Biomimetic Hydroxyapatite Crystallization in Gelatin Nanoparticles Synthesized Using a Miniemulsion Process

Here, we report a novel biomimetic strategy to synthesize hydroxyapatite (HAP) inside of crosslinked gelatin nanoparticles, which serve as a nanoenvironment for crystal growth in the aqueous phase. The synthesis of gelatin nanoparticles with the inverse miniemulsion technique is very intriguing because of the flexibility offered by the technique in tailoring the properties of the gelatin nanoparticles. It can be shown that the nanoenvironment promotes a different growth environment for the crystal because of the confinement inside the particle. The formation of HAP inside the particles follows Ostwald's rule of stages. At first an amorphous phase is formed, which itself has a great potential to be used as a resorbable bone substitute. This further transforms into single crystalline HAP via an octacalcium phosphate intermediate. The solution‐mediated transformation into the HAP phase without any calcination step is studied in detail using transmission electron microscopy (TEM) and X‐ray diffraction (XRD) measurements.     

Two are Better than One: Combining ZnO and MgF2 Nanoparticles Reduces Streptococcus pneumoniae and Staphylococcus aureus Biofilm Formation on Cochlear Implants

Streptococcus pneumoniae (S. pneumoniae) and Staphylococcus aureus (S.aureus) are considered the most common colonizers of cochlear implants (CI), which have prompted the search for new ways to inhibit their growth and biofilm development. In the current study, CI‐based platforms are prepared and sonochemically coated with ZnO or MgF₂ nanoparticles (NPs), two agents previously shown to possess antibacterial properties. Additionally, a method is developed for coating both ZnO and MgF₂ on the same platform to achieve synergistic activity against both pathogens. Each surface is characterized, and the optimal conditions for the NP homogenous distribution on the surface are determined. The ZnO‐MgF₂ surface significantly reduces the S. pneumoniae and S. aureus biofilm compared with the surfaces coated with either ZnO or MgF₂, even though it contains smaller amounts of each NP type. Importantly, leaching assays show that the NPs remain anchored to the surface for at least 7 d. Finally, biocompatibility studies demonstrate that coating with low concentrations of ZnO‐MgF₂ results in no toxicity toward primary human fibroblasts from the auditory canal. Taken together, these findings underscore the potential of using NP combinations such as the one presented here to efficiently inhibit bacterial colonization and growth on medical devices such as CIs.     

Off/On Fluorescent Nanoparticles for Tunable High‐Temperature Threshold Sensing

Herein, a versatile threshold temperature sensor based on the glass transition temperature‐triggered fluorescence activation of a dye/developer duo, encapsulated in polymeric nanoparticles is reported. The emission enhancement, detectable even by unaided eye is completed within a narrow temperature range and activates at adjustable threshold temperatures up to 200 °C. Fluorescence is chosen as sensing probe due to its high detection sensitivity together with an advanced spatial and temporal resolution. The strategy is based on nanoparticles prepared from standard thermoplastic polymers, a fluorescence developer, and the commercially available Rhodamine B base dye, a well‐known and widely used fluorescent molecule. By making nanoparticles of different thermoplastic polymers, fast, abrupt, and irreversible disaggregation induced fluorescence enhancement, with tunable threshold temperature depending on the nanoparticles polymer glass transition is achieved. As a proof‐of‐concept for the versatility of this novel family of NPs, their use for sensing the thermal history of environments and surfaces exposed to the threshold temperature is showed.     

Effect of Exchange Interactions on the Coercivity of SmCo5 Nanoparticles Made by Cluster Beam Deposition

Single crystal SmCo₅ nanoparticles with an average size of 3.5 nm are produced by cluster‐beam deposition. When deposited without matrix, the nanoparticles showed a super‐paramagnetic behavior with a blocking temperature of 145 K. Dispersion of the SmCo₅ nanoparticles in a carbon matrix results in an increase in both the coercivity and the blocking temperature. Room temperature coercivities as high as 12 kOe are obtained for the first time in mono‐layers of SmCo₅ nanoparticles dispersed in C matrix. δM plots show that the interactions in the samples are of exchange type, which can decrease the overall effective anisotropy and coercivity according to the random‐anisotropy model. Coercivity is found to be inversely proportional to the packing density of the particles. SmCo₅ nanoparticles with high coercivity are potential candidates for the next generation ultra high‐density magnetic recording media.     

