡Department of Chemical Engineering, §Department of Interdepartmental Biological Sciences, and ∥International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 19, 10530–10574Publication Date (Web):August 27, 2015Publication History Received29 May 2015Published online27 August 2015Published inissue 14 October 2015https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00321https://doi.org/10.1021/acs.chemrev.5b00321review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views28319Altmetric-Citations849LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Cancer,Cells,Fluorescence,Nanoparticles,Peptides and proteins Get e-Alerts

The amyloid-β oligomer (AβO) hypothesis was introduced in 1998. It proposed that the brain damage leading to Alzheimer's disease (AD) was instigated by soluble, ligand-like AβOs. This hypothesis was based on the discovery that fibril-free synthetic preparations of AβOs were potent CNS neurotoxins that rapidly inhibited long-term potentiation and, with time, caused selective nerve cell death (Lambert et al., 1998). The mechanism was attributed to disrupted signaling involving the tyrosine-protein kinase Fyn, mediated by an unknown toxin receptor. Over 4,000 articles concerning AβOs have been published since then, including more than 400 reviews. AβOs have been shown to accumulate in an AD-dependent manner in human and animal model brain tissue and, experimentally, to impair learning and memory and instigate major facets of AD neuropathology, including tau pathology, synapse deterioration and loss, inflammation, and oxidative damage. As reviewed by Hayden and Teplow in 2013, the AβO hypothesis "has all but supplanted the amyloid cascade." Despite the emerging understanding of the role played by AβOs in AD pathogenesis, AβOs have not yet received the clinical attention given to amyloid plaques, which have been at the core of major attempts at therapeutics and diagnostics but are no longer regarded as the most pathogenic form of Aβ. However, if the momentum of AβO research continues, particularly efforts to elucidate key aspects of structure, a clear path to a successful disease modifying therapy can be envisioned. Ensuring that lessons learned from recent, late-stage clinical failures are applied appropriately throughout therapeutic development will further enable the likelihood of a successful therapy in the near-term.

A historical overview of the activation and porosity of MOFs including strategies to design and preserve permanent porosity in MOFs.

A new class of gold nanostructures, concave nanocubes, enclosed by 24 high-index {720} facets, have been prepared in a monodisperse fashion by a modified seed-mediated synthetic method. The Cl(-) counterion in the surfactant plays an essential role in controlling the concave morphology of the final product. The concave nanocubes exhibit higher chemical activities compared with low-index {111}-faceted octahedra.

Careful processing of four representative metal-organic framework (MOF) materials with liquid and supercritical carbon dioxide (ScD) leads to substantial, or in some cases spectacular (up to 1200%), increases in gas-accessible surface area. Maximization of surface area is key to the optimization of MOFs for many potential applications. Preliminary evidence points to inhibition of mesopore collapse, and therefore micropore accessibility, as the basis for the extraordinarily efficacious outcome of ScD-based activation.

Intracellular delivery of nucleic acids as gene regulation agents typically requires the use of cationic carriers or viral vectors, yet issues related to cellular toxicity or immune responses hamper their attractiveness as therapeutic candidates. The discovery that spherical nucleic acids (SNAs), polyanionic structures comprised of densely packed, highly oriented oligonucleotides covalently attached to the surface of nanoparticles, can effectively enter more than 50 different cell types presents a potential strategy for overcoming the limitations of conventional transfection agents. Unfortunately, little is known about the mechanism of endocytosis of SNAs, including the pathway of entry and specific proteins involved. Here, we demonstrate that the rapid cellular uptake kinetics and intracellular transport of SNAs stem from the arrangement of oligonucleotides into a 3D architecture, which supports their targeting of class A scavenger receptors and endocytosis via a lipid-raft-dependent, caveolae-mediated pathway. These results reinforce the notion that SNAs can serve as therapeutic payloads and targeting structures to engage biological pathways not readily accessible with linear oligonucleotides.

Porous heterogeneous catalysts play a pivotal role in the chemical industry. Herein a new Hf-based metal–organic framework (Hf-NU-1000) incorporating Hf6 clusters is reported. It demonstrates high catalytic efficiency for the activation of epoxides, facilitating the quantitative chemical fixation of CO2 into five-membered cyclic carbonates under ambient conditions, rendering this material an excellent catalyst. As a multifunctional catalyst, Hf-NU-1000 is also efficient for other epoxide activations, leading to the regioselective and enantioretentive formation of 1,2-bifuctionalized systems via solvolytic nucleophilic ring opening.

Amine-functionalized polyvalent oligonucleotide gold nanoparticles (DNA-Au NPs) were derivatized with a cisplatin prodrug, and the resulting DNA-Au NP conjugates were used to internalize multiple platinum centers. A platinum(IV) complex, c,c,t-[Pt(NH(3))(2)Cl(2)(OH)(O(2)CCH(2)CH(2)CO(2)H)], was tethered to the surface of DNA-Au NPs through amide linkages. The platinum-tethered gold nanoparticles were taken into several cancer cells. The drop in intracellular pH facilitated reductive release of cisplatin from the prodrug, which then formed 1,2-d(GpG) intrastrand cross-links in the cell nuclei, as confirmed by an antibody specific for this adduct. The cytotoxicity of the platinum(IV) complex increases significantly in several cancer cell lines when the complex is attached to the surface of the DNA-Au NPs and in some instances exceeds that of cisplatin.

A critical review of the emerging field of MOFs for photon collection and subsequent energy transfer is presented. Discussed are examples involving MOFs for (a) light harvesting, using (i) MOF-quantum dots and molecular chromophores, (ii) chromophoric MOFs, and (iii) MOFs with light-harvesting properties, and (b) energy transfer, specifically via the (i) Förster energy transfer and (ii) Dexter exchange mechanism.

