Efficient biotinylation of methacryloyl-functionalized nonadherent cells for formation of cell microarrays

In order to obtain cell microarrays formed with human promyelocytic leukemia cells (HL-60), biotinylation of methacryloyl-functionalized HL-60 cells was performed via a thiol-ene reaction with thiol-terminated 4-arm poly(ethylene glycol) (PEG(4)10K-SH). Biotinylated HL-60 cells were selectively adhered onto an avidin-patterned surface with high viability.     

A purification system for 64Cu produced by a biomedical cyclotron for antibody PET imaging

Ion exchange is a simple and efficient method for separating no-carrier-added ⁶⁴Cu from an irradiated Ni target. We developed a semi-automated two-round ⁶⁴Cu separation system equipped with a strong-base anion exchange resin column. We first verified the efficiency of the system using a non-radioactive substitute consisting of 25 mg of Ni and 127 ng of Cu, and confirmed that Cu was completely eluted at the second round of the separation step. After the bombardment, separation of ⁶⁴Cu from the Ni target was achieved with high radiochemical purity. ⁶⁴Cu produced and separated in this study had an extremely low level of Ni impurity. It could be used for labeling monoclonal antibodies for antibody positron emission tomography imaging and synthesizing radiopharmaceuticals.     

Magnetic transition in dimerized radical cation salt of (BPDT-TTF)2ICl2 studied by heat capacity measurements

Thermodynamic investigation using the relaxation calorimetry technique and the microchip calorimetry technique is performed to clarify low-temperature behaviors of a radical cation salt consisting of a donor molecule of bispropylenedithiotetrathiafulvalene (BPDT-TTF) and a linear anion of ${{\text{ICl}}_{2}^{-}}$ ICl 2 ? . This compound has a layered structure similar to numerous BEDT-TTF compounds. The donor molecules form a dimerized arrangement in the layer. Temperature dependence of heat capacity obtained by the relaxation technique shows a broad hump structure around 20–25 K corresponding to the temperature where the magnetic susceptibility shows a drastic decrease due to the formation of the singlet spin state. The microchip calorimetry technique detected a step-like anomaly around 23 K in the temperature dependence of C _p T ^?1 of which entropy is evaluated as only few % of Rln2 corresponding to the full entropy of localized π-electrons located on each dimer unit. The negligibly small T-linear term in the low-temperature heat capacity and absence of magnetic fields dependence below 3.2 K predict opening of rigid gap structure in the spin excitations, which is consistent with a spin-singlet formation due to the formation of spin-Peierls type ordering or charge ordering state.     

Polycyclic N‐heterocyclic compounds. Part 66: Synthesis of N‐[2‐([1,2,4]oxadiazol‐5‐yl)cyclopenten‐1‐yl]formamide oximes and their evaluation as inhibitors of platelet aggregation

N‐[2‐([1,2,4]Oxadiazol‐5‐yl)cyclopenten‐1‐yl]formamide oximes were synthesized by fusion of (6,7‐dihydro‐5H‐cyclopenta[1,2‐d]pyrimidin‐4‐yl)amidines and/or their amide oximes with hydroxylamine hydrochloride through a subsequent rearrangement reaction. Assay of the products for anti‐platelet aggregation activity revealed that certain of them showed promising inhibitory effect on arachidonic acid‐induced platelet aggregation. J. Heterocyclic Chem., (2011).     

Protein nanotubes with an enzyme interior surface

This report describes the synthesis and enzyme activities of multilayered protein nanotubes with an α-glucosidase (αGluD) interior surface. The nanotubes were prepared by using an alternating layer-by-layer (LbL) assembly of human serum albumin (HSA) and oppositely charged poly-L-arginine (PLA) into a track-etched polycarbonate (PC) membrane (pore size=400 nm) followed by addition of αGluD as the last layer of the wall. Subsequent dissolution of the PC template yielded (PLA/HSA)(2)PLA/αGluD nanotubes. SEM measurements revealed the formation of uniform hollow cylinders with (413±17) nm outer diameter and (52±3) nm wall thickness. In aqueous media, the nanotubes captured a fluorogenic glucopyranoside, 4-methyl-umbelliferyl-α-D-glucopyranoside (MUGlc), into their one-dimensional pore space and hydrolyzed the substrate efficiently to form α-D-glucose. We determined the enzyme parameters (Michaelis constant, K(M), and catalytic constant, k(cat), values) of the protein nanotubes. The several-micrometers-long cylinders were of sufficient length to be spun down by centrifugation at 4000 g, so the product could therefore be easily separated. Similar biocatalysts were prepared by complexation of biotinylated-αGluD into HSA-based nanotubes bearing a single avidin layer as an internal surface. The obtained hybrid nanotubes also exhibited the same enzyme activity for the MUGlc hydrolysis.     

