Plasmon‐Enhanced Spectroscopies with Shell‐Isolated Nanoparticles

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), due to its versatility, has been able to break the long‐term limitations of the material‐ and substrate‐specific generalities in the traditional field of surface‐enhanced Raman spectroscopy. With a shell‐isolated work principle, this method provides an opportunity to investigate successfully in surface, biological systems, energetic materials, and environmental sciences. Both the shell material and core morphology are being improved continuously to meet the requirements in diverse systems, such as the electrochemical studies at single crystal electrode surfaces, in situ monitoring of photoinduced reaction processes, practical applications in energy conversion and storage, inspections in food safety, and the surface‐enhanced fluorescence. Predictably, the concept of shell‐isolated nanoparticle‐enhancement could be expanded to the wider range for the performance of plasmon‐enhanced spectral modifications.     

Ferritin Protein Regulates the Degradation of Iron Oxide Nanoparticles

Proteins implicated in iron homeostasis are assumed to be also involved in the cellular processing of iron oxide nanoparticles. In this work, the role of an endogenous iron storage protein—namely the ferritin—is examined in the remediation and biodegradation of magnetic iron oxide nanoparticles. Previous in vivo studies suggest the intracellular transfer of the iron ions released during the degradation of nanoparticles to endogenous protein cages within lysosomal compartments. Here, the capacity of ferritin cages to accommodate and store the degradation products of nanoparticles is investigated in vitro in the physiological acidic environment of the lysosomes. Moreover, it is questioned whether ferritin proteins can play an active role in the degradation of the nanoparticles. The magnetic, colloidal, and structural follow‐up of iron oxide nanoparticles and proteins in lysosome‐like medium confirms the efficient remediation of potentially harmful iron ions generated by nanoparticles within ferritins. The presence of ferritins, however, delays the degradation of particles due to a complex colloidal behavior of the mixture in acidic medium. This study exemplifies the important implications of intracellular proteins in processes of degradation and metabolization of iron oxide nanoparticles.     

Poly(N‐phenylglycine)‐Based Nanoparticles as Highly Effective and Targeted Near‐Infrared Photothermal Therapy/Photodynamic Therapeutic Agents for Malignant Melanoma

Malignant melanoma is a highly aggressive tumor resistant to chemotherapy. Therefore, the development of new highly effective therapeutic agents for the treatment of malignant melanoma is highly desirable. In this study, a new class of polymeric photothermal agents based on poly(N‐phenylglycine) (PNPG) suitable for use in near‐infrared (NIR) phototherapy of malignant melanoma is designed and developed. PNPG is obtained via polymerization of N‐phenylglycine (NPG). Carboxylate functionality of NPG allows building multifunctional systems using covalent bonding. This approach avoids complicated issues typically associated with preparation of polymeric photothermal agents. Moreover, PNPG skeleton exhibits pH‐responsive NIR absorption and an ability to generate reactive oxygen species, which makes its derivatives attractive photothermal therapy (PTT)/photodynamic therapy (PDT) dual‐modal agents with pH‐responsive features. PNPG is modified using hyaluronic acid (HA) and polyethylene glycol diamine (PEG‐diamine) acting as the coupling agent. The resultant HA‐modified PNPG (PNPG‐PEG‐HA) shows negligible cytotoxicity and effectively targets CD44‐overexpressing cancer cells. Furthermore, the results of in vitro and in vivo experiments reveal that PNPG‐PEG‐HA selectively kills B16 cells and suppresses malignant melanoma tumor growth upon exposure to NIR light (808 nm), indicating that PNPG‐PEG‐HA can serve as a very promising nanoplatform for targeted dual‐modality PTT/PDT of melanoma.     

