A theoretical study of the electron paramagnetic resonance spectra and local environment in copper(II) complexes with different imidazole and chlorido ligands.

Copper(II) chloride anionic coordination complexes with different imidazole-derived ligands due to the potential cytotoxic activity play the important role in protein. By investigating the experimental electron paramagnetic resonance (EPR) and ultraviolet-visible (UV-vis) spectra of [CuCl(C6H10N2)4]Cl, [CuCl(C6H10N2)4]Cl, [CuCl2(C4H6N2)4], and [Cu2Cl2(C5H8N2)6]Cl2·2H2O, the local structure of the corresponding Cu2+ centers and the role of different ligands are obtained. Based on the well-agreed EPR parameters and the d-d transitions (10Dq), the four Cu2+ centers show tetragonal and orthorhombic distortion, corresponding to the different anisotropies of EPR signals. In addition, the general rules of governing the impact of methanol in imidazolylalkyl derivatives are also discussed, especially the influence on the local environment (symmetry, distortion, covalency, and crystal field) of above four copper(II) chloride anionic coordination complexes. Therefore, the obtained results in this study will be beneficial to provide a theoretical basis for the experimental design of desired copper-containing imidazolyl alkyl derivatives.

Large enhancement of red upconversion luminescence in beta Ba2Sc0.67Yb0.3Er0.03AlO5 phosphor via Mn2+ ions doping for thermometry.

Here, this study reports single-band red upconversion emission in ß-Ba2ScAlO5: Yb3+/Er3+ phosphor by doping Mn2+. The optimum concentration of Mn2+ ions in ß-Ba2ScAlO5: Yb3+/Er3+ phosphor was 0.20. The intensity of red and green emissions is increased by 27.4 and 19.3 times, respectively. Compared with the samples without Mn2+ ions, the red-green integral strength ratio of ß-Ba2ScAlO5: Yb3+/Er3+/Mn2+ sample was significantly increased by 28.4 times, reaching 110.9. The UCL mechanism was explored by analyzing the down-conversion luminescence spectra, absorption spectra, UCL spectra, and upconversion fluorescence lifetime decay curves of Yb3+/Er3+/Mn2+ co-doped ß-Ba2ScAlO5. The enhancement of upconversion red light is achieved through energy transfer between defect bands and Er3+ ions, as well as energy transfer between Mn2+ ions and Er3+ ions. In addition, the Mn2+ doped ß-Ba2ScAlO5: Yb3+/Er3+ red UCL phosphors have great potential for ambient temperature sensing in the 298-523 K temperature range. The maximum sensitivity of ß-Ba2ScAlO5: Yb3+/Er3+/Mn2+ phosphor as a temperature sensor at 523 K is 0.0247 K-1.

Comparison of Repair Methods for Cracked Titanium Alloy Aircraft Structures with Single-Sided Adhesively Bonded Composite Patches.

Composite patches are widely accepted as a useful practice for the repair of cracked aircraft components and the repair method is of vital importance to the final performance of the repaired structures. The present research experimentally studied the repair efficiency and processing stability of pre-cured, prepreg (including unidirectional and plain weave prepregs) and wet-layup methods for use on cracked Ti-alloy panels through the configuration of a butt joint bonded with a one-sided composite patch. The efficiency and stability of these repair methods were elaborately evaluated and compared via the load bearing behavior, the microstructure of the bonding interface, and the structural failure morphology through two batches of testing specimens. Typical patterns were found in load-displacement curves where the initial damage and ultimate bearing load points divided them into elastic-linear, damage propagation and complete fracture phases. Although the co-cure process of both unidirectional prepreg and wet-layup methods can form a jigsaw-like demarcation interface between the adhesive layer and the composite patch to achieve a good bonding force and a high recovery of loading performance, the latter presents porous patches with a high coefficient of variation in load-carrying capacity. Conversely, the pre-cured laminate and the plain weave prepreg patches failed to restore the mechanical properties owing to the weak bonding interface and the low axial patch strength, respectively. The unidirectional prepreg patch was proven to be the optimal repair method for the cracked metallic structures when balancing repair efficiency and processing stability.

