Ligation of D1-His332 and D1-Asp170 to the manganese cluster of photosystem II from Synechocystis assessed by multifrequency pulse EPR spectroscopy.

Multifrequency electron spin-echo envelope modulation (ESEEM) spectroscopy is used to ascertain the nature of the bonding interactions of various active site amino acids with the Mn ions that compose the oxygen-evolving cluster (OEC) in photosystem II (PSII) from the cyanobacterium Synechocystis sp. PCC 6803 poised in the S(2) state. Spectra of natural isotopic abundance PSII ((14)N-PSII), uniformly (15)N-labeled PSII ((15)N-PSII), and (15)N-PSII containing (14)N-histidine ((14)N-His/(15)N-PSII) are compared.

Direct spectroscopic observation of large quenching of first-order orbital angular momentum with bending in monomeric, two-coordinate Fe(II) primary amido complexes and the profound magnetic effects of the absence of Jahn- and Renner-Teller distortions in rigorously linear coordination.

The monomeric iron(II) amido derivatives Fe{N(H)Ar*}(2) (1), Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Pr(i)(3))(2), and Fe{N(H)Ar(#)}(2) (2), Ar(#) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2), were synthesized and studied in order to determine the effects of geometric changes on their unusual magnetic properties. The compounds, which are the first stable homoleptic primary amides of iron(II), were obtained by the transamination of Fe{N(SiMe(3))(2)}(2), with HN(SiMe(3))(2) elimination, by the primary amines H(2)NAr* or H(2)NAr(#). X-ray crystallography showed that they have either strictly linear (1) or bent (2, N-Fe-N = 140.

Multifrequency pulsed electron paramagnetic resonance study of the S2 state of the photosystem II manganese cluster.

Multifrequency electron spin-echo envelope modulation (ESEEM) spectroscopy is employed to measure the strength of the hyperfine coupling of magnetic nuclei to the paramagnetic (S = 1/2) S2 form of photosystem II (PSII). Previous X-band-frequency ESEEM studies indicated that one or more histidine nitrogens are electronically coupled to the tetranuclear manganese cluster in the S2 state of PSII. However, the spectral resolution was relatively poor at the approximately 9 GHz excitation frequency, precluding any in-depth analysis of the corresponding bonding interaction between the detected histidine and the manganese cluster.

Probing defect sites on TiO2 with [Re3(CO)12H3]: spectroscopic characterization of the surface species.

Samples of the anatase phase of titania were treated under vacuum to create Ti(3+) surface-defect sites and surface O(-) and O(2) (-) species (indicated by electron paramagnetic resonance (EPR) spectra), accompanied by the disappearance of bridging surface OH groups and the formation of terminal Ti(3+)-OH groups (indicated by IR spectra). EPR spectra showed that the probe molecule [Re(3)(CO)(12)H(3)] reacted preferentially with the Ti(3+) sites, forming Ti(4+) sites with OH groups as the [Re(3)(CO)(12)H(3)] was adsorbed. Extended X-ray absorption fine structure (EXAFS) spectra showed that these clusters were deprotonated upon adsorption, with the triangular metal frame remaining intact; EPR spectra demonstrated the simultaneous removal of surface O(-) and O(2) (-) species.

Multifrequency electron spin-echo envelope modulation studies of nitrogen ligation to the manganese cluster of photosystem II.

The CalEPR Center at UC-Davis (http://brittepr.ucdavis.edu) is equipped with five research grade electron paramagnetic resonance (EPR) instruments operating at various excitation frequencies between 8 and 130GHz.

The preparation of a phosphorus doped silicon film from phosphorus containing silicon nanoparticles.

Phosphorus containing and octyl-terminated silicon nanoparticles (NPs) are generated by a solution reduction route under room temperature conditions for the first time and characterized by TEM, HRTEM, EDX, 1H/13C/31P NMR, EPR, and PL spectroscopy, then annealed to form a thin film with phosphorus doping confirmed by microprobe elemental analyses.

High-frequency and -field EPR spectroscopy of tris(2,4-pentanedionato)manganese(III): investigation of solid-state versus solution Jahn-Teller effects.

High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy of a classical coordination complex, Mn(acac)(3) (Hacac = 2,4-pentanedione), has been performed on both solid powder and frozen solution (in CH(2)Cl(2)/toluene, 3:2 v/v) samples. Parallel mode detection X-band EPR spectra exhibiting resolved (55)Mn hyperfine coupling were additionally obtained for frozen solutions. Magnetic susceptibility and field-dependent magnetization measurements were also made on powder samples.