The Stone-Wales bond rotation isomerization of nonicosahedral C60 (C2v-C60) into isolated-pentagon rule following icosahedral C60 (Ih-C60 or IPR-C60) is a limiting step in the synthesis of Ih-C60. However, extensive previous studies indicate that the potential energy barrier of the Stone-Wales bond rotation is between 6 and 8 eV, extremely high to allow for bond rotation at the temperatures used to produce fullerenes conventionally. This is also despite data indicating a possible fullerene road mechanism that necessitates low-temperature annealing. However, these previous investigations often have limiting factors, such as using the harmonic approximation to determine free energies at high temperatures or considering only the reverse Ih-C60 to C2v-C60 transition as a basis. Indeed, when the difference in energy between Ih-C60 and C2v-C60 is accounted for, this barrier is generally reduced by ∼1.5 eV. Thus, utilizing the recently developed density functional tight binding metadynamics (DFTB-MTD) interface, the effects of temperature on the bond rotation in the conversion of C2v-C60 to Ih-C60 have been investigated. We found that Stone-Wales bond rotations are complex processes with both in-plane and out-of-plane transition states, and which transition path dominates depends on temperature. Our results clearly show that at temperatures of 2000 K, the free energy for a C2v-C60 to Ih-C60 transition is only ∼4.21 eV and further reduces to ∼3.77 eV at 3000 K. This translates to transition times of ∼971 μs at 2000 K and ∼34 ns at 3000 K, indicating that defect healing is a fast process at temperatures typical of arc jet or laser ablation experiments. Conversely, below ∼2000 K, bond rotation becomes prohibitively slow, putting a lower threshold limit on the temperature of fullerene formation and subsequent annealing.Blood and plasma proteins are heavily investigated as biomarkers for different diseases. However, the post-translational modification states of these proteins are rarely analyzed since blood contains many enzymes that rapidly remove these modifications after sampling. In contrast to the well-described role of protein ADP-ribosylation in cells and organs, its role in blood remains mostly uncharacterized. Here, we discovered that plasma phosphodiesterases and/or ADP-ribosylhydrolases rapidly demodify in vitro ADP-ribosylated proteins. Thus, to identify the in vivo whole blood and plasma ADP-ribosylomes, we established a mass-spectrometry-based workflow that was applied to blood samples collected from LPS-treated pigs (Sus scrofa domesticus), which serves as a model for human systemic inflammatory response syndrome. These analyses identified 60 ADP-ribosylated proteins, 17 of which were ADP-ribosylated plasma proteins. This new protocol provides an important step forward for the rapidly developing field of ADP-ribosylation and defines the blood and plasma ADP-ribosylomes under both healthy and disease conditions.We have developed a new set of norm-conserving pseudopotentials and companion Gaussian basis sets for the actinide (An) series (Ac-Lr) using the Goedecker, Teter, and Hutter (GTH) formalism with the Perdew, Burke, and Ernzerhof (PBE) exchange-correlation functional of generalized gradient approximation. To test the accuracy and reliability of the newly parameterized An-GTH pseudopotentials and basis sets, a variety of benchmarks on actinide-containing molecules were carried out and compared to all-electron and available experimental results. The new pseudopotentials include both medium- ([Xe]4f14) and large-core ([Xe]4f145d10) options that successfully reproduce the structures and energetics, particularly redox processes. The medium-core size set, in particular, reproduces all-electron calculations over multiple oxidation states from 0 to VII, whereas the large-core set is suitable only for the early series elements and low oxidation states. The underlying reason for these transferability issues is discussed in detail. This work fills a critical void in the literature for studying the chemistry of 5f-block elements in the condensed phase.Biomolecules with metal ion(s) (e.g., metalloproteins) play many important biological roles. However, accurate structural determination of metalloproteins, particularly those containing transition metal ion(s), is challenging due to their complicated electronic structure, complex bonding of metal ions, and high number of conformations in biomolecules. Quantum refinement, which was proposed to combine crystallographic data with computational chemistry methods by several groups, can improve the local structures of some proteins. In this study, a quantum refinement method combining several multiscale computational schemes with experimental (X-ray diffraction) information was developed for metalloproteins. Various quantum refinement approaches using different ONIOM (our own N-layered integrated molecular orbital and molecular mechanics) combinations of quantum mechanics (QM), semiempirical (SE), and molecular mechanics (MM) methods were conducted to assess the performance and reliability on the refined local struations, which can be regarded as novel pseudo-three- and pseudo-four-layer ONIOM methods, respectively, to refine the key Zn binding site at the coupled-cluster singles and doubles (CCSD) level. These refined results indicate that multiscale quantum refinement schemes can be used to improve the structural accuracy obtained for local metal binding site(s) in metalloproteins with high efficiency.Air-stable organic radicals and radical ions have attracted great attention for their far-reaching application ranging from bioimaging to organic electronics. However, because of the highly reactive nature of organic radicals, the design and synthesis of air-stable organic radicals still remains a challenge. https://www.selleckchem.com/products/prgl493.html Herein, an air-stable organic radical from a controllable photoinduced domino reaction of a hexa-aryl substituted anthracene is described. The domino reaction involves a photoinduced [4 + 2] cycloaddition reaction, rearrangement, photolysis, and an elimination reaction; 1H/13C NMR spectroscopy, high resolution mass spectrometry, single-crystal X-ray diffraction, and EPR spectroscopy were exploited for characterization. Furthermore, a photoinduced domino reaction mechanism is proposed according to the experimental and theoretical studies. In addition, the effects of employing push and pull electronic groups on the controllable photoinduced domino reaction were investigated. This article not only offers a new blue emitter and novel air-stable organic radical compound for potential application in organic semiconductor applications, but also provides a perspective for understanding the fundamentals of the reaction mechanism on going from anthracene to semiquinone in such anthracene systems.