CH Activation Generates Period‐Shortening Molecules That Target Cryptochrome in the Mammalian Circadian Clock

The synthesis and functional analysis of KL001 derivatives, which are modulators of the mammalian circadian clock, are described. By using cutting‐edge C? H activation chemistry, a focused library of KL001 derivatives was rapidly constructed, which enabled the identification of the critical sites on KL001 derivatives that induce a rhythm‐changing activity along with the components that trigger opposite modes of action. The first period‐shortening molecules that target the cryptochrome (CRY) were thus discovered. Detailed studies on the effects of these compounds on CRY stability implicate the existence of an as yet undiscovered regulatory mechanism.     

Vapour–liquid equilibrium for the systems diethyl sulphide + 1-butene, +cis-2-butene, +2-methylpropane, +2-methylpropene, +n-butane, +trans-2-butene

Isothermal vapour–liquid equilibrium was measured for the systems of diethyl sulphide + 1-butene, +cis-2-butene, and +2-methylpropene at 312.6 K, diethyl sulphide + n-butane was measured at 317.6 K, diethyl sulphide + trans-2-butene at 317.5 K, and diethyl sulphide + 2-methylpropane at 308.0 K. The pressure–temperature–total composition data were converted into pressure–temperature–liquid–vapour composition data using the method of Barker. Error estimates are provided for each variable. The isothermal parameters for the Wilson, NRTL and UNIQUAC activity coefficient models were regressed. The measurements were compared with the predictions by COSMO segment activity coefficient (COSMO-SAC) and UNIFAC.     

Exploiting a C–N Bond Forming Cytochrome P450 Monooxygenase for C–S Bond Formation

C–S bond formation reactions are widely distributed in the biosynthesis of biologically active molecules, and thus have received much attention over the past decades. Herein, we report intramolecular C–S bond formation by a P450 monooxygenase, TleB, which normally catalyzes a C−N bond formation in teleocidin biosynthesis. Based on the proposed reaction mechanism of TleB, a thiol-substituted substrate analogue was synthesized and tested in the enzyme reaction, which afforded the unprecedented sulfur-containing thio-indolactam V, in addition to an unusual indole-fused 6/5/8-tricyclic product whose structure was determined by the crystalline sponge method. Interestingly, conformational analysis revealed that the SOFA conformation is stable in thio-indolactam V, in sharp contrast to the major TWIST form in indolactam V, resulting in differences in their biological activities.     

Drug Molecular Immobilization and Photofunctionalization of Calcium Phosphates for Exploring Theranostic Functions

Theranostics (bifunction of therapeutics and diagnostics) has attracted increasing attention due to its efficiency that can reduce the physical and financial burden on patients. One of the promising materials for theranostics is calcium phosphate (CP) and it is biocompatible and can be functionalized not only with drug molecules but also with rare earth ions to show photoluminescence that is necessary for the diagnostic purpose. Such the CP-based hybrids are formed in vivo by interacting between functional groups of organic molecules and inorganic ions. It is of great importance to elucidate the interaction of CP with the photofunctional species and the drug molecules to clarify the relationship between the existing state and function. Well-designed photofunctional CPs will contribute to biomedical fields as highly-functional ormultifunctional theranostic materials at the nanoscales. In this review, we describe the hybridization between CPs and heterogeneous species, mainly focusing on europium(III) ion and methylene blue molecule as the representative photofunctional species for theranostics applications.     

Energetic proton emission in heavy ion collisions at intermediate energy: Pre-equilibrium and cooperative effects

Energetic proton emission has been investigated as a function of the centrality in the reaction ⁵⁸Ni + ⁵⁸Ni at 30 AMeV. Protons with energy extending up to a relevant fraction of the total available energy in the reaction were measured and studied. The dependence on the reaction centrality has been extensively investigated and data have been compared with the results of microscopic transport calculations. The more striking observation concerns the extremely energetic proton (E^NN _P ≥ 130 MeV) multiplicity which is found to increase almost quadratically with the number of participant nucleons thus indicating the onset of a mechanism beyond one and two-body dynamics.     

