Local Oxidation States in {FeNO} Porphyrins: Insights from DMRG/CASSCF-CASPT2 Calculations.

A first DMRG/CASSCF-CASPT2 study of a series of paradigmatic {FeNO}, {FeNO}, and {FeNO} heme-nitrosyl complexes has led to substantial new insight as well as uncovered key shortcomings of the DFT approach. By virtue of its balanced treatment of static and dynamic correlation, the calculations have provided some of the most authoritative information available to date on the energetics of low- versus high-spin states of different classes of heme-nitrosyl complexes. Thus, the calculations indicate low doublet-quartet gaps of 1-4 kcal/mol for {FeNO} complexes and high singlet-triplet gaps of ≳20 kcal/mol for both {FeNO} and {FeNO} complexes.

Characteristics of LED light-induced geometrical isomerization and degradation of astaxanthin and improvement of the color value and crystallinity of astaxanthin utilizing the photoisomerization.

The effects of light-emitting diode (LED) irradiation characterized by different emission wavelengths on the E/Z-isomerization and degradation of astaxanthin were investigated. LED irradiation slightly promoted Z-isomerization of astaxanthin, whereas the all-E-isomerization was highly efficiently promoted at specific wavelengths, especially at 365 nm. Astaxanthin isomers did not degrade significantly when dissolved in ethanol and subjected to LED irradiation conditions for 300 min.

Measuring mechanical properties with high-speed atomic force microscopy.

High-speed atomic force microscopy (HS-AFM) is now a widely used technique to study the dynamics of single biomolecules and complex structures. In the past, it has mainly been used to capture surface topography as structural analysis, leading to important discoveries not attainable by other methods. Similar to conventional AFM, the scope of HS-AFM was recently expanded to encompass quantities beyond topography, such as the measurement of mechanical properties.

Multiple Roles of a Conserved Glutamate Residue for Unique Biophysical Properties in a New Group of Microbial Rhodopsins Homologous to TAT Rhodopsin.

TAT rhodopsin, a microbial rhodopsin found in the marine SAR11 bacterium HIMB114, uniquely possesses a Thr-Ala-Thr (TAT) motif in the third transmembrane helix. Because of a low pK value of the retinal Schiff base (RSB), TAT rhodopsin exhibits both a visible light-absorbing state with the protonated RSB and a UV-absorbing state with the deprotonated RSB at a neutral pH. The UV-absorbing state, in contrast to the visible light-absorbing one, converts to a long-lived photointermediate upon light absorption, implying that TAT rhodopsin functions as a pH-dependent light sensor.

Protocol to investigate the neural basis for copulation posture of Drosophila using a closed-loop real-time optogenetic system.

In internal fertilization animals, maintaining a copulation posture facilitates the process of transporting gametes from male to female. Here, we present a protocol to investigate the neural basis for copulation posture of fruit flies using a closed-loop real-time optogenetic system. We describe steps for using deep learning analysis to enable optogenetic manipulation of neural activity only during copulation with high efficiency.

Structure of the human ATAD2 AAA+ histone chaperone reveals mechanism of regulation and inter-subunit communication.

ATAD2 is a non-canonical ATP-dependent histone chaperone and a major cancer target. Despite widespread efforts to design drugs targeting the ATAD2 bromodomain, little is known about the overall structural organization and regulation of ATAD2. Here, we present the 3.

Glucose absorption activity and gene expression of sugar transporters in the trophotaenia of the viviparous teleost Xenotoca eiseni.

In viviparous reproductive systems, nutrient transfer from mother to embryo plays a critical role in the generation of offspring. Herein, we investigated the mother-to-embryo nutrient transfer machinery in the viviparous teleost Xenotoca eiseni, which belongs to the family Goodeidae. The intraovarian embryo absorbs maternal supplements via the hindgut-derived placental structure termed the trophotaenia.

Dissociative ionization and Coulomb explosion of CH in two-color asymmetric intense laser fields.

Directional fragment ejection from a tetrahedral molecule CH in linearly polarized two-color ( and 2) asymmetric intense laser fields (50 fs, 1.4 × 10 W cm, 800 nm and 400 nm) has been studied by three-dimensional ion coincidence momentum imaging. The H fragment produced from dissociative ionization, CH → H + CH + e, is preferentially ejected on the larger amplitude side of the laser electric fields.

Topological capture of mRNA for silencing gene expression.

We describe herein topological mRNA capture using branched oligodeoxynucleotides (ODNs) with multiple reactive functional groups. These fragmented ODNs efficiently formed topological complexes on template mRNA . In cell-based experiments targeting AcGFP mRNA, the bifurcated reactive ODNs showed a much larger gene silencing effect than the corresponding natural antisense ODN.

Visualizing the membrane disruption action of antimicrobial peptides by cryo-electron tomography.

The abuse of antibiotics has led to the emergence of multidrug-resistant microbial pathogens, presenting a pressing challenge in global healthcare. Membrane-disrupting antimicrobial peptides (AMPs) combat so-called superbugs via mechanisms different than conventional antibiotics and have good application prospects in medicine, agriculture, and the food industry. However, the mechanism-of-action of AMPs has not been fully characterized at the cellular level due to a lack of high-resolution imaging technologies that can capture cellular-membrane disruption events in the hydrated state.

Unraveling the Spin-State Energetics of FeN Complexes with Ab Initio Methods.

