Lasing Action with Gold Nanorod Hyperbolic Metamaterials

Coherent nanoscale photon sources are of paramount importance to achieving all-optical communication. Several nanolasers smaller than the diffraction limit have been theoretically proposed and experimentally demonstrated using plasmonic cavities to confine optical fields. Such compact cavities exhibit large Purcell factors, thereby enhancing spontaneous emission, which feeds into the lasing mode. However, most plasmonic nanolasers reported so far have employed resonant nanostructures and therefore had the lasing restricted to the proximity of the resonance wavelength. Here, we report on an approach based on gold nanorod hyperbolic metamaterials for lasing. Hyperbolic metamaterials provide broadband Purcell enhancement due to large photonic density of optical states, while also supporting surface plasmon modes to deliver optical feedback for lasing due to nonlocal effects in nanorod media. We experimentally demonstrate the advantage of hyperbolic metamaterials in achieving lasing action by its comparison with that obtained in a metamaterial with elliptic dispersion. The conclusions from the experimental results are supported with numerical simulations comparing the Purcell factors and surface plasmon modes for the metamaterials with different dispersions. We show that although the metamaterials of both types support lasing, emission with hyperbolic samples is about twice as strong with 35% lower threshold vs. the elliptic ones. Hence, hyperbolic metamaterials can serve as a convenient platform of choice for nanoscale coherent photon sources in a broad wavelength range

Nanometric Resolution in the Hydrodynamic Size Analysis of Ligand-Stabilized Gold Nanorods

The stability and hydrodynamic size of ligand-coated gold nanorods (GNRs; aspect ratio 3.6) have been characterized by nanoparticle tracking analysis (NTA)a single-particle counting method that can measure size distributions with low nanometer resolution. Stable aqueous suspensions of citrate-stabilized GNRs (cit-GNRs) are amenable to surface functionalization without loss of dispersion control. Cit-GNRs can be treated with chemisorptive ligands (thiols and dithiocarbamates), nonionic surfactants (Tween 20), and proteins (human serum albumin), all of which produce stable suspensions at low surfactant concentrations. The precision of NTA (relative standard deviation 10–12%, standard error <2%) is sufficient to allow differences in the hydrodynamic size of coated GNRs to be interpreted in terms of surfactant structure and conformation

Glycal Assembly by the in Situ Generation of Glycosyl Dithiocarbamates

Glycal assembly offers an expedient entry into β-linked oligosaccharides, but epoxyglycal donors can be capricious in their reactivities. Treatment with Et₂NH and CS₂ enables their in situ conversion into glycosyl dithiocarbamates, which can be activated by copper triflate for coupling with complex or sterically congested acceptors. The coupling efficiency can be further enhanced by in situ benzoylation, as illustrated in an 11-step synthesis of a branched hexasaccharide from glucals in 28% isolated yield and just four chromatographic purifications

Micellization and Single-Particle Encapsulation with Dimethylammoniopropyl Sulfobetaines

Sulfobetaines (SBs) are a class of zwitterionic surfactants with a reputation for enhancing colloidal stability at high salt concentrations. Here, we present a systematic study on the self-assembly of SB amphiphiles (sultaines or hydroxysultaines) in aqueous solutions, as a function of chain length and composition, ionic strength, and in the presence of alkanethiol-coated Au nanoparticles (GNPs). The diameters of the micelles assembled from SB and amidosulfobetaine (ASB) generally increase monotonically with chain length, although ASB micelles are smaller relative to alkyl SB micelles with similarly sized tailgroups, and oleyl sulfobetaine (OSB) micelles are slightly larger. SB amphiphiles can stabilize alkanethiol-coated GNPs in physiologically relevant buffers at concentrations well below their CMC, with size increases corresponding to single-particle encapsulation. SB-encapsulated GNPs were prepared by three different methods with SB:GNP weight ratios of 10:1, followed by dispersion in water or 1 M NaCl. The low hydrodynamic size of the SB micelles and SB-coated NPs is within the range needed for efficient renal clearance

Glycosyl Dithiocarbamates: β‑Selective Couplings without Auxiliary Groups

In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS₂. Glycosyl DTCs are readily activated with Cu­(I) or Cu­(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the efficient construction of a tri-β-1,6-linked tetrasaccharide. Glycosyl DTC couplings are highly β-selective despite the absence of a preexisting C2 auxiliary group. We provide evidence that the directing effect is mediated by the C2 hydroxyl itself via the putative formation of a cis-fused bicyclic intermediate

Preparation of Super-Stable Gold Nanorods via Encapsulation into Block Copolymer Micelles

Gold nanorods (GNRs) have the potential to be used as imaging and hyperthermia agents for cancer theranostics. Clinical applications of as-synthesized GNRs (i.e., cetyl trimethylammonium bromide (CTAB)-coated GNRs) are currently limited by their cytotoxicity and insufficient colloidal stability. With an aim to address these problems, we developed a self-assembly processing technique for encapsulating GNRs in poly­(ethylene oxide)-poly­(<i>n</i>-butyl acrylate) (PEO-PnBA) block copolymer (BCP) micelles. This technique uses simple steps of solvent exchange processes, based on the known principles of block copolymer self-assembly. The resultant BCP-encapsulated GNRs were found to be stable against aggregation under physiological salt conditions for indefinite periods of time, which has rarely previously been achieved by other means of encapsulation

Characterization of Asphaltene Deposits by Using Mass Spectrometry and Raman Spectroscopy