Multifunctional gold nanorods in low-temperature photothermal interactions for combined tumor starvation and RNA interference therapy.

Collateral damage to healthy tissue, uneven heat distribution, inflammatory diseases, and tumor metastasis induction hinder the translation of high-temperature photothermal therapy (PTT) from bench to practical clinical applications. In this report, a multifunctional gold nanorod (GNR)-based nanosystem was designed by attaching siRNA against B7-H3 (B7-H3si), glucose oxidase (GOx), and hyaluronic acid (HA) for efficient low-temperature PTT. Herein, GOx can not only exhaust glucose to induce starvation therapy but also reduce the heat shock protein (HSP), realizing the ablation of tumors without damage to healthy tissues. Evidence shows that B7-H3, a type I transmembrane glycoprotein molecule, plays essential roles in growth, metastasis, and drug resistance. By initiating the downregulation of B7-H3 by siRNA, siRNA-GOx/GNR@HA NPs may promote the effectiveness of treatment. By targeting cluster of differentiation 44 (CD44) and depleting B7-H3 and HSPs sequentially, siRNA-GOx/GNR@HA NPs showed 12.9-fold higher lung distribution than siRNA-GOx/GNR NPs. Furthermore, 50% of A549-bearing mice in the siRNA-GOx/GNR NPs group survived over 50 days. Overall, this low-temperature phototherapeutic nanosystem provides an appropriate strategy for eliminating cancer with high treatment effectiveness and minimal systemic toxicity. STATEMENT OF SIGNIFICANCE: To realize efficient tumor ablation under mild low-temperature (42-45 â„ƒ) and RNA interference simultaneously, here we developed a multifunctional gold nanorod (GNR)-based nanosystem (siRNA-GOx/GNR@HA NPs). This nanoplatform can significantly inhibit tumor cell proliferation and induce cell apoptosis by downregulation of HSP90α, HSP70, B7-H3, p-AKT, and p-ERK and upregulation of cleaved caspase-9 at mild low-temperature due to its superior tumor homing ability and the combined effect of photothermal effect, glucose deprivation-initiated tumor starvation, and B7-H3 gene silence effect. It is believed that this multifunctional low-temperature photothermal nanosystem with efficient and specific anticancer properties, shows a potential application in clinical tumor treatment.

Effect of hole perpendicularity error and squeeze force on the mechanical behaviors of riveted joints.

In the automatic drilling and riveting process, the perpendicular error of the hole is inevitable, which has a great influence on the assembly quality. In the current research, the shear and pull-out behaviors of riveted joints under different perpendicularity errors and squeeze forces were investigated and compared by the quasi-static tests. The fracture of the failed samples was characterized by a scanning electron microscope and the formation process of fracture was discussed. The failure mechanisms of riveted joints were analyzed in detail to guide engineering applications. The test results demonstrated that the shear load and pull-out load of riveted joints increased slightly with the increase of the tilt angle from 0° to 4°. The perpendicularity error did not affect the shear and pull-out failure modes of the riveted joints. However, the squeeze force had a significant effect on the failure modes of the pull-out samples. Fracture analysis showed that the failure of all shear samples occurred at the rivet shaft. Besides, when the squeeze force increased from 15 kN to 23 kN, the failure modes of the pull-out samples changed from the sheet to the rivet itself.

Module-Patterned Polymerization towards Crystalline 2D sp2 -Carbon Covalent Organic Framework Semiconductors.

