The Theoretical Research for the Rotor/Fuselage Unsteady Aerodynamic Interaction Problem

ABSTRACT Based on coupled unsteady panel/free-wake method, a universal analysis model was established, which provides a good prediction for the rotor/fuselage unsteady aerodynamic interaction. Considering the deficiencies of the traditional time-marching rotor free-wake algorithms, notably on stability and efficiency, the CB3D algorithm with 3rd-order accuracy is proposed. For solving the problem that part of the wake vortices may penetrate the fuselage, a “material line” rectification method with 3rd-order accuracy is proposed. An analysis for the model accuracy was then conducted to validate the accuracy of the new model, and a comparison against the available experimental data is performed. The simulated results show a good agreement with these experimental data. With the new model, several simulations are conducted for the typical rotor/fuselage aerodynamic interaction, and the results are analyzed.</div

Quenching of Quantum Dot Emission by Fluorescent Gold Clusters: What It Does and Does Not Share with the Förster Formalism

Understanding the interactions that control the energy transfer between dyes, or luminescent quantum dots (QDs), and gold nanoparticles still has several unanswered questions. In this study we probed these interactions using a unique model where CdSe-ZnS QDs were coupled to fluorescent gold nanoclusters (AuNCs). Steady-state and time-resolved fluorescence measurements were used to investigate the effects of spectral overlap and separation distance on the quenching of QD photoemission in these assemblies, using three different size QDs with distinct emission spectra and a variable length polyethylene glycol bridge. We found that the QD photoluminescence quenching efficiency depends on the spectral overlap and separation distance, with larger quenching efficiencies than what would be expected for a QD-dye pair with similar overlap. Moreover, despite the large losses in QD PL, we found no resonance enhancement in the cluster emission for any of the sample configurations used. These results indicate that the mechanism driving the quenching by metal clusters shares an important feature (namely dependence on the spectral overlap) with the Förster dipole–dipole coupling at the heart of fluorescence resonance energy transfer (FRET) and widely validated for dye-dye and QD-dye assemblies. They also prove that the energy losses induced by metal nanostructures are governed by a process that is different from the Förster mechanism

Self-Organized Tubular Structures as Platforms for Quantum Dots

The combination of top-down and bottom-up approaches offers great opportunities for the production of complex materials and devices. We demonstrate this approach by incorporating luminescent CdSe-ZnS nanoparticles into macroscopic tube structures that form as the result of externally controlled self-organization. The 1–2 mm wide hollow tubes consist of silica-supported zinc oxide/hydroxide and are formed by controlled injection of aqueous zinc sulfate into a sodium silicate solution. The primary growth region at the top of the tube is pinned to a robotic arm that moves upward at constant speed. Dispersed within the injected zinc solution are 3.4 nm CdSe-ZnS quantum dots (QDs) capped by DHLA-PEG–OCH₃ ligands. Fluorescence measurements of the washed and dried tubes reveal the presence of trapped QDs at an estimated number density of 10¹⁰ QDs per millimeter of tube length. The successful inclusion of the nanoparticles is further supported by electron microscopy and energy dispersive X-ray spectroscopy, with the latter suggesting a nearly homogeneous QD distribution across the tube wall. Exposure of the samples to copper sulfate solution induces quenching of about 90% of the tubes’ fluorescence intensity. This quenching shows that the large majority of the QDs is chemically accessible within the microporous, about 15-μm-wide tube wall. We suggest possible applications of such QD-hosting tube systems as convenient sensors in microfluidic and related applications

Data_Sheet_1_Proteins Are Well-Preserved in Shells Toasted at 300°C Revealed by Proteomics.ZIP

The development of protein anti-degradation strategies is important for storage at ambient conditions, for example in vaccine storage. Despite that it is known that biominerals, typical inorganic-organic composites, can preserve proteins at room temperature for a long time, it is unclear the extent of protein degradation under high temperatures. In this study, we examined remaining proteins in the toasted abalone shell under high temperatures (200 and 300°C) by biomineral proteomics method. Surprisingly, 21 proteins including carbonic anhydrase, hemocyanin, actin can still be identified from shells even after toasting under 300°C, not much decreased compared to that in the 200°C-treated and the native shell. However, the microstructure and composition (both mineral and organic matrix) of shells were altered significantly revealed by scanning electron microscopy, infrared spectroscopy, and X-ray diffraction. The well-preserved proteins may be partially due to the sacrifice of mineral/organic interfaces and the formation of nanopores in the shell at high temperatures. Moreover, the extracted proteins from both groups were able to affect calcium carbonate in vitro, indicating certain remaining bioactivities of proteins. This study has potential implications in various fields such as protein storage at high temperatures and palaeoproteomics.</p

