Anion Sensing Porphyrin Functionalized Nanoparticles

Disulfide and dithiocarbamate functionalized porphyrins have been synthesized and used as protecting ligands for gold nanoparticle formation either via ligand substitution reactions or by direct synthesis. These nanoparticles have been shown to recognize anions via changes in the absorbance spectrum of the surface adsorbed porphyrin moieties. Association constants, derived from quantitative titrations, indicate a remarkable surface enhancement effect where the surface bound porphyrins bind anions much more strongly than the free receptor in solution.     

Effect of composition on gelation kinetics of unfilled and nanoapatite-filled poly(lactide-ethylene oxide-fumarate) hydrogels

Oscillatory shear rheometry at small strains was used to investigate the effects of composition (concentration of macromer, crosslinker, initiator/accelerator, and filler) on the gel point and ultimate storage modulus of poly(l-lactide-co-ethylene oxide-co-fumarate) (PLEOF) hydrogels. PLEOF in situ polymerizing hydrogels can be used as biodegradable scaffolds for cell encapsulation and tissue regeneration. The time evolution of the viscoelastic properties of the polymerizing mixture during the sol-gel transition was monitored using mechanical rheometry. According to the results, while the ultimate storage modulus linearly increased with the concentration of methylene bisacrylamide (BISAM) crosslinker, the values of the storage and loss moduli at the gel point were insensitive to the concentration of BISAM. Similar behavior was observed for PLEOF hydrogels reinforced with hydroxyapatite nanoparticles.     

青城子矿田小佟家堡子金银矿床地质特征及成矿物质来源探讨

小佟家堡子金银矿床赋存在辽河群大石桥组PtLd^5 3和PtLd^4 3的互层带之中。矿体受层间滑脱构造控制。容矿岩石以自云石大理岩和硅质岩为主，矿体呈层就、似层就。矿石中的金以不可见金为主，金古量与毒砂关系最密切。成矿物质来源于地层——即海底火山喷气和喷流作用形成含矿热卤水，经运移在海盆边缘沉积形成矿源层或维集区，经区域变质作用和岩浆作用的改造，在印支期就位。矿床成因类型为同生沉积-变质一岩浆热液叠加再造型金银矿床。     

Effect of Aminated Chitosan-Coated Fe3O4 Nanoparticles with Applicational Potential in Nanomedicine on DPPG,DSPC, and POPC Langmuir Monolayers as Cell Membrane Models

An adsorption process of magnetite nanoparticles functionalized with aminated chitosan (Fe₃O₄-AChit) showing application potential in nanomedicine into cell membrane models was studied. The cell membrane models were formed using a Langmuir technique from three selected phospholipids with different polar head-groups as well as length and carbon saturation of alkyl chains. The research presented in this work reveals the existence of membrane model composition-dependent regulation of phospholipid-nanoparticle interactions. The influence of the positively charged Fe₃O₄-AChit nanoparticles on a Langmuir film stability, phase state, and textures is much greater in the case of these formed by negatively charged 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG) than those created by zwitterionic 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC). The adsorption kinetics recorded during penetration experiments show that this effect is caused by the strongest adsorption of the investigated nanoparticles into the DPPG monolayer driven very likely by the electrostatic attraction. The differences in the adsorption strength of the Fe₃O₄-AChit nanoparticles into the Langmuir films formed by the phosphatidylcholines were also observed. The nanoparticles adsorbed more easily into more loosely packed POPC monolayer.     

Red Emissive Carbon Dots Prepared from Polymers as an Efficient Nanocarrier for Coptisine Delivery in vivo and in vitro

Negatively charged fluorescent carbon dots (CDs, E_m=608 nm) were hydrothermally prepared from thiophene phenylpropionic acid polymers and then successfully loaded with the positively charged anticancer cargo coptisine, which suffers from poor bioavailability. The formed CD-coptisine complexes were thoroughly characterized by particle size, morphology, drug loading efficiency, drug release, cellular uptake and cellular toxicity in vitro and antitumor activities in vivo. In this nano-carrier system, red emissive CDs possess multiple advantages as follows: 1) high drug loading efficiency (>96 %); 2) sustained drug release; 3) enhanced drug efficacy towards cancer cells; 4) EPR effect; 5) drug release tracing with near-infrared imaging. These properties indicated that red emissive CDs prepared from polymers could be used as a novel drug delivery system with integrated therapeutic and imaging functions in cancer therapy, which are expected to have great potential in future clinical applications.     

Continuous size fractionation of magnetic nanoparticles by using simulated moving bed chromatography

The size fractionation of magnetic nanoparticles is a technical problem, which until today can only be solved with great effort. Nevertheless, there is an important demand for nanoparticles with sharp size distributions, for example for medical technology or sensor technology. Using magnetic chromatography, we show a promising method for fractionation of magnetic nanoparticles with respect to their size and/or magnetic properties. This was achieved by passing magnetic nanoparticles through a packed bed of fine steel spheres with which they interact magnetically because single domain ferro-/ferrimagnetic nanoparticles show a spontaneous magnetization. Since the strength of this interaction is related to particle size, the principle is suitable for size fractionation. This concept was transferred into a continuous process in this work using a so-called simulated moving bed chromatography. Applying a suspension of magnetic nanoparticles within a size range from 20 to 120 nm, the process showed a separation sharpness of up to 0.52 with recovery rates of 100%. The continuous feed stream of magnetic nanoparticles could be fractionated with a space-time-yield of up to 5 mg/(L∙min). Due to the easy scalability of continuous chromatography, the process is a promising approach for the efficient fractionation of industrially relevant amounts of magnetic nanoparticles.     

