Search

O3-NaNi0.33Mn0.33Fe0.33O2 layered oxide has attracted increasing attention as one of the most promising materials for Na-ion battery applications due to air stability and environmental friendliness, but the complex phase transitions and inferior cycling stability are extremely challenging to overcome. Cation substitution has been widely used to stabilize crystal structures and improve electrochemical performance for SIBs. Based on past experimental results, it was discovered that the transition metal–oxygen bond energy of the introduced dopant is an important factor for optimizing electrochemical performance. In this study, we validated our hypothesis that yttrium (Y)-which possesses high bond energy for oxygen-is most likely to be an ideal doping element by conducting a comparative study of substituting Mn in O3-NaNi0.33Mn0.33Fe0.33O2 layered oxide with aluminum (Al) and Y through elemental doping. As hypothesized, the electrochemical properties of NaNi0.33Mn0.33Fe0.33O2 have increased markedly by introducing a small amount of Y and Al, and the Y-doped materials showed superior rate performance and cycling stability due to enhanced Na+ diffusion reaction kinetics and layered structure stability. Furthermore, the substitution of Y for Mn can improve thermal stability and alleviate phase transformations. The improvement mechanism of Y substitution can be attributed to a larger d-spacing and stronger metal–oxygen bond. These results suggest that structural modulation is an effective strategy to reinforce electrochemical properties of layered oxides and provides some guidance about designing promising electrode materials.

O3-NaNi0.33Mn0.33Fe0.33O2 layered oxide has attracted increasing attention as one of the most promising materials for Na-ion battery applications due to air stability and environmental friendliness, but the complex phase transitions and inferior cycling stability are extremely challenging to overcome. Cation substitution has been widely used to stabilize crystal structures and improve electrochemical performance for SIBs. Based on past experimental results, it was discovered that the transition metal-oxygen bond energy of the introduced dopant is an important factor for optimizing electrochemical performance. In this study, we validated our hypothesis that yttrium (Y)-which possesses high bond energy for oxygen-is most likely to be an ideal doping element by conducting a comparative study of substituting Mn in O3-NaNi0.33Mn0.33Fe0.33O2 layered oxide with aluminum (Al) and Y through elemental doping. As hypothesized, the electrochemical properties of NaNi0.33Mn0.33Fe0.33O2 have increased markedly by introducing a small amount of Y and Al, and the Y-doped materials showed superior rate performance and cycling stability due to enhanced Na+ diffusion reaction kinetics and layered structure stability. Furthermore, the substitution of Y for Mn can improve thermal stability and alleviate phase transformations. The improvement mechanism of Y substitution can be attributed to a larger d-spacing and stronger metal-oxygen bond. These results suggest that structural modulation is an effective strategy to reinforce electrochemical properties of layered oxides and provides some guidance about designing promising electrode materials.

Drug to carrier ratio is an important consideration in designing drug platforms, since a low loading capacity necessitates the use of high doses of carriers, which can result in side effects. Here, we have engineered a platform to co-deliver small molecule drugs and small interfering RNA (siRNA). This platform consists of cyclodextrin-grafted polyethylenimine (CP) functionalized mesoporous silica nanoparticles (MSNP). A unique multi-step encapsulation procedure was used to obtain a high loading capacity for doxorubicin (DOX) and siRNA oligos specific for the PKM2 gene that encodes pyruvate kinase M2, an enzyme catalyzing the final rate-limiting step in glycolysis. We systematically characterized this platform (CP-MSNP@DOX/PKM2) in vitro and evaluated its therapeutic efficacy in vivo with a mouse model of triple negative breast cancer (TNBC). Exposure of TNBC cells to CP-MSNP@DOX/PKM2 resulted in suppressed target gene expression, reduced cell proliferation, and enhanced apoptosis. Intravenous administration of the drug substantially decreased the tumor burden in comparison to DOX or siRNA monotherapy. In conclusion, we have developed a platform for efficient co-delivery of small molecule drugs and therapeutic siRNA.

A facile, one-step method was developed for in situ forming fluorescent silicon nanocrystals (SiNC) in microspherical encapsulating matrix. The obtained SiNC encapsulated polymeric microcapsules (SiPM) possess uniform size (0.1–2.0 µm), strong fluorescence, and nanoporous structure. A unique two stage, time dependent reaction was developed, as the growth of SiNC was slower than the formation of polymeric microcapsules. The resulting SiPM with increasing reaction time exhibited two levels of stability, and in correspondence, the release of SiNC in aqueous media showed different behaviors. With reaction time < 1 h, the obtained low-density SiPM (LD-SiPM) as matrix microcapsules, would release encapsulated SiNC on demand. With >1 h reaction time, resulting high-density SiPM (HD-SiPM) became stable SiNC reservoirs. SiPM exhibits stable photoluminescence. The porous structure and fluorescence quenching effects make SiPM suitable for bioimaging, drug loading and sorption of heavy metals (Hg2+ as shown) with intrinsic indicator. SiPM was able to reduce metal ions, forming SiPM/Metal oxide and SiPM/Metal hybrids, and their application in bio-sensing and catalysis were also demonstrated.