Multidentate Zwitterionic Ligands Provide Compact and Highly Biocompatible Quantum Dots

Hydrophilic functional semiconductor nanocrystals that are also compact provide greatly promising platforms for use in bioinspired applications and are thus highly needed. To address this, we designed a set of metal coordinating ligands where we combined two lipoic acid groups, bis­(LA)-ZW, (as a multicoordinating anchor) with a zwitterion group for water compatibility. We further combined this ligand design with a new photoligation strategy, which relies on optical means instead of chemical reduction of the lipoic acid, to promote the transfer of CdSe-ZnS QDs to buffer media. In particular, we found that the QDs photoligated with this zwitterion-terminated bis­(lipoic) acid exhibit great colloidal stability over a wide range of pHs, to an excess of electrolytes, and in the presence of growth media and reducing agents, in addition to preserving their optical and spectroscopic properties. These QDs are also stable at nanomolar concentrations and under ambient conditions (room temperature and white light exposure), a very promising property for fluorescent labeling in biology. In addition, the compact ligands permitted metal–histidine self-assembly between QDs photoligated with bis­(LA)-ZW and two different His-tagged proteins, maltose binding protein and fluorescent mCherry protein. The remarkable stability of QDs capped with these multicoordinating and compact ligands over a broad range of conditions and at very small concentrations, combined with the compatibility with metal–histidine conjugation, could be very useful for a variety of applications, ranging from protein tracking and ligand–receptor binding to intracellular sensing using energy transfer interactions

Proteomics of Shell Matrix Proteins from the Cuttlefish Bone Reveals Unique Evolution for Cephalopod Biomineralization

In contrast to the external shells in bivalves and gastropods, most cephalopods are missing this external protection. The cuttlefish, belonging to class cephalopod, has an internal biomineralized structure made of mainly calcium carbonate for controlling buoyancy. However, the macromolecules, especially proteins that control cuttlebone mineral formation, are not sufficiently understood, limiting our understanding of the evolution of this internal shell. In this study, we extracted proteins from the cuttlebone of pharaoh cuttlefish Sepia pharaonis and performed liquid chromatography-tandem mass spectrometry to identify the shell matrix proteins (SMPs). In total, 41 SMPs were identified. Among them, hemocyanin, an oxygen-carrying protein, was the most abundant SMP. By comparison with SMPs of other marine biominerals, hemocyanin, apolipophorin, soul domain proteins, transferrin, FL-rich, and enolase were found to be unique to the cuttlebone. In contrast, typical SMPs of external shells such as carbonic anhydrase complement control protein, fibronectin type III, and G/A-rich proteins were lacking from the cuttlebone. Furthermore, the cluster analysis of biomineral SMPs suggests that the SMP repertoire of the cuttlebone does not resemble that of other species with external shells. Taken together, this study implies a potential relationship of the cuttlefish internal shell with other internal biominerals, which highlights a unique shell evolutionary pathway in invertebrates

A Multifunctional Polymer Combining the Imidazole and Zwitterion Motifs as a Biocompatible Compact Coating for Quantum Dots

We introduce a set of multicoordinating imidazole- and zwitterion-based ligands suited for surface functionalization of quantum dots (QDs). The polymeric ligands are built using a one-step nucleophilic addition reaction between poly­(isobutylene-<i>alt</i>-maleic anhydride) and distinct amine-containing functionalities. This has allowed us to introduce several imidazole anchoring groups along the polymer chain for tight coordination to the QD surface and a controllable number of zwitterion moieties for water solubilization. It has also permitted the introduction of reactive and biomolecular groups for further conjugation and targeting. The QDs capped with these new ligands exhibit excellent long-term colloidal stability over a broad range of pH, toward excess electrolyte, in cell-growth media, and in the presence of natural reducing agents such as glutathione. These QDs are also resistant to the oxidizing agent H₂O₂. More importantly, by the use of zwitterion moieties as the hydrophilic block, this polymer design provides QDs with a thin coating and compact overall dimensions. These QDs are easily self-assembled with full size proteins expressed with a polyhistidine tag via metal–histidine coordination. Additionally, the incorporation of amine groups allows covalent coupling of the QDs to the neurotransmitter dopamine. This yields redox-active QD platforms that can be used to track pH changes and detect Fe ions and cysteine through charge-transfer interactions. Finally, we found that QDs cap-exchanged with folic acid-functionalized ligands could effectively target cancer cells, where folate-receptor-mediated endocytosis of QDs into living cells was time- and concentration-dependent

