Reversible Ultra-Slow Crystal Growth of Mixed Lead Bismuth Perovskite Nanocrystals: The Presence of Dynamic Capping

An ultra-slow crystal growth over a period of 24 h of a newly synthesized CH₃NH₃Pb_1/2Bi_1/3I₃ perovskite (MPBI) nanocrystal in non-polar toluene medium is reported here. From several spectroscopic techniques as well as from TEM analysis we found that the size of nanocrystals changes continuously with time, in spite of being capped by the ligands. Using a single molecular spectroscopic technique, we also found that this size change is not due to the stacking of nanocrystals but due to crystal growth. The notable temperature dependence and reversible nature of the nanocrystals growth is explained by the dynamic nature of the capping. The observed temperature-dependent ultra-slow growth is believed to be a pragmatic step towards controlling the size of perovskite NC in a systematic manner.     

Multilayered 2D Cesium-Based Hybrid Perovskite with Strong Polarization Sensitivity: Dimensional Reduction of CsPbBr3

3D perovskite CsPbBr₃ has recently taken a blooming position for optoelectronic applications. However, due to the lack of natural anisotropy of optical attributes, it is a great challenge to fulfil polarization-sensitive photodetection. Here, for the first time, we exploited dimensionality reduction of CsPbBr₃ to tailor a 2D-multilayered hybrid perovskite, (TRA)₂CsPb₂Br₇ ( 1 , in which TRA is (carboxy)cyclohexylmethylammonium), serving as a potential polarized-light detecting candidate. Its unique quantum-confined 2D structure results in intrinsic anisotropy of electrical conductivity, optical absorbance, and polarization-dependent responses. Particularly, it exhibits remarkable dichroism with the photocurrent ratio (I_pc/I_pa) of ≈2.1, being much higher than that of the isotropic CsPbBr₃ crystal and reported CH₃NH₃PbI₃ nanowire (≈1.3), which reveals its great potentials for polarization-sensitive photodetection. Further, crystal-based detectors of 1 show fascinating responses to the polarized light, including high detectivity (>10¹⁰ Jones), fast responding time (≈300 μs), and sizeable on/off current ratios (>10⁴). To our best knowledge, this is the first study on 2D Cs-based hybrid perovskite exhibiting strong polarization-sensitivity. The work highlights an effective pathway to explore new polarization sensitive candidates for hybrid perovskites and promotes their future electronic applications.     

Antimicrobial Effect and Cytotoxic Evaluation of Mg-Doped Hydroxyapatite Functionalized with Au-Nano Rods

Hydroxyapatite (HA) is the main inorganic mineral that constitutes bone matrix and represents the most used biomaterial for bone regeneration. Over the years, it has been demonstrated that HA exhibits good biocompatibility, osteoconductivity, and osteoinductivity both in vitro and in vivo, and can be prepared by synthetic and natural sources via easy fabrication strategies. However, its low antibacterial property and its fragile nature restricts its usage for bone graft applications. In this study we functionalized a MgHA scaffold with gold nanorods (AuNRs) and evaluated its antibacterial effect against S. aureus and E. coli in both suspension and adhesion and its cytotoxicity over time (1 to 24 days). Results show that the AuNRs nano-functionalization improves the antibacterial activity with 100% bacterial reduction after 24 h. The toxicity study, however, indicates a 4.38-fold cell number decrease at 24 days. Although further optimization on nano-functionalization process are needed for cytotoxicity, these data indicated that Au-NRs nano-functionalization is a very promising method for improving the antibacterial properties of HA.     

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)₃P]₃[Bi₂Br₉] ( MTPBB ) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 μC cm⁻². Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d₃₃) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 μW cm⁻² at an optimal load of 4 MΩ. Moreover, the potential of MTPBB -based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.     