热处理对脉冲激光沉积羟基磷灰石薄膜组织和性能的影响

利用脉冲激光沉积技术在Ti6Al4V(TC4)合金表面制备了羟基磷灰石(HA)薄膜,研究了退火温度对薄膜组织和性能的影响。采用扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)和傅里叶红外光谱(FTIR)等分析手段对热处理前后薄膜的表面形貌、成分和组织结构进行了分析;采用轮廓仪、接触角测量仪分别对热处理前后薄膜的表面粗糙度和润湿性进行了测量。实验结果表明,利用脉冲激光沉积技术制备的HA薄膜致密、无缺陷,主要由非晶相组成。热处理后的薄膜结晶度提高、表面粗糙度增大,Ca/P比更接近于HA,具有更好的表面亲水性。但是过高的热处理温度(700℃)会导致薄膜中微裂纹的出现。     

Robust Red Organic Nanoparticles for In Vivo Fluorescence Imaging of Cancer Cell Progression in Xenografted Zebrafish

Bright and red‐emissive organic nanoparticles (NPs) are demonstrated as promising for in vivo fluorescence imaging. However, most red organic dyes show greatly weakened or quenched emission in the aggregated state. In this work, a robust red fluorophore (t‐BPITBT‐TPE) with strong aggregate‐state photoluminescence and good biocompatibility is presented. The NPs comprised of t‐BPITBT‐TPE aggregates encapsulated within 1,2‐distearoyl‐sn‐glycero‐3‐phosphoethanolamine‐N‐[methoxy(polyethylene glycol) (DSPE‐mPEG) micelles exhibit a photoluminescence peak at 660 nm with a high fluorescence quantum yield of 32% in aqueous media. The NPs can be facilely charged by using the same polymeric matrix with different terminal groups, e.g., methoxy (DSPE‐mPEG), amine (DSPE‐PEG‐NH₂), or carboxymethyl (DSPE‐PEG‐COOH) groups. The biocompatibility, toxicity, circulation, and biodistribution of the NPs are assessed using the zebrafish model through whole embryo soaking and intravenous delivery. Furthermore, HeLa and MCF‐7 cells tagged with t‐BPITBT‐TPE in DSPE‐PEG‐NH₂‐TAT polymer NPs are xenografted into zebrafish larvae to successfully track the cancer cell proliferation and metastasis, demonstrating that these new NPs are efficient cancer cell trackers. In addition, the NPs also show good in vivo imaging ability toward 4T1 tumors in xenografted BALB/c mice.     

Biocompatible Nanoparticles Based on Diketo‐Pyrrolo‐Pyrrole (DPP) with Aggregation‐Induced Red/NIR Emission for In Vivo Two‐Photon Fluorescence Imaging

Compared with traditional one‐photon fluorescence imaging, two‐photon fluorescence imaging techniques have shown advantages such as increased penetration depth, lower tissue autofluorescence, and reduced photo­damage, and therefore are particularly useful for imaging tissues and animals. In this work, the design and synthesis of two novel DPP ‐based compounds with large two‐photon absorption (2PA) cross‐sections (σ ≥ 8100 GM) and aggregation‐induced emission (AIE) properties are reported. The new compounds are red/NIR emissive and show large Stokes shifts (Δλ ≥ 3571 cm^?1). 1,2‐Distearoyl‐sn‐glycero‐3‐phosphoethanol amine‐N‐[maleimide(polyethylene glycol)‐2000 (DSPE‐PEG‐Mal) is used as the encapsulation matrix to encapsulate DPP‐2 , followed by surface functionalization with cell penetrating peptide (CPP) to yield DPP‐2‐CPP nanoparticles with high brightness, good water dispersibility, and excellent biocompatibility. DPP‐2 nanoparticles have been used for cell imaging and two‐photon imaging with clear visualization of blood vasculature inside mouse ear skin with a depth up to 80 μm.     

