RESUMO
Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through "hot" charge transfer down to the attosecond time scale.
RESUMO
BACKGROUND: Intracranial hypertension is a life-threatening condition that can be treated by decompressive craniectomy (DC), which involves removing a part of the skull and intracranial lesions. However, DC has many complications and requires a second surgery to repair the skull. Decompressive bone flap replacement (DBFR) or decompressive cranioplasty is a novel technique that replaces the bone flap with a titanium mesh, providing both decompression and skull integrity. METHODS: The materials and methods of DBFR are described in detail. A three-dimensional titanium mesh is fabricated based on the computed tomography (CT) data of previous DC patients. An appropriate titanium mesh is selected based on the preoperative and intraoperative assessments. After removing the intracranial lesions, the titanium mesh is fixed over the bone window. RESULTS: We successfully performed DBFR in three emergent cases. The postoperative CT scan showed adequate decompression in all cases. No reoperation for skull repair was needed, and there were no surgical complications. The cosmetic outcome was excellent. There were no relevant complications in the operative area. CONCLUSIONS: DBFR may be a safe and effective alternative to DC in a specific subgroup of patients, in whom complete removal of the bone flap is feasible. DBFR can reduce intracranial pressure while maintaining the integrity of the skull cavity, eliminating the need for additional surgery for skull repair. Possible improvements for DBFR in the future are suggested, such as using a greater curvature of the titanium mesh or a modified DBFR with a hinged titanium mesh.
RESUMO
OBJECTIVES: To investigate the antihyperuricemia and nephroprotective effects of Orthosiphon stamineus extracts on hyperuricemia (HUA) mice and explore the potential mechanisms. METHODS: Orthosiphon stamineus extracts were extracted using 50% ethanol and enriched using ethyl acetate, and characterised utilising UPLC/ESI-MS. A potassium oxonate (PO) induced hyperuricemic mouse model was used to evaluate antihyperuricemia and nephroprotective effects of O. stamineus ethyl acetate extracts (OSE). KEY FINDINGS: Eight constituents from OSE were identified and OSE treatment ameliorated HUA by regulating key indicators of kidney dysfunction and xanthine oxidase, adenosine deaminase activity and urate transporters in hyperuricemic mice. Moreover, in renal histopathology analysis, OSE significantly alleviated kidney injury. CONCLUSIONS: These findings demonstrate that OSE has antihyperuricemic and nephroprotective effects on PO-induced HUA mice and those results indicate that OSE could be a safe and effective agent or functional ingredient for treating HUA.