4 research outputs found
Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins
In haemoglobin (consisting of four globular myoglobin-like subunits), the
change from the low-spin (LS) hexacoordinated haem to the high spin (HS)
pentacoordinated domed form upon ligand detachment and the reverse process upon
ligand binding, represent the transition states that ultimately drive the
respiratory function. Visible-ultraviolet light has long been used to mimic the
ligand release from the haem by photodissociation, while its recombination was
monitored using time-resolved infrared to ultraviolet spectroscopic tools.
However, these are neither element- nor spin-sensitive. Here we investigate the
transition state in the case of Myoglobin-NO (MbNO) using femtosecond Fe Kalpha
and Kbeta non-resonant X-ray emission spectroscopy (XES) at an X-ray
free-electron laser upon photolysis of the Fe-NO bond. We find that the
photoinduced change from the LS (S = 1/2) MbNO to the HS (S = 2)
deoxy-myoglobin (deoxyMb) haem occurs in ca. 800 fs, and that it proceeds via
an intermediate (S = 1) spin state. The XES observables also show that upon NO
recombination to deoxyMb, the return to the planar MbNO ground state is an
electronic relaxation from HS to LS taking place in ca. 30 ps. Thus, the entire
ligand dissociation-recombination cycle in MbNO is a spin cross-over followed
by a reverse spin cross-over process
Visceral Fat Accumulation is Associated with Oxidative Stress and Increased Matrix Metalloproteinase-9 Expression in Atherogenic Factor-overlapped Model Rats
Visceral fat accumulation in lifestyle-related diseases increases the risk of atherosclerosis. Matrix metalloproteinases (MMPs) play an important role in the progression of atherosclerosis. We examined atherogenic factor-overlapped model rats to clarify the relationships among visceral fat, oxidative stress, and MMPs. We used four groups of male, 11-month-old, spontaneously hypertensive hyperlipidemic rats (SHHRs) or Sprague-Dawley (SD) rats. Animals were fed either a diet of high fat and 30% sucrose solution (HFDS) or a normal diet (ND) ad libitum for 6 months. The visceral fat weight increased by approximately three fold in SHHR-HFDS compared to SHHR-ND. The oxidative stress marker in plasma and MMP-9 mRNA expression in white blood cells increased in SHHR-HFDS compared to the other groups. A correlation was determined between oxidative stress and visceral fat or MMP-9 mRNA in all rats. Lipid deposition and immunostaining of CD68 and MMP-9 were observed mainly in the intima of aorta in SHHR-HFDS, while tissue inhibitor of metalloproteinase-1 mRNA expression decreased in both SHHR groups. The findings suggested that increased oxidative stress due to the visceral fat accumulation induced MMP-9 expression and macrophage accumulation in the intima of aorta in lifestyle-related disease model rats
Femtosecond X-ray spectroscopy of haem proteins
Processed XAS from the manuscript "Femtosecond X-ray spectroscopy of haem proteins".
Raw data generated at SwissFEL (PSI) and SACLA (Spring-8) and can be obtained by the authors under reasonable reques