Biocompatible Nanoparticles with Aggregation‐Induced Emission Characteristics as Far‐Red/Near‐Infrared Fluorescent Bioprobes for In Vitro and In Vivo Imaging Applications

Light emission of 2‐(2,6‐bis((E)‐4‐(diphenylamino)styryl)‐4H‐pyran‐4‐ylidene)malononitrile (TPA‐DCM) is weakened by aggregate formation. Attaching tetraphenylethene (TPE) units as terminals to TPA‐DCM dramatically changes its emission behavior: the resulting fluorogen, 2‐(2,6‐bis((E)‐4‐(phenyl(4′‐(1,2,2‐triphenylvinyl)‐[1,1′‐biphenyl]‐4‐yl)amino)styryl)‐4H‐pyran‐4‐ylidene)malononitrile (TPE‐TPA‐DCM), is more emissive in the aggregate state, showing the novel phenomenon of aggregation‐induced emission (AIE). Formulation of TPE‐TPA‐DCM using bovine serum albumin (BSA) as the polymer matrix yields uniformly sized protein nanoparticles (NPs) with high brightness and low cytotoxicity. Applications of the fluorogen‐loaded BSA NPs for in vitro and in vivo far‐red/near‐infrared (FR/NIR) bioimaging are successfully demonstrated using MCF‐7 breast‐cancer cells and a murine hepatoma‐22 (H₂₂)‐tumor‐bearing mouse model, respectively. The AIE‐active fluorogen‐loaded BSA NPs show an excellent cancer cell uptake and a prominent tumor‐targeting ability in vivo due to the enhanced permeability and retention effect.     

Synthetic Routes and Formation Mechanisms of Spherical Boron Nitride Nanoparticles

A new concept is proposed to explain the formation of spherical boron nitride (BN) nanoparticles synthesized by the chemical vapor deposition (CVD) reaction of trimethoxyborane (B(OMe)₃) with ammonia. The intermediate phases formed during the CVD under different reaction conditions are analyzed by X‐ray diffraction, electron microscopy, thermogravimetry, and spectroscopy techniques. The transition mechanism from an intermediate B(OMe)_3–xH_3–xN (x < 2) phase having single B? N bonds to the BN nanoparticles is elucidated. This particularly emphasizes the CVD temperature effect governing the conversion of the N? H···O? B hydrogen bonds in (OMe)₃B · NH₃ into the N? B bonds in B(OMe)_3–xH_3–xN. The spherical morphology strongly depends on the remnant impurity oxygen formed upon Me₂O group elimination in the intermediate. Two types of spherical BN nanoparticles primarily attractive for immediate commercialization (with C and H impurities at a level less than 1 wt %) are synthesized by the adjustment of experimental parameters: high oxygen‐containing (～6.3 wt %) BN spheres with a diameter of ～90 nm and a specific surface area of 26.8 m² g^?1; and low oxygen‐containing (<1 wt %) BN spheres with a diameter of ～30 nm and a surface area of 52.7 m² g^?1. Finally, the regarded synthetic techniques are fully optimized in the present work.     

Spray Deposition of Titania Films with Incorporated Crystalline Nanoparticles for All‐Solid‐State Dye‐Sensitized Solar Cells Using P3HT

Spray coating, a simple and low‐cost technique for large‐scale film deposition, is employed to fabricate mesoporous titania films, which are electron‐transporting layers in all‐solid‐state dye‐sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small‐angle X‐ray scattering, and nitrogen adsorption–desorption isotherms. The crystal phase and crystallite sizes are verified by X‐ray diffraction measurements. The photovoltaic performance of all‐solid‐state DSSCs is investigated. The findings reveal that an optimal active layer of the all‐solid‐state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam‐like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m² g^?1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%.     