Measurements on diproton emission from the break-up channels of 23Al and 22Mg

Two-proton relative momentum distributions from the break-up channels ²³Al→p+p+²¹Na and ²²Mg→p+p+²⁰Ne at an energy of 60–70 A MeV have been measured together with two-proton opening angles at the projectile fragment separator beamline (RIPS) in the RIKEN Ring Cyclotron Facility. The results demonstrate the existence of diproton emission component from single-step ²He for highly excited ²³Al and ²²Mg.     

UV-visible and 1H or 13C NMR spectroscopic studies on the specific interaction between lithium ions and the anion from tropolone or 4-isopropyltropolone (hinokitiol) and on the formation of protonated tropolones in acetonitrile or other solvents

The specific interaction between lithium ions and the tropolonate ion (C(7)H(5)O(2)-: L-) was examined by means of UV-visible and 1H or 13C NMR spectroscopy in acetonitrile and other solvents. On the basis of the electronic spectra, we can propose the formation of not only coordination-type species (Li+(L-)2) and the ion pair (Li+L-) but also a "triple cation" ((Li+)2L-) in acetonitrile and acetone; however, no "triple cation" was found in N,N-dimethylformamide (DMF) and in dimethylsulfoxide (DMSO), solvents of higher donicities and only ion pair formation between Li+ and L- in methanol of much higher donicity and acceptivity. The 1H NMR chemical shifts of the tropolonate ion with increasing Li+ concentration verified the formation of (Li+)2L- species in CD3CN and acetone-d6, but not in DMF-d6 or CD(3)OD. With increasing concentration of LiClO(4) in CD(3)CN, the 1H NMR signals of 4-isopropyltropolone (HL') in coexistence with an equivalent amount of Et(3)N shifted first toward higher and then toward lower magnetic-fields, which were explained by the formation of (Li+)(Et(3)NH+)L'- and by successive replacement of Et(3)NH+ with a second Li+ to give (Li+)2L'-. In CD(3)CN, the 1,2-C signal in the 13C NMR spectrum of tetrabutylammnium tropolonate (n-Bu(4)NC(7)H(5)O) appeared at an unexpectedly lower magnetic-field (184.4 ppm vs TMS) than that of tropolone (172.7 ppm), while other signals of the tropolonate showed normal shifts toward higher magnetic-fields upon deprotonation from tropolone. Nevertheless, with addition of LiClO(4) at higher concentrations, the higher and lower shifts of magnetic-fields for 1,2-C and other signals, respectively, supported the formation of the (Li+)2L- species, which can cause redissolution of LiL precipitates. All of the data with UV-visible and 1H and 13C NMR spectroscopy demonstrated that the protonated tropolone (or the dihydroxytropylium ion), H(2)L+, was produced by addition of trifluoromethanesulfonic or methanesulfonic acid to tropolone in acetonitrile. The order of the 5-C and 3,7-C signals in 13C NMR spectra of the tropolonate ions was altered by addition of less than an equivalent amount of H+ to the tropolonate ion in CD(3)CN. Theoretical calculations satisfied the experimental 13C NMR chemical shift values of L-, HL, and H(2)L+ in acetonitrile and were in accordance with the proposed reaction schemes.     

Quantum chemistry beyond Born–Oppenheimer approximation on a quantum computer: A simulated phase estimation study

We present an efficient quantum algorithm for beyond‐Born–Oppenheimer molecular energy computations. Our approach combines the quantum full configuration interaction method with the nuclear orbital plus molecular orbital method. We give the details of the algorithm and demonstrate its performance by classical simulations. Two isotopomers of the hydrogen molecule (H₂, HT) were chosen as representative examples and calculations of the lowest rotationless vibrational transition energies were simulated. © 2016 Wiley Periodicals, Inc.     

Synthetic studies of GKK1032s: the asymmetric synthesis of the decahydrofluorene skeleton via a novel cyclization of silyl enol ether and sequential retro Diels-Alder and intramolecular Diels-Alder reactions

GKK1032s, which were isolated from the culture broth of Penicillium sp. GKK1032, exhibit antitumor activity. We constructed the fully elaborated decahydrofluorene skeleton of GKK1032s. The C-ring was constructed by intramolecular cyclization reaction between a chiral epoxide and silyl enol ether, and the dienophile moiety was introduced concurrently. In addition, the AB-rings were stereoselectively constructed using novel sequential retro Diels-Alder (DA) and intramolecular Diels-Alder (IMDA) reactions. Several further modifications of the IMDA adduct were carried out, leading to the asymmetric synthesis of the desired hydroxyester including nine stereo centers.