Cardioinotropic Effects in Subchronic Intoxication of Rats with Lead and/or Cadmium Oxide Nanoparticles

Subchronic intoxication was induced in outbred male rats by repeated intraperitoneal injections with lead oxide (PbO) and/or cadmium oxide (CdO) nanoparticles (NPs) 3 times a week during 6 weeks for the purpose of examining its effects on the contractile characteristics of isolated right ventricle trabeculae and papillary muscles in isometric and afterload contractions. Isolated and combined intoxication with these NPs was observed to reduce the mechanical work produced by both types of myocardial preparation. Using the in vitro motility assay, we showed that the sliding velocity of regulated thin filaments drops under both isolated and combined intoxication with CdO–NP and PbO–NP. These results correlate with a shift in the expression of myosin heavy chain (MHC) isoforms towards slowly cycling β–MHC. The type of CdO–NP + PbO–NP combined cardiotoxicity depends on the effect of the toxic impact, the extent of this effect, the ratio of toxicant doses, and the degree of stretching of cardiomyocytes and muscle type studied. Some indices of combined Pb–NP and CdO–NP cardiotoxicity and general toxicity (genotoxicity included) became fully or partly normalized if intoxication developed against background administration of a bioprotective complex.     

X-ray Fluorescence Uptake Measurement of Functionalized Gold Nanoparticles in Tumor Cell Microsamples

Quantitative cellular in vitro nanoparticle uptake measurements are possible with a large number of different techniques, however, all have their respective restrictions. Here, we demonstrate the application of synchrotron-based X-ray fluorescence imaging (XFI) on prostate tumor cells, which have internalized differently functionalized gold nanoparticles. Total nanoparticle uptake on the order of a few hundred picograms could be conveniently observed with microsamples consisting of only a few hundreds of cells. A comparison with mass spectroscopy quantification is provided, experimental results are both supported and sensitivity limits of this XFI approach extrapolated by Monte-Carlo simulations, yielding a minimum detectable nanoparticle mass of just 5 pg. This study demonstrates the high sensitivity level of XFI, allowing non-destructive uptake measurements with very small microsamples within just seconds of irradiation time.     

Stereocomplex Crystallization Induced Significant Improvement in Transparency and Stiffness–Toughness Performance of Core-Shell Rubber Nanoparticles Toughened Poly(l-lactide) Blends

Toughening modification of poly(l -lactide) (PLLA) with rubber particles is often realized at the cost of transparency, mechanical strength, and modulus because high rubber loadings are generally required for toughening. In this work, a promising strategy to simultaneously improve the transparency and stiffness–toughness performance of poly(butyl acrylate)-poly(methyl methacrylate) (BAMMA) core-shell rubber nanoparticles toughened PLLA blends by utilizing the stereocomplex (SC) crystallization between PLLA and poly(d -lactide) (PDLA) is devised. The results reveal that the construction of SC crystallites in PLLA matrix via melt-mixing PLLA/BAMMA blends with PDLA can prevent BAMMA nanoparticles from aggregation and promote them to form network-like structure at lower contents. As a result, not only higher toughening efficiency with less rubber contents but also superior transparency is achieved in the PLLA/PDLA/BAMMA blends as compared with the PLLA/BAMMA ones where large aggregated BAMMA clusters are formed. Moreover, the outstanding reinforcement of SC crystallites network for PLLA can impart an enhanced tensile strength and modulus to PLLA/PDLA/BAMMA blends, thus improving the stiffness–toughness performance of PLLA/PDLA/BAMMA blends to a higher degree. This work demonstrates that SC crystallization is a promising solution to solve the contradiction between transparency and mechanical properties and then obtain superior comprehensive performances in rubber toughened PLLA blends.     

Micron-Scale Soft Actuators Fabricated from Multi-Shell Polystyrene Particle-Gold Nanoparticle Nanohybrids

Actuators made of soft matter are needed for a variety of fields ranging from biomedical devices to soft robotics to microelectromechanical systems. While there are a variety of excellent methods of soft actuation known, the field is still an area of intense research activity as new niches and needs emerge with new technology development. Here, a soft actuation system is described, based on a core-multi-shell particle, which moves via photothermal expansion. The system consists of a novel polystyrene-based thermally expandable microsphere, with a secondary shell of a silicate-silane graft copolymer, to which gold nanoparticles are covalently linked. The gold nanoparticles act as photothermal nano-transducers, converting light energy into the thermal energy necessary for microsphere expansion, which in turn results in material movement. Actuation is shown in isolated particles in thermal and photothermal regimes using metal ceramic heaters or 520 nm laser illumination, respectively. Macroscale actuation is demonstrated by making a composite material of particles suspended in the transparent elastomer polydimethylsiloxane. The sample demonstrates an inchworm-like movement by starting from an arched geometry. Overall, this work describes a new particle-based actuation method for soft materials, and demonstrates its utility in driving the movement of a composite elastomer.