Printing Ultrasensitive Artificially Intelligent Sensors Array with a Single Self‐Propelled Droplet Containing Nanoparticles

The fabrication and implementation of artificially intelligent sensor arrays has faced serious technical and/or cost‐effectiveness challenges. Here, a new printing method is presented to produce a fully functional array of sensors based on monolayer‐capped gold nanoparticles. The proposed printing technique is based on the so‐called self‐propelled antipinning ink droplet, from which evaporative deposition takes place along the path of motion. By applying actuating forces, different deposition line patterns with different thicknesses and morphology from a single droplet are generated. The functionality of the produced sensors is demonstrated by their ability to detect different representative volatile organic compounds (VOCs) belonging to different chemical families, including alcohols, alkanes, ethers, and aromatics, and under extremely different humidity levels resembling those encountered in real‐world conditions. The results show that the sensors exhibit ultrasensitive sensing features, with an ability to detect and differentiate between different VOCs at low ppb levels. Additionally, the results show that the sensors are able to accurately predict VOC concentrations, viz. enable quantification capabilities, while nevertheless being inexpensive, do not need complicated and expensive printing equipment and prepatterning processes, allow low voltage operation, and provide a platform for multifunctional applications.     

Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self‐Assembled Organometallic Diblock Copolymer Thin Films

The controlled adsorption of the iron‐containing cage protein ferritin at the nanoscale using stimuli‐responsive self‐assembled diblock copolymer thin‐film templates is reported. The diblock copolymer used study consists of a cylinder‐forming polystyrene‐block‐polyferrocenylsilane (PS‐b‐PFS), with PFS as the minor block, and shows reversible redox properties. To prevent any spontaneous protein adsorption on either block, the electrolyte pH is selected to leave the ferritin negatively charged, and the protein concentration and solution ionic strength are carefully tuned. Selective adsorption of ferritin on the PFS domains of the self‐assembled thin films is then triggered in situ by applying a positive potential, simultaneously oxidizing the PFS and attracting the ferritin electrostatically.     

In Situ Monitoring the Role of Working Metal Catalyst Nanoparticles for Ultrahigh Purity Single‐Walled Carbon Nanotubes

The high‐end applications of single‐walled carbon nanotubes (SWCNTs) are hindered by the existence of large amount of impurities, especially the graphene layers encapsulating metal nanoparticles (metal@C NPs). The role of working metal catalysts during chemical vapor deposition (CVD) growth and post purifications by oxidation are not yet fully understood. Herein, the in situ monitoring the role of working metal catalyst NPs for ultrahigh purity SWCNTs by CVD growth and CO₂ purifications is carried out in an online thermogravimetric reactor attached with a mass spectrometer. The growth of SWCNTs almost stops after the initial 2 min, then, the mass increase of the samples mainly originates from the metal@CNP formation. Therefore, high‐purity SWCNTs (98.5 wt%) with few metal@CNPs can be available by 2 min CVD growth. Furthermore, CO₂ oxidation of the SWCNTs is also investigated in a thermogravimetric reactor. The oxidation of graphene layers surrounding the metal NPs and the SWCNTs occurs during distinct temperature ranges, which is further demonstrated by the significant differences among their oxidation activation energies. Ultrahigh purity of SWNCT with a carbon content of 99.5 wt% can be available by a CO₂‐assited purification method. The in situ study of the CVD growth and CO₂ oxidation of SWCNTs provides the real time information on the working catalyst during reaction and the reactivity information of metal@CNPs and SWCNTs under an oxidizing atmosphere. The success for the preparation of high‐purity SWCNT lies in the efficient growth of SWCNTs with a low amount of nanocarbon impurities and partial oxidation of metal@CNPs by catalytic CO₂ oxidation with proper operation parameters.     