Mo掺杂NiMnSe2的制备及其超级电容器性能

成分和结构是影响多元过渡金属硒化物电化学活性的关键因素。适当掺杂其他金属元素可以有效提高电极材料的电化学性能。通过简单的一步水热法,在泡沫镍上制备出了一种无黏结剂的Mo掺杂NiMnSe₂(记作Ni_0.8Mo_0.2MnSe₂)。Mo的少量掺杂为电极材料提供了丰富的反应活性位点,大大提高了NiMnSe₂的电化学性能。在1 A·g^-1时,Ni_0.8Mo_0.2MnSe₂的比容量达到1 404.0 F·g^-1。掺杂Mo显著降低了NiMnSe₂的电荷转移电阻和扩散电阻。组装的混合超级电容器Ni_0.8Mo_0.2MnSe₂//AC (活性炭)比容量达到81.6 F·g^-1,且倍率性能优异。在2 A·g^-1下连续充放电10 000周,容量保持率为95.8%,表现出超高的循环稳定性。混合超级电容器Ni_0.8Mo_0.2MnSe₂//AC在376.6 W·kg^-1的功率密度下,能量密度达25.5 Wh·kg^-1,高于NiMnSe₂//AC (17.3 Wh·kg^-1)。     

Flash Nanoprecipitation Fabrication of PEI@Amorphous Calcium Carbonate Hybrid Nanoparticles for siRNA Delivery

RNA interference (RNAi) is a promising approach for disease treatments. But the development of safe and effective delivery carriers remains a major challenge. Organic–inorganic hybrid nanoparticles (NPs), with the integration of functions from distinct materials, show great potential in small interfering RNA (siRNA) delivery. Herein, pH responsive amorphous calcium carbonate NPs (ACC NPs) are prepared using flash nanoprecipitation and hybrid NPs are constructed by coating ACC NPs with polyethyleneimine (PEI) for efficient siRNA delivery. PEI/ACC NPs show robust pH responsiveness and stability as well as effective siRNA loading and protection. Furthermore, siRNA-loaded PEI/ACC NPs demonstrate enhanced cellular uptake and efficient endosomal escape, mediating improved siRNA delivery compared to pure PEI. These findings suggest that PEI/ACC NPs may have great potential in siRNA delivery for RNAi-based therapy.     

硫酸镉无机层和原位反应生成的吡啶基四氮唑有机配体构筑的两个层-柱状三维无机-有机杂化材料:合成和表征

以硫酸镉、叠氮化钠和4-氰基吡啶或3-氰基吡啶为反应物,在水热条件下,通过原位反应分别得到了2个基于硫酸根离子和5-(4-吡啶基)四氮唑(4-Hptz)或5-(3-吡啶基)四氮唑(3-Hptz)配体的,具有三维层-柱状框架结构的无机-有机杂化材料,即[Cd₂(H₂O)(OH)(SO₄)(4-ptz)]_n(1)和[Cd₂(OH)(SO₄)(3-ptz)]_n(2)。通过元素分析、红外光谱、热重分析以及单晶和粉末X-射线衍射分析对它们的组成和结构进行了表征。在配合物1和2的结构中,每个镉(Ⅱ)离子的配位数均为6,处于扭曲的八面体配位环境中,SO₄^2-和OH-阴离子连接镉(Ⅱ)离子扩展形成碱式硫酸镉的二维无机阳离子层结构[Cd₂(H₂O)(OH)(SO₄)]_nⁿ⁺(1)或[Cd₂(OH)(SO₄)]_nⁿ⁺(2),相邻的二维无机阳离子层间再通过4-ptz^-(1)或3-ptz^-(2)进一步柱连接,形成三维层-柱状结构的无机-有机杂化框架结构。室温下的固体荧光实验表明,在350nm的光激发下,配合物1和2分别在481和489nm处出现强烈的荧光发射。     

Can Helical Peptides Unwind One Turn at a Time? ‐ Controlled Conformational Transitions in α,β2,3‐Hybrid Peptides

Unfolding of helical trans‐β^2,3‐hybrid peptides with (α–β)_nα composition, when executed by increasing solvent polarity or temperature, proceeded in a systematic manner with the turns unwinding sequentially; C‐terminal region of these peptides were first to unwind and the process propagated towards N terminus with more and more β residues equilibrating from the gauche to the anti rotameric state across C_α?C_β. This is evidenced by clear change in their C_βH signal splitting, ³J_CαH–CβH values, and sequential disappearance of i,i+2 NOEs.     

Threading Chalcogenide Layers with Polymer Chains

Inserting polymers into a crystalline inorganic matrix to understand the structure, position, and the structure–property relationships of the resulting composites is important for designing new inorganic‐organic materials and tuning their properties. Single crystals of polymer‐chalcogenide composites were successfully prepared by trapping polyethyleneglycol within a selenidostannate matrix under surfactant‐thermal conditions. This work might provide a new strategy for preparing novel crystalline polymer‐inorganic composites through encapsulating polymer chains within inorganic matrices.