Excited States of Metal-Adsorbed Dimethyl Disulfide: A TDDFT Study with Cluster Model.

The optical near field refers to a localized light field near a surface that can induce photochemical phenomena such as dipole-forbidden transitions. Recently, the photodissociation of the S-S bond of dimethyl disulfide (DMDS) was investigated using a scanning tunneling microscope with far- and near-field light. This reaction is thought to be initiated by the lowest-energy highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition of the DMDS molecule under far-field light. In near-field light, photodissociation proceeds at lower photon energies than in far-field light. To gain insight into the underlying mechanism, we theoretically investigated the excited states of DMDS adsorbed on Cu and Ag surfaces modeled by a tetrahedral 20-atom cluster. The frontier orbitals of the molecule were delocalized by the interaction with the metal, resulting in narrowing of the HOMO-LUMO gap energy. The excited-state distribution was analyzed using the Mulliken population analysis, decomposing molecular orbitals into metal and DMDS fragments. The excited states of the intra-DMDS transitions were found over a wider energy range, but at low energies, their oscillator strengths were negligible, which is consistent with the experimental results. Sparse modeling analysis showed that typical electronic transitions differed between the higher and lower excited states. If these low-lying excited states are efficiently excited by near-field light with different selection rules, the S-S bond dissociation reaction can proceed.

Regularization Methods Based on the Lq-Likelihood for Linear Models with Heavy-Tailed Errors.

We propose regularization methods for linear models based on the Lq-likelihood, which is a generalization of the log-likelihood using a power function. Regularization methods are popular for the estimation in the normal linear model. However, heavy-tailed errors are also important in statistics and machine learning. We assume q-normal distributions as the errors in linear models. A q-normal distribution is heavy-tailed, which is defined using a power function, not the exponential function. We find that the proposed methods for linear models with q-normal errors coincide with the ordinary regularization methods that are applied to the normal linear model. The proposed methods can be computed using existing packages because they are penalized least squares methods. We examine the proposed methods using numerical experiments, showing that the methods perform well, even when the error is heavy-tailed. The numerical experiments also illustrate that our methods work well in model selection and generalization, especially when the error is slightly heavy-tailed.

Buffalo rat liver cells produce factors that support preimplantation development of mouse embryos cultured in vitro.

To examine the effects of buffalo rat liver (BRL) cells on the preimplantation development of mouse embryos in vitro, we first cultured two-cell mouse embryos alone in serum-free Dulbecco modified Eagle medium. As expected, the embryos did not develop to subsequent stages. However, when cocultured with BRL cells, the embryos developed to the blastocyst stage efficiently. Direct contact of embryos with BRL cells was not necessary for development: the medium conditioned by BRL cells contained soluble factors that supported the preimplantation development of mouse embryos. Embryos cultured with BRL-conditioned medium that was replaced at various intervals had a further increased rate of development to the blastocyst stage. This finding indicated that the activities of the factors were maintained only briefly. Seven proteins between 35 and 44 kDa that were detected in the medium were highly beneficial to the development of the embryos. Follistatin-related protein and pigment epithelium-derived factor are believed to be the factors supporting embryo development. The other five proteins also may improve the environment for the development of mouse embryos cultured in vitro.

Zona-float method for separating mouse eggs from other cells.

We have developed a new method for separating mouse eggs from other cells, such as cumulus cells, using centrifugation with Percoll. Solutions of 45, 22.5, 11.3, and 5.6% Percoll were tested. With the 22.5% solution, 99% of whole eggs obtained by in vitro fertilization were collected from the upper part of the Percoll solution, and 98% of 2-cell embryos collected from these eggs developed to the blastocyst stage. Offspring were obtained after transfer of collected embryos to female mice. The greatest advantage of this method is that undamaged eggs are separated from other cells in one simple operation, regardless of the number of eggs.

Pregnancy by the tubal transfer of embryos developed after injection of round spermatids into oocyte cytoplasm of the cynomolgus monkey (Macaca fascicularis).

BACKGROUND: Round spermatids have been used as substitute gametes in basic reproductive research and in infertility clinics. In humans, however, the efficiency of fertilization and pregnancy is generally much lower after round spermatid injection (ROSI) than after injection with mature sperm. We examined the ability of round spermatids to support embryonic development using a non-human primate as a model. We chose cynomolgus monkeys because, as in humans, their round spermatids have the oocyte-activating capacity of mature sperm. METHODS: We examined fertilization and subsequent development of embryos after ROSI and then transferred the embryos into the oviducts of female monkeys. RESULTS: Seventy-seven per cent of survived oocytes were activated and had formed pronuclei or the second polar body; 79% of the oocytes cultured developed to the 2-cell stage, and 23% developed to the blastocyst stage. Ultrasonography showed a normal-sized fetus in the uterus of a recipient, but the fetus spontaneously aborted at day 103. CONCLUSIONS: The round spermatids of cynomolgus monkeys can be used as substitute gametes to support embryonic development at least to mid-gestation. This non-human primate is a suitable animal model for round spermatid conception in mammals, especially humans, and for biological and genetic characterization of events following ROSI.

Aspiration method to collect epithelial cells from mouse, rat, and monkey oviducts.

When oviduct epithelial cells are collected by using enzymatic methods that involve protease such as trypsin, other cells unintentionally are collected as well, especially from small laboratory animals such as mice and rats, thus contaminating the collected sample. We therefore developed a simple nonenzymatic method that involves using a glass micropipette to aspirate the oviduct epithelial cells from the oviduct. This aspiration method easily removed oviduct epithelial cells from mice, rats, and cynomolgus monkeys. Culture of the collected oviduct epithelial cells confirmed that the cells could adhere and grow on a petri dish. Although this aspiration technique was developed for use in small animals, our results show that it can be applied to cynomolgus monkeys. The advantages of this technique are its simplicity and its success in collecting oviduct epithelial cells from oviducts.