Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Crystalline phase of TiO2 nanotube arrays on Ti–35Nb–4Zr alloy: Surface roughness,electrochemical behavior and cellular response

An investigation was made into the electrochemical, structural and biological properties of self-organized amorphous and anatase/rutile titanium dioxide (TiO₂) nanotubes deposited on Ti–35Nb–4Zr alloy through anodization-induced surface modification. The surface of as-anodized and heat-treated TiO₂ nanotubes was analyzed by field emission scanning electron microscopy (FE-SEM), revealing morphological parameters such as tube diameter, wall thickness and cross-sectional length. Glancing angle X-ray diffraction (GAXRD) was employed to identify the structural phases of titanium dioxide, while atomic force microscopy (AFM) was used to measure surface roughness associated with cell interaction properties. The electrochemical stability of TiO₂ was examined by electrochemical impedance spectroscopy (EIS) and the results obtained were correlated with the microstructural characterization. The in vitro bioactivity of as-anodized and crystallized TiO₂ nanotubes was also analyzed as a function of the presence of different TiO₂ polymorphic phases. The results indicated that anatase TiO₂ showed higher surface corrosion resistance and greater cell viability than amorphous TiO₂, confirming that TiO₂ nanotube crystallization plays an important role in the material's electrochemical behavior and biocompatibility.     

对“垃圾衍生燃料”RDF之探析

当前,我国水泥工业在可燃废弃物应用技术方面都还处于一家一户、自制自用、效率极低的初级阶段。发达国家的替代燃料:“垃圾衍生燃料”RDF、“固体回收燃料”SRF、“次煤”Subcoal和“纸塑垃圾衍生燃料”RPF制成的原材料都是可燃废弃物,只是处理工艺技术不同或者由垃圾中分拣出的可燃废弃物不同,制成颗粒状衍生燃料的品质不同,这些都可以替代部分甚或替代全部化石燃料在水泥窑炉中应用。我国大力发展“替代燃料”产业,有助于水泥工业消纳更多的“可燃废弃物”,为改善环境尤其是城镇环境和面貌,为我国的节能减排和绿色高质量发展发挥更大的作用。     

Photoregulation of Gene Expression with Ligand-Modified Caged siRNAs through Host/Guest Interaction

Small interfering RNA (siRNA) can effectively silence target genes through Argonate 2 (Ago2)-induced RNA interference (RNAi). It is very important to control siRNA activity in both spatial and temporal modes. Among different masking strategies, photocaging can be used to regulate gene expression through light irradiation with spatiotemporal and dose-dependent resolution. Many different caging strategies and caging groups have been reported for light-activated siRNA gene silencing. Herein, we describe a novel caging strategy that increases the blocking effect of RISC complex formation/process through host/guest (including ligand/receptor) interactions, thereby enhancing the inhibition of caged siRNA activity until light activation. This strategy can be used as a general approach to design caged siRNAs for the photomodulation of gene silencing of exogenous and endogenous genes.     

Treatment of Brain Metastases of Non-Small Cell Lung Carcinoma

Lung cancer is one of the most common malignant neoplasms. As a result of the disease’s progression, patients may develop metastases to the central nervous system. The prognosis in this location is unfavorable; untreated metastatic lesions may lead to death within one to two months. Existing therapies—neurosurgery and radiation therapy—do not improve the prognosis for every patient. The discovery of Epidermal Growth Factor Receptor (EGFR)—activating mutations and Anaplastic Lymphoma Kinase (ALK) rearrangements in patients with non-small cell lung adenocarcinoma has allowed for the introduction of small-molecule tyrosine kinase inhibitors to the treatment of advanced-stage patients. The Epidermal Growth Factor Receptor (EGFR) is a transmembrane protein with tyrosine kinase-dependent activity. EGFR is present in membranes of all epithelial cells. In physiological conditions, it plays an important role in the process of cell growth and proliferation. Binding the ligand to the EGFR causes its dimerization and the activation of the intracellular signaling cascade. Signal transduction involves the activation of MAPK, AKT, and JNK, resulting in DNA synthesis and cell proliferation. In cancer cells, binding the ligand to the EGFR also leads to its dimerization and transduction of the signal to the cell interior. It has been demonstrated that activating mutations in the gene for EGFR-exon19 (deletion), L858R point mutation in exon 21, and mutation in exon 20 results in cancer cell proliferation. Continuous stimulation of the receptor inhibits apoptosis, stimulates invasion, intensifies angiogenesis, and facilitates the formation of distant metastases. As a consequence, the cancer progresses. These activating gene mutations for the EGFR are present in 10–20% of lung adenocarcinomas. Approximately 3–7% of patients with lung adenocarcinoma have the echinoderm microtubule-associated protein-like 4 (EML4)/ALK fusion gene. The fusion of the two genes EML4 and ALK results in a fusion gene that activates the intracellular signaling pathway, stimulates the proliferation of tumor cells, and inhibits apoptosis. A new group of drugs—small-molecule tyrosine kinase inhibitors—has been developed; the first generation includes gefitinib and erlotinib and the ALK inhibitor crizotinib. These drugs reversibly block the EGFR by stopping the signal transmission to the cell. The second-generation tyrosine kinase inhibitor (TKI) afatinib or ALK inhibitor alectinib block the receptor irreversibly. Clinical trials with TKI in patients with non-small cell lung adenocarcinoma with central nervous system (CNS) metastases have shown prolonged, progression-free survival, a high percentage of objective responses, and improved quality of life. Resistance to treatment with this group of drugs emerging during TKI therapy is the basis for the detection of resistance mutations. The T790M mutation, present in exon 20 of the EGFR gene, is detected in patients treated with first- and second-generation TKI and is overcome by Osimertinib, a third-generation TKI. The I117N resistance mutation in patients with the ALK mutation treated with alectinib is overcome by ceritinib. In this way, sequential therapy ensures the continuity of treatment. In patients with CNS metastases, attempts are made to simultaneously administer radiation therapy and tyrosine kinase inhibitors. Patients with lung adenocarcinoma with CNS metastases, without activating EGFR mutation and without ALK rearrangement, benefit from immunotherapy. This therapeutic option blocks the PD-1 receptor on the surface of T or B lymphocytes or PD-L1 located on cancer cells with an applicable antibody. Based on clinical trials, pembrolizumab and all antibodies are included in the treatment of non-small cell lung carcinoma with CNS metastases.     