Tuning the Redox Coupling between Quantum Dots and Dopamine in Hybrid Nanoscale Assemblies

We explored the charge transfer interactions between CdSe–ZnS core–shell quantum dots (QDs) and the redox active neurotransmitter dopamine, using covalently assembled QD–dopamine conjugates. We combined steady-state fluorescence, time-resolved fluorescence, and transient absorption bleach measurements to probe the effects of changing the QD size (thus the QD energy levels) and the conjugate valence on the rate of QD photoluminescence quenching when the pH of the medium was adjusted from acidic to alkaline. We measured substantially larger quenching efficiencies, combined with more pronounced shortening of the carrier dynamics of these assemblies for smaller size QDs and in alkaline pH. Moreover, we found that changes in the QD size alter the electron and hole relaxation of photoexcited QDs but with different extents. For instance, a pronounced change in the hole relaxation was measured in alkaline buffers. Moreover, the hole relaxation was faster for conjugates of green-emitting QDs as compared to their red-emitting counterparts. We attribute these results to the more favorable electron transfer rates from the reduced form of the dopamine to the valence band of the QDs, a process that becomes more efficient for green-emitting QDs. The latter benefits from lower oxidation potential and larger energy mismatch with the green QDs in alkaline buffers. In comparison, the effects of pH changes on the rates of electron transfer from excited QDs to dopamine are less affected by the QD size. These findings reflect the importance of the energy mismatch between the QD energy levels and the redox levels of dopamine, and shed light onto the complex interactions involved in these assemblies. Such conjugates also provide promising sensing and imaging tools for use in <i>in vivo</i> experiments

Multifunctional and High Affinity Polymer Ligand that Provides Bio-Orthogonal Coating of Quantum Dots

We detail the design of hydrophilic metal-coordinating ligands and their use for the effective coating of luminescent quantum dots (QDs). The ligand design exploits the specific, reagent-free nucleophilic addition reaction of amine-modified molecules toward maleic anhydride to introduce several lipoic acid metal anchors, hydrophilic zwitterion moieties, and specific reactive groups along a poly­(isobutylene-alt-maleic anhydride) (PIMA) chain. Tunable reactive groups tested in this study include azide, biotin, carboxyl, and amine. Cap exchange with these multilipoic acid ligands via a photochemical ligation strategy yields homogeneous QD dispersions that are colloidally stable over several biologically relevant conditions and for extended periods of time. The zwitterionic coating yields compact nanoparticle size and imparts nonsticky surface properties onto the QDs, preventing protein absorption. The introduction of a controllable number of reactive groups allows conjugation of the QDs to biomolecules via bio-orthogonal coupling chemistries including (1) attachment of the neurotransmitter dopamine to QDs via amine-isothiocyanate reaction to produce a platform capable of probing interactions with cysteine in proteins, based on charge transfer interactions; (2) self-assembly of biotinylated QDs with streptavidin-dye; and (3) ligation of azide-functionalized QDs to cyclooctyne-modified transferrin via copper-free click chemistry, used for intracellular delivery. This ligand design strategy can be used to prepare an array of metal-coordinating ligands adapted for coating other inorganic nanoparticles, including magnetic and plasmonic nanomaterials

Proteomics of Shell Matrix Proteins from the Cuttlefish Bone Reveals Unique Evolution for Cephalopod Biomineralization

In contrast to the external shells in bivalves and gastropods, most cephalopods are missing this external protection. The cuttlefish, belonging to class cephalopod, has an internal biomineralized structure made of mainly calcium carbonate for controlling buoyancy. However, the macromolecules, especially proteins that control cuttlebone mineral formation, are not sufficiently understood, limiting our understanding of the evolution of this internal shell. In this study, we extracted proteins from the cuttlebone of pharaoh cuttlefish Sepia pharaonis and performed liquid chromatography-tandem mass spectrometry to identify the shell matrix proteins (SMPs). In total, 41 SMPs were identified. Among them, hemocyanin, an oxygen-carrying protein, was the most abundant SMP. By comparison with SMPs of other marine biominerals, hemocyanin, apolipophorin, soul domain proteins, transferrin, FL-rich, and enolase were found to be unique to the cuttlebone. In contrast, typical SMPs of external shells such as carbonic anhydrase complement control protein, fibronectin type III, and G/A-rich proteins were lacking from the cuttlebone. Furthermore, the cluster analysis of biomineral SMPs suggests that the SMP repertoire of the cuttlebone does not resemble that of other species with external shells. Taken together, this study implies a potential relationship of the cuttlefish internal shell with other internal biominerals, which highlights a unique shell evolutionary pathway in invertebrates