There are now a variety of preparatory procedures for nanoscale gold rods, triangular prisms, and spheres. Many of these methods rely on seed-mediated approaches with cetyltrimethylammonium bromide (CTABr) as a surfactant. Interestingly, seemingly similar preparatory procedures yield very different morphologies, and although there have been a variety of proposals regarding the importance of different steps in shape control, there is no self-consistent procedure that allows one to take one batch of spherical seeds and grow either rods, prisms, or larger polyhedra in a controlled manner. In this report, it is shown that CTABr, depending upon supplier, has an iodide contaminant (at a significant but varying level), which acts as a key shape-directing element because it can strongly and selectively bind to the Au (111) facet and favor the formation of anisotropic structures. Furthermore, by starting with pure CTABr and deliberately adjusting iodide concentration, one can reproducibly drive the reaction to predominantly produce one of the three target morphologies.

, which contrasts with apparent activated conductivity for polycrystalline films. Microscopy studies further reveal that these MOFs are not isostructural as previously reported. Notably, single rods exhibit conductivities up to 150 S/cm, which persist even after prolonged exposure to ambient conditions. These single crystal studies confirm that 2D MOFs hold promise as molecularly tunable platforms for fundamental science and applications where porosity and conductivity are critical.

We develop the first mechanochemical and solvent-free routes for zirconium metal-organic frameworks, making the frameworks UiO-66 and UiO-66-NH2 accessible on the gram scale without strong acids, high temperatures or excess reactants. The frameworks form either by milling, or spontaneous self-assembly by simply exposing solid mixtures of reactants to organic vapour. The generated frameworks exhibit high porosity and catalytic activity in the hydrolysis of model nerve agents, on par with their solvothermally generated counterparts.

A new urea-containing metal-organic framework (MOF) was synthesized to act as a heterogeneous catalyst. Ureas are well-known for self-recognition and aggregation behavior, resulting in loss of catalytic competency. The catalyst spatial isolation achievable in a porous MOF environment suggests a potentially general solution. The combination of a symmetrical urea tetracarboxylate strut, 4,4'-bipyridine, and Zn(NO(3))(2)·6H(2)O under solvothermal conditions afforded a new microporous MOF (NU-601). This material is indeed an effective hydrogen-bond-donor catalyst for Friedel-Crafts reactions between pyrroles and nitroalkenes, whereas a homogeneous urea is much less competent. The higher rates of reaction of small substrates relative to larger ones with NU-601 strongly suggest that catalysis primarily occurs within the pores of this new material rather than on its exterior. To the best of our knowledge, this approach is the first example of specific engineering of successful hydrogen-bonding catalysis into a MOF material.

Lots of writing on the wall: A simple and flexible approach for performing high-throughput, large-area, direct-write molecular patterning, without tip feedback, is demonstrated by using a 55 000-pen two-dimensional array of atomic force microscope (AFM) cantilevers. The use of low-aspect-ratio pyramidal tips, curved cantilevers, and a novel gravity-driven alignment method allows parallel patterning of molecules across 1-cm2 substrate areas at sub-100-nm resolution. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z603142_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

This review discusses recent advances in the nonlinear optics of environmental interfaces. We discuss the quantitative aspects of the label-free approaches presented here and demonstrate that nonlinear optics has now assumed the role of a Swiss Army knife that can be used to dissect, with molecular detail, the fundamental and practical aspects of environmental interfaces and heterogeneous geochemical environments. In this work, nonlinear optical methods are applied to complex organic molecules, such as veterinary antibiotics, and to small inorganic anions and cations, such as nitrate and chromate, or cadmium, zinc, and manganese. The environmental implications of the thermodynamic, kinetic, spectroscopic, structural, and electrochemical data are discussed.

We report the synthesis of a new porous organic polymer based on condensation of inexpensive anhydride- and amine-bearing building blocks. The condensation produces a remarkably robust polyimide (nominally a diamond-type network) that retains its porosity after solvent evacuation and after prolonged soaking in water, aq. 0.1M HCl, or 50:50 triethylamine:DMF. This material features high surface area (900 m2/g) and pores of appropriate size and composition to capture CO2 from mixtures with methane.

Non-annealed graphene paper, prepared via reduction of prefabricated graphene oxide paper with hydrazine hydrate, was employed as the sole component of a binder-free lithium-ion battery anode, circumventing the polymer binders and other additives required for the fabrication of conventional electrodes. The binder-free anode fabricated from this non-annealed paper possessed excellent cyclability, while exhibiting a voltage versus capacity profile similar to that of a polymer-bound graphene powder anode. Kinetic barriers may exist for Li ion diffusion through the layered paper structure as decreasing the current rate from 50 to 10 mA·g−1 increased the reversible capacity by over 150%.

Cobalt ferrite magnetic nanostructures were synthesized via a high temperature solution phase method. Spherical nanostructures of various sizes were synthesized with the help of seed mediated growth of the nanostructures in organic phase, while faceted irregular (FI) cobalt ferrite nanostructures were synthesized via the same method but in the presence of a magnetic field. Magnetic properties were characterized by SQUID magnetometry, relaxivity measurements and thermal activation under RF field, as a function of size and shape. The results show that the saturation magnetization of the nanostructures increases with an increase in size, and the FI nanostructures exhibit lower saturation magnetization than their spherical counterparts. The relaxivity coefficient of cobalt ferrite nanostructures increases with increase in size; while FI nanostructures show a higher relaxivity coefficient than spherical nanostructures with respect to their saturation magnetization. In the case of RF thermal activation, the specific absorption rate (SAR) of nanostructures increases with increase in the size. The contribution sheds light on the role of size and shape on important magnetic properties of the nanostructures in relation to their biomedical applications.

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge-storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large-scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two-dimensional imine-linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.