ABSTRACT
The effect of hydrogen bonds around the active site of Anabaena [2Fe-2S] ferredoxin (Fd) on a vertical ionization potential of the reduced state (IP(red)) is examined based on the density functional theory (DFT) calculations. The results indicate that a single hydrogen bond increases the relative stability of the reduced state, and shifts IP(red) to a reductive side by 0.31-0.33 eV, regardless of the attached sulfur atoms. In addition, the IP(red) value can be changed by the number of hydrogen bonds around the active site. The results also suggest that the redox potential of [2Fe-2S] Fd is controlled by the number of hydrogen bonds because IP(red) is considered to be a major factor in the redox potential. Furthermore, there is a possibility that the redox potentials of artificial iron-sulfur clusters can be finely controlled by the number of the hydrogen bonds attached to the sulfur atoms of the cluster.
ABSTRACT
Yoichi Yusa, Natsumi Yasuda, Tomoko Yamamoto, Hiromi Kayama Watanabe, Takuo Higashiji, Atsushi Kaneko, Kazuki Nishida, and Jens T. Høeg (2018) Little is known about the growth rates of invertebrates living in ordinary deep-sea habitats such as continental slopes. Thus, the growth rates of two species of the deep-sea scalpellid barnacles, Scalpellum stearnsii and Graviscalpellum pedunculatum, were studied in two aquaria (at Nara and Okinawa Churaumi, Japan). In addition, growth of an S. stearnsii individual after 1 year of deployment was measured in the field. Overall, adult individuals of both species showed slow growths over 8 months (at Nara) and 2 years (at Okinawa) of rearing (e.g., at Nara: 2.0 ± 3.6 µm d-1 for S. stearnsii and 5.9 ± 2.7 µm d-1 for G. pedunculatum; mean ± SD). In contrast, growth rates of juvenile S. stearnsii at Nara were greater (15 ± 7.7 µm d-1). The in situ growth rate of the adult S. stearnsii (3.4 µm d-1) was greater than the average, but within the range of the rates of similar-sized individuals recorded in aquaria. Compared with other pedunculate barnacles, both species show small growth rates typical for deep-sea animals.
ABSTRACT
The spin-unrestricted Hartree-Fock (UHF)-based coupled cluster singles and doubles (UHF-CCSD) and Mukherjee's state-specific multireference CCSD (MkCCSD) methods are applied to four ring-opening reactions. The spin-restricted Hartree-Fock (RHF)-based CCSD (RHF-CCSD) calculations are also performed for comparison. In the case of the UHF-CCSD method, an approximate spin-projection (AP) method is applied to the broken-symmetry (BS) singlet solution to remove the spin contamination effect. For potential energy curves (PECs) of all reactions presented in this study, the results of RHF-CCSD and UHF-CCSD are substantially different from those of MkCCSD, while the results after the AP method (AP-UCCSD) reproduce the MkCCSD results well. It strongly suggests that the spin contamination effect should be removed by the AP correction even at the UHF-CCSD level to predict reliable energetics of these reactions.