A facile, one-step method was developed for the in situ formation of fluorescent silicon nanocrystals (SiNC) in a microspherical encapsulating matrix. The obtained SiNC encapsulated polymeric microcapsules (SiPM) possess uniform size (0.1-2.0 μm), strong fluorescence, and nanoporous structure. A unique two stage, time dependent reaction was developed, as the growth of SiNC was slower than the formation of polymeric microcapsules. The resulting SiPM with increasing reaction time exhibited two levels of stability, and correspondingly, the release of SiNC in aqueous media showed different behavior. With reaction time1 h, the obtained low-density SiPM (LD-SiPM) as matrix microcapsules, would release encapsulated SiNC on demand. With1 h reaction time, resulting high-density SiPM (HD-SiPM) became stable SiNC reservoirs. SiPM exhibit stable photoluminescence. The porous structure and fluorescence quenching effects make SiPM suitable for bioimaging, drug loading and sorption of heavy metals (Hg(2+) as shown) as an intrinsic indicator. SiPM were able to reduce metal ions, forming SiPM/metal oxide and SiPM/metal hybrids, and their applications in bio-sensing and catalysis were also demonstrated.

Non-invasive and real-time imaging of the gastrointestinal (GI) tract is particularly desirable for research and clinical studies of patients with symptoms arising from gastrointestinal diseases. Here, we designed and fabricated silica-coated bismuth sulfide nanorods (Bi2S3@SiO2 NRs) for a non-invasive spatial-temporally imaging of the GI tract. The Bi2S3 NRs were synthesized by a facile solvothermal method and then coated with a SiO2 layer to improve their biocompatibility and stability in the harsh environments of the GI tract, such as the stomach and the small intestine. Due to their strong X-ray- and near infrared-absorption abilities, we demonstrate that, following oral administration in mice, the Bi2S3@SiO2 NRs can be used as a dual-modal contrast agent for the real-time and non-invasive visualization of NRs distribution and the GI tract via both X-ray computed tomography (CT) and photoacoustic tomography (PAT) techniques. Importantly, integration of PAT with CT provides complementary information on anatomical details with high spatial resolution. In addition, we use Caenorhabditis Elegans (C. Elegans) as a simple model organism to investigate the biological response of Bi2S3@SiO2 NRs by oral administration. The results indicate that these NRs can pass through the GI tract of C. Elegans without inducing notable toxicological effects. The above results suggest that Bi2S3@SiO2 NRs pave an alternative way for the fabrication of multi-modal contrast agents which integrate CT and PAT modalities for a direct and non-invasive visualization of the GI tract with low toxicity.

The toxicity grade for a bulk material can be approximately determined by three factors (chemical composition, dose, and exposure route). However, for a nanomaterial it depends on more than ten factors. Interestingly, some nano-factors (like huge surface adsorbability, small size, etc.) that endow nanomaterials with new biomedical functions are also potential causes leading to toxicity or damage to the living organism. Is it possible to create safe nanomaterials if such a number of complicated factors need to be regulated? We herein try to find answers to this important question. We first discuss chemical processes that are applicable for nanosurface modifications, in order to improve biocompatibility, regulate ADME, and reduce the toxicity of carbon nanomaterials (carbon nanotubes, fullerenes, metallofullerenes, and graphenes). Then the biological/toxicological effects of surface-modified and unmodified carbon nanomaterials are comparatively discussed from two aspects: the lowered toxic responses or the enhanced biomedical functions. We summarize the eight biggest challenges in creating low-toxicity and safer nanomaterials and some significant topics of future research needs: to find out safer nanofactors; to establish controllable surface modifications and simpler chemistries for low-toxic nanomaterials; to explore the nanotoxicity mechanisms; to justify the validity of current toxicological theories in nanotoxicology; to create standardized nanomaterials for toxicity tests; to build theoretical models for cellular and molecular interactions of nanoparticles; and to establish systematical knowledge frameworks for nanotoxicology.

The utilization of up-conversion nanoparticles (UCNPs) for photodynamic therapy (PDT) has gained significant interest due to their unique ability to convert near infrared light to UV/visible light. Previous work mainly focused on the fabrication of green and red emitting UCNPs to load photosensitizers (PSs) for PDT. In this work, we firstly developed a new multifunctional nanoplatform combining blue-emitting UCNPs with blue-light excited PS (hypocrellin A, HA) as a NIR photosensitizing nanoplatform for PDT of cancer cells. Tween 20 coated NaYbF4:Tm, Gd@NaGdF4 UCNPs (Tween 20-UCNPs) with strong blue up-conversion luminescence and good water dispersibility were prepared for use as PS carriers. The blue emission band matched well with the efficient absorption band of HA, thereby facilitating the resonance energy transfer from UCNPs to HA and then activating HA to produce singlet oxygen ((1)O2). The in vitro study showed that these Tween 20-UCNPs@HA complexes could efficiently produce (1)O2 to kill cancer cells under 980 nm NIR excitation. Moreover, these Gd(3+) and Yb(3+) containing nanoparticles also exhibited positive contrast effects in both T1 weighted magnetic resonance imaging (MRI) and computed tomography (CT) imaging, making them become a multifunctional platform for simultaneous PDT and bio-imaging.