Dielectron production in 12C+12C collisions at 2A GeV with the HADES spectrometer

The invariant-mass spectrum of e+e- pairs produced in 12C+12C collisions at an incident energy of 2 GeV per nucleon has been measured for the first time. The measured pair production probabilities span over 5 orders of magnitude from the pi(0)-Dalitz to the rho/omega invariant-mass region. Dalitz decays of pi(0) and eta account for all the yield up to 0.15 GeV/c(2), but for only about 50% above this mass. A comparison with model calculations shows that the excess pair yield is likely due to baryon-resonance and vector-meson decays. Transport calculations based on vacuum spectral functions fail, however, to describe the entire mass region.     

Comparison between different ways to determine diffusion coefficient and by solving Fick’s equation for spherical coordinates

The following document covers the determination of the diffusion coefficient of two powder materials: LiFePO₄ and LiMn₂O₄ by using potentiostatic intermittent titration technique (PITT) and impedance spectroscopy methodology and compares relevant results with the following relation: , which is obtained by solving Fick’s spherical coordinate equation (where I ₀ is the initial step current in the PITT experiment, R is the particle radius, Q is the charge that intercalated during the step, and α is the percentage of the theoretical intercalated charge). This procedure allowed the verification of the validity of the spherical model for the powder materials, the accuracy of the expression proposed for the diffusion coefficient determination, and the correctness of the measures that had been taken.     

Exact algorithms for the bin packing problem with fragile objects

We are given a set of objects, each characterized by a weight and a fragility, and a large number of uncapacitated bins. Our aim is to find the minimum number of bins needed to pack all objects, in such a way that in each bin the sum of the object weights is less than or equal to the smallest fragility of an object in the bin. The problem is known in the literature as the Bin Packing Problem with Fragile Objects, and appears in the telecommunication field, when one has to assign cellular calls to available channels by ensuring that the total noise in a channel does not exceed the noise acceptance limit of a call.We propose a branch-and-bound and several branch-and-price algorithms for the exact solution of the problem, and improve their performance by the use of lower bounds and tailored optimization techniques. In addition we also develop algorithms for the optimal solution of the related knapsack problem with fragile objects. We conduct an extensive computational evaluation on the benchmark set of instances, and show that the proposed algorithms perform very well.     

Breakup temperature of target spectators in 197Au + 197Au collisions at E/A = 1000 MeV

Breakup temperatures were deduced from double ratios of isotope yields for target spectators produced in the reaction ¹⁹⁷Au + ¹⁹⁷Au at 1000 MeV per nucleon. Pairs of ^3,4He and ^6,7Li isotopes and pairs of ^3,4He and H isotopes (p, d and d, t) yield consistent temperatures after feeding corrections, based on the quantum statistical model, are applied. The temperatures rise with decreasing impact parameter from 4 MeV for peripheral to about 10 MeV for the most central collisions. The good agreement with the breakup temperatures measured previously for projectile spectators at an incident energy of 600 MeV per nucleon confirms the universality established for the spectator decayat relativistic bombarding energies. The measured temperatures also agree with the breakup temperatures predicted by the statistical multifragmentation model. For these calculations a relation between the initial excitation energy and mass was derived which gives good simultaneous agreement for the fragment charge correlations. The energy spectra of light charged particles, measured at τ_lab = 150°, exhibit Maxwellian shapes with inverse slope parameters much higher than the breakup temperatures. The statistical multifragmentation model, because Coulomb repulsion and sequential decay processes are included, yields light-particle spectra with inverse slope parameters higher than the breakup temperatures but considerably below the measured values. The systematic behavior of the differences suggests that they are caused by light-charged-particle emission prior to the final breakup stage.