Despite rapid progress over the past decade, most polycondensation systems even upon a small structural variation of the building units eventually result in amorphous polymers other than the desired crystalline covalent organic frameworks. This synthetic dilemma is a central and challenging issue of the field. Here we report a novel approach based on module-patterned polymerization to enable efficient and designed synthesis of crystalline porous polymeric frameworks. This strategy features a wide applicability to allow the use of various knots of different structures, enables polycondensation with diverse linkers, and develops a diversity of novel crystalline 2D polymers and frameworks, as demonstrated by using the C=C bond-formation polycondensation reaction. The new sp2 -carbon frameworks are highly emissive and enable up-conversion luminescence, offer low band gap semiconductors with tunable band structures, and achieve ultrahigh charge mobilities close to theoretically predicted maxima.

Upconversion core/shell nanoparticles with lowered surface quenching for fluorescence detection of Hg2+ ions.

In this study, we reported a fluorescent nanoprobe assembled with upconversion core/shell nanoparticles and a chromophore ruthenium complex (N719@UCNPs). Functional groups (NCS) of the ruthenium complex N719 could react with Hg2+, which made N719 lose the efficacy in quenching the fluorescence of upconversion nanoparticles (UCNPs) and resulted in the recovery of the fluorescence intensity of UCNPs eventually. This fluorescent nanoprobe could provide a rapid and efficient detection of Hg2+ ions in vivo based on the fluorescence resonance energy transfer (FRET) between UCNPs and N719, and a detection limit of 0.1 µg mL-1 can be achieved based on this nanoprobe. It's worth mentioning that, compared with bare core upconversion nanoparticles, the core/shell UCNPs could greatly reduce the surface quenching of the fluorescence induced by solvents instead of N719, thus leading to the enhancement of signal-to-noise ratios. Moreover, the excitation of core/shell UCNPs requires a much lower power (0.06 W cm-2) than that of bare cores, which is beneficial for reducing the decomposition of N719 to stabilize the FRET processes.

Core/shell upconversion nanoparticles with intense fluorescence for detecting doxorubicin in vivo.

Doxorubicin (Dox) is a chemotherapy medication used to treat cancer. Herein, we report a rapid and efficient method for detecting Dox in vivo based on a NaGdF4:Yb3+,Er3+@NaYF4 core/shell upconversion nanoparticles (UCNPs) probe. We found that the intensity ratio of green to red emission (IGVRE) bands of the core/shell NaGdF4:Yb3+,Er3+@NaYF4 nanoparticles was sensitive to Dox in blood samples, and drops as the concentration of Dox increases. In addition, the proposed UCNPs probe possessed the advantage that no nanoparticles leaked into the living body, thus overcoming the intrinsic defect (difficulty in removing UCNPs from blood vessels) of the fluorescence resonance energy transfer (FRET) approach. This proposed UCNP probe design and results may provide some guidance for the real-time and efficient detection of Dox, and can be helpful in biomedical applications.

Correction: Core/shell upconversion nanoparticles with intense fluorescence for detecting doxorubicin in vivo.

[This corrects the article DOI: 10.1039/C8RA02928H.].

Magnetic tuning of upconversion luminescence in Au/NaGdF4:Yb3+/Er3+ nanocomposite.

Lanthanide-doped upconversion nanoparticles (UCNPs) NaGdF4:Yb3+/Er3+ have received increasing attention due to their unique optical-magnetic bifunctional properties. Here, we show that the luminescent intensity from NaGdF4:Yb3+/Er3+ nanoparticles decreases monotonously with increasing the applied magnetic field from 0 to 37.1 T, while plasmon-enhanced upconversion luminescence in Au/NaGdF4:Yb3+/Er3+ nanocomposite is independent of a magnetic field lower than 6 T. The surface plasmon resonances could compensate for the energetic mismatching between the excitation light and the energy-level gaps induced by magnetic field and enhance the radiative efficiency, which is the main factor for achieving this stable upconversion emission in this nanocomposite under a magnetic field not higher than 6 T. These findings provide a novel route for exploring the magnetic control of upconversion luminescence in lanthanide-doped bifunctional nanoparticles.