Porous Polymersomes with Encapsulated Gd‐Labeled Dendrimers as Highly Efficient MRI Contrast Agents

The use of nanovesicles with encapsulated Gd as magnetic resonance (MR) contrast agents has largely been ignored due to the detrimental effects of the slow water exchange rate through the vesicle bilayer on the relaxivity of encapsulated Gd. Here, the facile synthesis of a composite MR contrast platform is described; it consists of dendrimer conjugates encapsulated in porous polymersomes. These nanoparticles exhibit improved permeability to water flux and a large capacity to store chelated Gd within the aqueous lumen, resulting in enhanced longitudinal relaxivity. The porous polymersomes, ～130 nm in diameter, are produced through the aqueous assembly of the polymers, polyethylene oxide‐b‐polybutadiene (PBdEO), and polyethylene oxide‐b‐polycaprolactone (PEOCL). Subsequent hydrolysis of the caprolactone (CL) block resulted in a highly permeable outer membrane. To prevent the leakage of small Gd‐chelate through the pores, Gd was conjugated to polyamidoamine (PAMAM) dendrimers via diethylenetriaminepentaacetic acid dianhydride (DTPA dianhydride) prior to encapsulation. As a result of the slower rotational correlation time of Gd‐labeled dendrimers, the porous outer membrane of the nanovesicle, and the high Gd payload, these functional nanoparticles are found to exhibit a relaxivity (R1) of 292 109 mM ^?1 s^?1 per particle. The polymersomes are also found to exhibit unique pharmacokinetics with a circulation half‐life of >3.5 h and predominantly renal clearance.     

Modulation of Mechanical Interactions by Local Piezoelectric Effects

Piezoelectricity is a well‐established property of biological materials, yet its functional role has remained unclear. Here, a mechanical effect of piezoelectric domains resulting from collagen fibril organisation is demonstrated, and its role in tissue function and application to material design is described. Using a combination of scanning probe and nonlinear optical microscopy, a hierarchical structuring of piezoelectric domains in collagen‐rich tissues is observed, and their mechanical effects are explored in silico. Local electrostatic attraction and repulsion due to shear piezoelectricity in these domains modulate fibril interactions from the tens of nanometre (single fibril interactions) to the tens of micron (fibre interactions) level, analogous to modulated friction effects. The manipulation of domain size and organisation thus provides a capacity to tune energy storage, dissipation, stiffness, and damage resistance.     

Interpretation of Absolute Laser Reflectance During Optical Monitoring of Polycrystalline GaAs Deposition on Quartz Using Metalorganic Chemical Vapor Deposition

Gallium arsenide (GaAs) was deposited by metalorganic chemical vapor deposition in a horizontal quartz reactor tube using trimethylgallium and arsine at 400°C to 500°C. Nucleation time and deposition rate were monitored using in situ laser reflectometry. This allowed differentiation between film and parasitic growth, which was not possible with other optical techniques. An absolute reflectance model was developed using measurements prior to GaAs deposition, and then employed to calculate values for GaAs on quartz. Detected reflectance intensities during experimental GaAs deposition were low compared with the model due to three-dimensional island growth, causing scattering of the incident laser radiation.     

Strain Anisotropies and Self‐Limiting Capacities in Single‐Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium‐Ion Battery Anodes

This study examines the crystallographic anisotropy of strain evolution in model, single‐crystalline silicon anode microstructures on electrochemical intercalation of lithium atoms. The 3D hierarchically patterned single‐ crystalline silicon microstructures used as model anodes were prepared using combined methods of photolithography and anisotropic dry and wet chemical etching. Silicon anodes, which possesses theoretically ten times the energy density by weight compared to conventional carbon anodes, reveal highly anisotropic but more importantly, variably recoverable crystallographic strains during cycling. Model strain‐limiting silicon anode architectures that mitigate these impacts are highlighted. By selecting a specific design for the silicon anode microstructure, and exploiting the crystallographic anisotropy of strain evolution upon lithium intercalation to control the direction of volumetric expansion, the volume available for expansion and thus the charging capacity of these structures can be broadly varied. We highlight exemplary design rules for this self‐strain‐limited charging in which an anode can be variably optimized between capacity and stability. Strain‐limited capacities ranging from 677 mAhg^?1 to 2833 mAhg^?1 were achieved by constraining the area available for volumetric expansion via the design rules of the microstructures.     

