Control of the Speed of a Light-Induced Spin Transition through Mesoscale Core-Shell Architecture.
The rate of the light-induced spin transition in a coordination polymer network solid dramatically increases when included as the core in mesoscale core-shell particles. A series of photomagnetic coordination polymer core-shell heterostructures, based on the light-switchable Rb aCo b[Fe(CN)6] c· mH2O (RbCoFe-PBA) as core with the isostructural K jNi k[Cr(CN)6] l· nH2O (KNiCr-PBA) as shell, are studied using temperature-dependent powder X-ray diffraction and SQUID magnetometry. The core RbCoFe-PBA exhibits a charge transfer-induced spin transition (CTIST), which can be thermally and optically induced. When coupled to the shell, the rate of the optically induced transition from low spin to high spin increases. Isothermal relaxation from the optically induced high spin state of the core back to the low spin state and activation energies associated with the transition between these states were measured. The presence of a shell decreases the activation energy, which is associated with the elastic properties of the core. Numerical simulations using an electro-elastic model for the spin transition in core-shell particles supports the findings, demonstrating how coupling of the core to the shell changes the elastic properties of the system. The ability to tune the rate of optically induced magnetic and structural phase transitions through control of mesoscale architecture presents a new approach to the development of photoswitchable materials with tailored properties.
Core-Shell Heterostructured CuFe@FeFe Prussian Blue Analogue Coupling with Silver Nanoclusters via a One-Step Bioinspired Approach: Efficiently Nonlabeled Aptasensor for Detection of Bleomycin in Various Aqueous Environments.
We synthesized novel core-shell heterostructured Prussian blue analogue (PBA) nanospheres coupled with silver nanoclusters (AgNCs) via a one-step bioinspired approach and further exploited these as aptasensors for the detection of a trace antibiotic, bleomycin (BLM). Using FeFe Prussian blue (FeFe PB) as the core, a bimetallic CuFe@FeFe PBA layer was prepared by coupling with AgNCs synthesized by taking the BLM-targeted aptamer as a template (denoted by AgNCs/Apt@CuFe@FeFe). The coupling of AgNCs/Apt via a one-step bioinspired approach not only can improve the sensing performance of CuFe@FeFe-based aptasensors but also can shorten the aptasensor fabrication procedure. Due to the strong coordination interaction between abundant Fe(II) ions contained in CuFe@FeFe PBA nanospheres and BLM (represented by Fe(II)·BLM), the Fe(II)·BLM complex formed enables aptamer strands to undergo an irreversible cleavage event that can result in a significant change in electrochemical activity. Electrochemical results displayed that both CuFe@FeFe- and AgNCs/Apt@CuFe@FeFe-based aptasensors exhibited high sensitivity and selectivity, good stability and reproducibility, and acceptable applicability toward BLM. In comparison with the pristine CuFe@FeFe-based aptasensor (limit of detection (LOD) = 0.49 fg mL-1 within the BLM concentration from 1.0 to 2.0 ng mL-1), the as-prepared AgNCs/Apt@CuFe@FeFe-based aptasensor gave a extremely lower LOD value of 0.0082 fg mL-1 within a relatively narrow BLM concentration range (0.01 fg mL-1 to 0.1 pg mL-1). The proposed method can broaden the application of PBA nanomaterials in food safety and biosensing fields and provides a potential determination method for rapidly detecting BLM in various aqueous environments.
X-rays and photocarcinogenesis in hairless mice
It is well known that excessive X-ray radiation can cause non-melanoma skin cancers. With the increased incidence of sun-related skin cancer there is a need to investigate the combination of sunlight and X-rays. Immunocompetent C3.Cg/TifBomTac mice (n = 298) were divided into 12 groups. Mice were irradiated with 12, 29 or 50 kV X-rays. The mice received a total dose of 45 Gy. They were irradiated with 3 SED simulated solar radiation (SSR) either before or after irradiation with X-rays. The groups irradiated with X-rays alone, 0, 3, 9 and 10 mice (0, 12, 29 and 50 kV, respectively) developed squamous cell carcinoma. In the groups irradiated with SSR after X-rays the development of tumours was significantly faster in the 50 kV group than in the corresponding control group (175 vs. 194 days, p < 0.001). In the groups irradiated with SSR prior to the X-ray radiation the development of tumours was significantly faster in the 29 and the 50 kV groups than in the corresponding control group (175 vs. 202 days, p < 0.001 and 158 vs. 202 days, p < 0.001, respectively). In conclusion, X-ray radiation alone is a weak carcinogen in hairless mice. There is an added carcinogenic effect if X-ray radiation is given on prior sun-exposed skin or if the skin is sun-exposed after X-rays. We still believe that X-ray radiation is a safe and effective therapy for various dermatological diseases but caution should be observed if a patient has severely sun-damaged skin or has a high-risk sun behaviour.