Mild Binding of Protein to C2N Monolayer Reveals Its Suitable Biocompatibility

The development of biocompatible nanomaterials for smart drug delivery and bioimaging has attracted great interest in recent years in biomedical fields. Here, the interaction between the recently reported nitrogenated graphene (C₂N) and a prototypical protein (villin headpiece HP35) utilizing atomistic molecular dynamics simulations is studied. The simulations reveal that HP35 can form a stable binding with the C₂N monolayer. Although the C₂N–HP35 attractive interactions are constantly preserved, the binding strength between C₂N and the protein is mild and does not cause significant distortion in the protein's structural integrity. This intrinsic biofriendly property of native C₂N is distinct from several widely studied nanomaterials, such as graphene, carbon nanotubes, and MoS₂, which can induce severe protein denaturation. Interestingly, once the protein is adsorbed onto C₂N surface, its transverse migration is highly restricted at the binding sites. This restriction is orchestrated by C₂N's periodic porous structure with negatively charged “holes,” where the basic residues—such as lysine—can form stable interactions, thus functioning as “anchor points” in confining the protein displacement. It is suggested that the mild, immobilized protein attraction and biofriendly aspects of C₂N would make it a prospective candidate in bio‐ and medical‐related applications.     

Structure and Magnetic Property Control of Copper Hydroxide Acetate by Non‐Classical Crystallization

Copper hydroxide acetate (CHA), one layered hydroxide compound with tunable magnetism, attracts great interest because of its potential applications in memory devices. However, ferromagnetism for CHA is only demonstrated by means of GPa pressure. Herein, a new method is reported, involving the combination of different crystallization pathways to control crystallization of amorphous CHA toward the formation of CHA/polymer composites with tunable magnetic properties and even a tunability that can be tested at room temperature. By using poly[(ethylene glycol)₆ methyl ether methacrylate]‐block‐poly[2‐(acetoacetoxy) ethyl methacrylate] (PEGMA‐b‐PAEMA) diblock copolymers as additives in combination with a post‐treatment process by ultracentrifugation, it is demonstrated that CHA and PEGMA‐b‐PAEMA form composites exhibiting different magnetic properties, depending on CHA in‐plane nanostructures. Analytical characterization reveals that crystallization of CHA is induced by ultracentrifugation, during which CHA nanostructures can be well controlled by changing the degrees of polymerization of the PEGMA and PAEMA blocks and their block length ratios. These findings not only present the first example of using crystallization from polymer stabilized amorphous precursors toward the generation of magnetic nanomaterials with tunable magnetism but also pave the way for the future design of functional composite materials.     

Anionic Regulated NiFe (Oxy)Sulfide Electrocatalysts for Water Oxidation

The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, rechargeable metal–air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS‐2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm^?2 and the fastest kinetics being 56.3 mV dec^?1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in‐depth understanding of electrocatalysis at the electronic and atomic level.     

The Genetic Heterogeneity among Different Mouse Strains Impacts the Lung Injury Potential of Multiwalled Carbon Nanotubes

Genetic variation constitutes an important variable impacting the susceptibility to inhalable toxic substances and air pollutants, as reflected by epidemiological studies in humans and differences among animal strains. While multiwalled carbon nanotubes (MWCNTs) are capable of causing lung fibrosis in rodents, it is unclear to what extent the genetic variation in different mouse strains influence the outcome. Four inbred mouse strains, including C57Bl/6, Balb/c, NOD/ShiLtJ, and A/J, to test the pro‐fibrogenic effects of a library of MWCNTs in vitro and in vivo are chosen. Ex vivo analysis of IL‐1β production in bone marrow‐derived macrophages (BMDMs) as molecular initiating event (MIE) is performed. The order of cytokine production (Balb/c > A/J > C57Bl/6 > NOD/ShiLtJ) in BMDMs is also duplicated during assessment of IL‐1β production in the bronchoalveolar lavage fluid of the same mouse strains 40 h after oropharyngeal instillation of a representative MWCNT. Animal test after 21 d also confirms a similar hierarchy in TGF‐β1 production and collagen deposition in the lung. Statistical analysis confirms a correlation between IL‐1β production in BMDM and the lung fibrosis. All considered, these data demonstrate that genetic background indeed plays a major role in determining the pro‐fibrogenic response to MWCNTs in the lung.