增强"软实力"中国企业成为全球明星不可或缺的因素

随着中国经济的发展,许多中国企业希望"百尺竿头,更进一步".对某些企业来说,这意味着跨出国门,在全球范围内同世界一流的公司同台竞技.而对另一些公司而言,这意味着增强自己在国内的实力,巩固市场地位,以便对抗日益强大的国内外竞争对手.     

A Modular Vaccine Platform Combining Self‐Assembled Peptide Cages and Immunogenic Peptides

Subunit vaccines use delivery platforms to present minimal antigenic components for immunization. The benefits of such systems include multivalency, self‐adjuvanting properties, and more specific immune responses. Previously, the design, synthesis, and characterization of self‐assembling peptide cages (SAGEs) have been reported. In these, de novo peptides are combined to make hubs that assemble into nanoparticles when mixed in aqueous solution. Here it is shown that SAGEs are nontoxic particles with potential as accessible synthetic peptide scaffolds for the delivery of immunogenic components. To this end, SAGEs functionalized with the model antigenic peptides tetanus toxoid_632‐651 and ovalbumin_323‐339 drive antigen‐specific responses both in vitro and in vivo, eliciting both CD4⁺ T cell and B cell responses. Additionally, SAGEs functionalized with the antigenic peptide hemagglutinin_518‐526 from the influenza virus are also able to drive a CD8⁺ T cell response in vivo. This work demonstrates the potential of SAGEs to act as a modular scaffold for antigen delivery, capable of inducing and boosting specific and tailored immune responses.     

Polydopamine Encapsulation of Fluorescent Nanodiamonds for Biomedical Applications

Fluorescent nanodiamonds (FNDs) are promising bioimaging probes compared with other fluorescent nanomaterials such as quantum dots, dye‐doped nanoparticles, and metallic nanoclusters, due to their remarkable optical properties and excellent biocompatibility. Nevertheless, they are prone to aggregation in physiological salt solutions, and modifying their surface to conjugate biologically active agents remains challenging. Here, inspired by the adhesive protein of marine mussels, encapsulation of FNDs within a polydopamine (PDA) shell is demonstrated. These PDA surfaces are readily modified via Michael addition or Schiff base reactions with molecules presenting thiol or nitrogen derivatives. Modification of PDA shells by thiol terminated poly(ethylene glycol) (PEG‐SH) molecules to enhance colloidal stability and biocompatibility of FNDs is described. Their use as fluorescent probes for cell imaging is demonstrated; it is found that PEGylated FNDs are taken up by HeLa cells and mouse bone marrow‐derived dendritic cells and exhibit reduced nonspecific membrane adhesion. Furthermore, functionalization with biotin‐PEG‐SH is demonstrated and long‐term high‐resolution single‐molecule fluorescence based tracking measurements of FNDs tethered via streptavidin to individual biotinylated DNA molecules are performed. This robust polydopamine encapsulation and functionalization strategy presents a facile route to develop FNDs as multifunctional labels, drug delivery vehicles, and targeting agents for biomedical applications.     

Interface dipole engineering at buried organic–organic semiconductor heterojunctions

A general technique for modifying energy level alignment at organic–organic heterojunctions is introduced, and is demonstrated here for phenyl-C₆₁-butyric acid methyl ester (PCBM) and N,N′-Di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl)-4,4′-diamine (α-NPD). An ultra-thin layer (∼1 nm) of TiO₂ is used as an adhesion template to attach a self-assembled monolayer of dipolar phosphonate (PA) molecules to the lower interface of a two-stack ensemble. This modification induces shifts in the vacuum level and work function over ∼1.0 eV depending on the molecular dipole moment of the PA, which in turn modifies the electronic level alignment across the organic heterojunction interface by up to 0.5 eV.     

Ochratoxin A in dried vine fruit: method development and survey

A method is described for the determination of concentrations of the mycotoxin ochratoxin A in dried vine fruits (currants, raisins and sultanas) using acidic methanolic extraction,immunoaffinity chromatography clean-up and HPLC determination. The limit of detection was estimated as 0.2mug/kg, and recoveries of 63-77% were achieved at 5mug/kg. HPLC-mass spectrometric confirmation of the identity of ochratoxin was obtained. Ochratoxin A and aflatoxins were determined in 60 samples of retail dried vine fruits purchased in the United Kingdom. Ochratoxin A was found in excess of 0.2mug/kg in 19 of 20 currant, 17 of 20 sultana and 17 of 20 raisin samples examined, an overall incidence of 88% . The maximum level found was 53.6mug/kg. No aflatoxin was found in any sample analysed, using a method with a detection limit of 0.2mug/kg for each of aflatoxin B1, B2, G1 and G2.