Crude oil deposition in oil transfer pipelines and bore wells afflicts many oil reservoirs. Asphaltenes play a major role in this process because of their tendency to precipitate in pipelines upon changes in temperature and/or pressure. Asphaltenes are defined by their lack of solubility in <i>n</i>-alkane solvents, which means that they likely contain many compounds that do not actively contribute to the deposition of crude oil in pipelines. The preponderance of studies in the literature have focused on asphaltenes derived from crude oil, whereas far fewer investigations have focused on asphaltenes derived from oil deposits. In this study, structural parameters of oil-deposit asphaltenes were examined using Raman spectroscopy and tandem mass spectrometry and compared to results reported previously for petroleum asphaltenes. On the basis of D1 and G band intensities in the Raman spectrum of oil-deposit asphaltenes, the average aromatic sheet size of these molecules was 21.0 Å, slightly larger than earlier values reported for petroleum asphaltenes (15.2–18.8 Å). Mass spectrometric experiments of oil-deposit asphaltenes ionized via atmospheric pressure chemical ionization (APCI) using CS₂ solvent were used to measure the molecular weight distribution (MWD), saturated carbon content, and the number of fused aromatic rings in the cores of the asphaltene molecules. The MWD was found to be 150–1050 Da with an average molecular weight (average <i>M</i>_W) of 497 Da, which are significantly lower than those reported previously for petroleum asphaltenes (200–1500 Da and 570–700 Da, respectively). Aromatic core sizes were estimated to contain 8 fused rings on average for the most abundant species in oil-deposit asphaltenes, with 5–15 carbons in their alkyl side chains, as compared to averages of 3–7 aromatic rings and 17–41 alkyl carbons for petroleum asphaltenes

Cys34-PEGylated Human Serum Albumin for Drug Binding and Delivery

Polyethylene glycol (PEG) derivatives were conjugated onto the Cys-34 residue of human serum albumin (HSA) to determine their effects on the solubilization, permeation, and cytotoxic activity of hydrophobic drugs such as paclitaxel (PTX). PEG­(C34)­HSA conjugates were prepared on a multigram scale by treating native HSA (n-HSA) with 5- or 20-kDa mPEG-maleimide, resulting in up to 77% conversion of the mono-PEGylated adduct. Nanoparticle tracking analysis of PEG­(C34)­HSA formulations in phosphate buffer revealed an increase in the number of nanosized aggregates relative to n-HSA, both in the absence and presence of PTX. Cell viability studies conducted with MCF-7 breast cancer cells indicated that PTX cytotoxicity was enhanced by PEG­(C34)­HSA when mixed at 10:1 mol ratios, up to a 2-fold increase in potency relative to n-HSA. The PEG­(C34)­HSA conjugates were also evaluated as PTX carriers across monolayers of HUVEC and hCMEC/D3 cells, and found to have permeation profiles nearly identical to those of n-HSA

Synthesis and Reactivity of 4′-Deoxypentenosyl Disaccharides

4-Deoxypentenosides (4-DPs) are versatile synthons for rare or higher-order pyranosides, and they provide an entry for structural diversification at the C5 position. Previous studies have shown that 4-DPs undergo stereocontrolled DMDO oxidation; subsequent epoxide ring-openings with various nucleophiles can proceed with both <i>anti</i> or <i>syn</i> selectivity. Here, we report the synthesis of α- and β-linked 4′-deoxypentenosyl (4′-DP) disaccharides, and we investigate their post-glycosylational C5′ additions using the DMDO oxidation/ring-opening sequence. The α-linked 4′-DP disaccharides were synthesized by coupling thiophenyl 4-DP donors with glycosyl acceptors using BSP/Tf₂O activation, whereas β-linked 4′-DP disaccharides were generated by the decarboxylative elimination of glucuronyl disaccharides under microwave conditions. Both α- and β-linked 4′-DP disaccharides could be epoxidized with high stereoselectivity using DMDO. In some cases, the α-epoxypentenosides could be successfully converted into terminal l-iduronic acids via the <i>syn</i> addition of 2-furylzinc bromide. These studies support a novel approach to oligosaccharide synthesis, in which the stereochemical configuration of the terminal 4′-DP unit is established at a post-glycosylative stage

Vascular toxicity of silver nanoparticles to developing zebrafish (<i>Danio rerio</i>)

<p>Nanoparticles (NPs, 1–100 nm) can enter the environment and result in exposure to humans and other organisms leading to potential adverse health effects. The aim of the present study is to evaluate the effects of early life exposure to polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs, 50 nm), particularly with respect to vascular toxicity on zebrafish embryos and larvae (<i>Danio rerio</i>). Previously published data has suggested that PVP-AgNP exposure can inhibit the expression of genes within the vascular endothelial growth factor (VEGF) signaling pathway, leading to delayed and abnormal vascular development. Here, we show that early acute exposure (0–12 h post-fertilization, hpf) of embryos to PVP-AgNPs at 1 mg/L or higher results in a transient, dose-dependent induction in VEGF-related gene expression that returns to baseline levels at hatching (72 hpf). Hatching results in normoxia, negating the effects of AgNPs on vascular development. Interestingly, increased gene transcription was not followed by the production of associated proteins within the VEGF pathway, which we attribute to NP-induced stress in the endoplasmic reticulum (ER). The impaired translation may be responsible for the observed delays in vascular development at later stages, and for smaller larvae size at hatching. Silver ion (Ag⁺) concentrations were < 0.001 mg/L at all times, with no significant effects on the VEGF pathway. We propose that PVP-AgNPs temporarily delay embryonic vascular development by interfering with oxygen diffusion into the egg, leading to hypoxic conditions and ER stress.</p