A systematic analysis was conducted to explore the spin-state energetics of a series of 19 FeN complexes. The performance of a large number of multireference methods was assessed, highlighting the significant challenges associated with accurately describing the spin-state energetics of FeN complexes. Most multireference methods were found to be susceptible to errors originating from the reference CASSCF wavefunction, leading to an overstabilization of high-spin states.

Design and Synthesis of Poly(2,2'-Bipyridyl) Ligands for Induction of Cell Death in Cancer Cells: Control of Anticancer Activity by Complexation/Decomplexation with Biorelevant Metal Cations.

Chelation therapy is a medical procedure for removing toxic metals from human organs and tissues and for the treatment of diseases by using metal-chelating agents. For example, iron chelation therapy is designed not only for the treatment of metal poisoning but also for some diseases that are induced by iron overload, cancer chemotherapy, and related diseases. However, the use of such metal chelators needs to be generally carried out very carefully, because of the side effects possibly due to the non-specific complexation with intracellular metal cations.

Phosphate starvation response precedes abscisic acid response under progressive mild drought in plants.

Drought severely damages crop production, even under conditions so mild that the leaves show no signs of wilting. However, it is unclear how field-grown plants respond to mild drought. Here, we show through six years of field trials that ridges are a useful experimental tool to mimic mild drought stress in the field.

Insights into the protonation state and spin structure for the = 2 multiline electron paramagnetic resonance signal of the oxygen-evolving complex.

In photosystem II (PSII), one-electron oxidation of the most stable oxidation state of the MnCaO cluster (S) leads to formation of two distinct states, the open-cubane S conformation [Mn1(III)Mn2(IV)Mn3(IV)Mn4(IV)] with low spin and the closed-cubane S conformation [Mn1(IV)Mn2(IV)Mn3(IV)Mn4(III)] with high spin. In electron paramagnetic resonance (EPR) spectroscopy, the open-cubane S conformation exhibits a = 2 multiline signal. However, its protonation state remains unclear.

Changes in the hydrophobic network of the FliG domain induce rotational switching of the flagellar motor.

The FliG protein plays a pivotal role in switching the rotational direction of the flagellar motor between clockwise and counterclockwise. Although we previously showed that mutations in the Gly-Gly linker of FliG induce a defect in switching rotational direction, the detailed molecular mechanism was not elucidated. Here, we studied the structural changes in the FliG fragment containing the middle and C-terminal regions, named FliG, and the switch-defective FliG-G215A, using nuclear magnetic resonance (NMR) and molecular dynamics simulations.

Molecular Structure Related to an = 5/2 High-Spin S State Manganese Cluster of Photosystem II Investigated by Q-Band Pulse EPR Spectroscopy.

The high-spin S state of the photosynthetic oxygen-evolving cluster MnCaO, corresponding to the = 4.1 signal for X-band electron paramagnetic resonance (EPR), was investigated using Q-band pulsed EPR, which detected a main peak at = 3.10 and satellite peaks at 5.

5D Analysis of Capacity Degradation in Battery Electrodes Enabled by Operando CT-XANES.

For devices encountering long-term stability challenges, a precise evaluation of degradation is of paramount importance. However, methods for comprehensively elucidating the degradation mechanisms in devices, particularly those undergoing dynamic chemical and mechanical changes during operation, such as batteries, are limited. Here, a method is presented using operando computed tomography combined with X-ray absorption near-edge structure spectroscopy (CT-XANES) that can directly track the evolution of the 3D distribution of the local capacity loss in battery electrodes during (dis)charge cycles, thereby enabling a five-dimensional (the 3D spatial coordinates, time, and chemical state) analysis of the degradation.

Advancing cryo-electron microscopy data analysis through accelerated simulation-based flexible fitting approaches.

Flexible fitting based on molecular dynamics simulation is a technique for structure modeling from cryo-EM data. It has been utilized for nearly two decades, and while cryo-EM resolution has improved significantly, it remains a powerful approach that can provide structural and dynamical insights that are not directly accessible from experimental data alone. Molecular dynamics simulations provide a means to extract atomistic details of conformational changes that are encoded in cryo-EM data and can also assist in improving the quality of structural models.

Searching for Heavy Dark Matter near the Planck Mass with XENON1T.

Multiple viable theoretical models predict heavy dark matter particles with a mass close to the Planck mass, a range relatively unexplored by current experimental measurements. We use 219.4 days of data collected with the XENON1T experiment to conduct a blind search for signals from multiply interacting massive particles (MIMPs).

Expression analyses of WAC, a responsible gene for neurodevelopmental disorders, during mouse brain development.

WAC is an adaptor protein involved in gene transcription, protein ubiquitination, and autophagy. Accumulating evidence indicates that WAC gene abnormalities are responsible for neurodevelopmental disorders. In this study, we prepared anti-WAC antibody, and performed biochemical and morphological characterization focusing on mouse brain development.

Oxidation and phase transfer of individual Cr-doped dendritic FeO particles visualized by full-field nano-XAFS spectroimaging.

Iron oxides with various compositions and polymorphs have been widely used as compounds that require reversible redox properties, such as catalysts. However, partial decomposition during phase transitions often causes irreversible degradation of the redox properties of iron oxides. Cr doping into the crystalline framework of iron oxide dendrites improves the stability of the structural transformation of iron oxides.