Designing independent water transport channels to improve water flooding in ultra-thin nanoporous film cathodes for PEMFCs

Utilization of 3D nanostructured Pt cathodes could obviously improve performances of proton exchange membrane fuel cells (PEMFCs) owing to the reduced tortuosity and the bi-continuous nanoporous structure. However, these cathodes usually suffer from the flooding problem ascribed to the ionomer-free and nanoscale pores which are more susceptible to water condensation. In this paper, ultra-thin nanoporous metal films (100 nm) were utilized to construct PEMFC cathodes and independent transport channels were designed separately for water and gas aiming at the flooding problem. Nanoporous gold (NPG) film was used as the model support for loading Pt nanoparticles owing to its controllable and stable structure. After optimizing the polytetrafluoroethylene (PTFE) content and carbon loading in the gas diffusion layer (GDL), plasma treatment under O₂ atmosphere was used to pattern the GDL with independent water transport channels. The obtained liquid permeation coefficients and oxygen gains demonstrated the obviously improved water and O₂ transport. By using a home-made optimized GDL and a nanoporous film cathode with pore size ～60 nm, the flooding problem could be facilely solved. With a Pt loading of ～16 μg cm^?2, this 3D nanostructured cathode exhibits a PEMFC performance of ～957 mW cm^?2 at 80 °C. The Pt power efficiency is about 4 times higher than that of the commercial Pt/C cathode (50 μg cm^?2, 756 mW cm^?2). Obviously, this study provides a simple but effective methodology to solve the water flooding problem in the ultra-thin nanoporous film cathodes which is applicable for other types of 3D nanostructured PEMFC cathodes.     

Salt-assisted solution combustion synthesis of NiFe2O4: Effect of salt type

The effects of three types of salt including NaF, KCl, and NaCl on the properties of NiFe₂O₄ nanoparticles using salt-assisted solution combustion synthesis (SSCS) have been investigated. The synthesized powders were evaluated by SEM, TEM, FTIR, XRD, and VSM analysis. Also, the specific surface area (SSA), as well as size distribution and volume of the porosities of NiFe₂O₄ powders were determined by the BET apparatus. The visual observations showed that the intensity and time of combustion synthesis of nanoparticles have been severely influenced by the type of salt. The highest crystallinity was observed in the synthesized powder using NaCl. The SSA has also been correlated completely to the type of salt. The quantities of SSA was achieved about 91.62, 64.88, and 47.22 m²g^-1 for the powders synthesized by KCl, NaCl, and NaF respectively. Although the magnetic hysteresis loops showed the soft ferromagnetic behavior of the NiFe₂O₄ nanoparticles in all conditions, KCl salt could produce the particles with the least coercivity and remanent magnetization. Based on the present study, the salt type is a key parameter in the SSCS process for the preparation of spinel ferrites. Thermodynamic evaluation also showed that the melting point and heat capacity are important parameters for the proper selection of the salt.     

High-surface-area mesoporous silica-yttria-zirconia ceramic materials prepared by coprecipitation method ― the role of silicon

A high surface area is one of desired properties for yttria-zirconia (Y₂O₃–ZrO₂) ceramic materials given their catalytic applications. The objective of this study is to develop high-surface-area Y₂O₃–ZrO₂ materials by silicon (Si) modification and investigate the role of Si. Si-modified yttrium-zirconium hydroxides were prepared via a one-step precipitation process and calcined at 800 or 950 °C to form Si-modified Y₂O₃–ZrO₂ (denoted as SiO₂–Y₂O₃–ZrO₂) materials containing 0-20 wt% Si as SiO₂. These hydroxides or materials were characterized by ²⁹Si NMR, XPS, TG-DSC, XRD, UV Raman, TEM, and N₂ physisorption measurements. Si species uniformly distributed in the hydroxides tended to be enriched on the material surface at high temperatures. These Si species dominated by the silicates blocked the migration of Y and Zr atoms, which resisted the crystallite growth of Y₂O₃–ZrO₂ components and reduced their crystallite size. Therefore, the SiO₂–Y₂O₃–ZrO₂ possessed a surface area of 59-112 m²/g after calcination at 950 °C for 9 h, which was significantly higher than that of the Y₂O₃–ZrO₂ (23 m²/g). This study may stimulate ideas for developing high-surface-area crystalline ceramic materials calcined at high temperatures.