Nano Spray‐Dried Block Copolymer Nanoparticles and Their Transformation into Hybrid and Inorganic Nanoparticles

A novel combination of block copolymer (BCP) nano spray‐drying (NSD), solvent annealing, and selective metal oxide growth is utilized to create functional polymer nanoparticles, polymer‐metal‐oxide hybrid nanoparticles, and templated metal oxide nanoparticles with tunable composition, internal morphology, and porosity. NSD of BCPs from chloroform and toluene solutions results in porous and nonporous nanoparticles, respectively, with various degrees of phase separation. Further tuning of the nanoparticle internal morphology is performed by solvent annealing the spray‐dried particles with judicious choice of the nonsolvent dispersion medium and the surfactant, yielding assembly of both blocks at the surface of the nanoparticles. Finally, ZnO and Al₂O₃ are grown inside the polar blocks of phase‐ordered nanoparticles using a sequential infiltration synthesis method, in a post‐assembly process, resulting in hybrid BCP‐ZnO particles and BCP‐templated Al₂O₃ nanoparticles, as demonstrated by scanning transmission electron microscopy tomography. These structure engineering methods open new ways to direct and template functional nanoparticles.     

激光熔覆HA生物陶瓷梯度涂层的微观组织结构

利用激光熔覆的方法在纯钛表面制备了羟基磷灰石(HA)生物陶瓷梯度涂层，通过电子探针和X射线衍射仪(XRD)对不同工艺参数下制备的涂层进行了微观组织观察和物相分析。实验结果表明，当激光功率为600W，扫描速度为3．5mm／s时，在纯钛表面可获得组织致密结合形态好的HA生物陶瓷梯度涂层，涂层的组织为胞枝晶和枝状晶，与人体骨组织的结构相似，主要由生物活性较好的HA相以及α—Ca2P2O7，Ca2(PO4)2等钙磷相组成，涂层下部的Ca，P的原子比例与HA中的Ca，P的原子比例相当，涂层表面因P的丢失而使其比例略高。随着功率的提高，涂层组织出现了少量的微孔，微孔的出现有利于骨组织在其上面植入生长，但涂层中Ca，P的原子比例升高，涂层的生物活性降低。随着扫描速度的加快，涂层熔化不充分，组织疏松，强度降低，影响了其使用。     

Novel Magnetic Hydroxyapatite Nanoparticles as Non‐Viral Vectors for the Glial Cell Line‐Derived Neurotrophic Factor Gene

Nanoparticles (NPs) of synthetic hydroxyapatite (Hap) and natural bone mineral (NBM) are rendered magnetic by treatment with iron ions using a wet‐chemical process. The magnetic NPs (mNPs), which are about 300 nm in diameter, display superparamagnetic properties in a superconducting quantum interference device, with a saturation magnetization of about 30 emu g^?1. X‐ray diffraction and transmission electron microscopy reveal that the magnetic properties of the NPs are the result of the hetero‐epitaxial growth of magnetite on the Hap and NBM crystallites. The mNPs display a high binding affinity for plasmid DNA in contrast to magnetite NPs which do not bind the plasmid well. The mHap and mNBM NPs result in substantial increases in the transfection of rat marrow‐derived mesenchymal stem cells with the gene for glial cell line‐derived neurotrophic factor (GDNF), with magnetofection compared to transfection in the absence of a magnet. The amount of GDNF recovered in the medium approaches therapeutic levels despite the small amount of plasmid delivered by the NPs.     

Encapsulation of Noble Metal Nanoparticles through Seeded Emulsion Polymerization as Highly Stable Plasmonic Systems

The implementation of plasmonic nanoparticles in vivo remains hindered by important limitations such as biocompatibility, solubility in biological fluids, and physiological stability. A general and versatile protocol is presented, based on seeded emulsion polymerization, for the controlled encapsulation of gold and silver nanoparticles. This procedure enables the encapsulation of single nanoparticles as well as nanoparticle clusters inside a protecting polymer shell. Specifically, the efficient coating of nanoparticles of both metals is demonstrated, with final dimensions ranging between 50 and 200 nm, i.e., sizes of interest for bio‐applications. Such hybrid nanocomposites display extraordinary stability in high ionic strength and oxidizing environments, along with high cellular uptake, and low cytotoxicity. Overall, the prepared nanostructures are promising candidates for plasmonic applications under biologically relevant conditions.