Immunological Evaluation of Co-Assembling a Lipidated Peptide Antigen and Lipophilic Adjuvants: Self-Adjuvanting Anti-Breast-Cancer Vaccine Candidates

Co-assembling vaccines composed of a lipidated HER2-derived antigenic CH401 peptide and either a lipophilic adjuvant, Pam₃CSK₄, α-GalCer, or lipid A 506, were evaluated as breast cancer vaccine candidates. This vaccine design was aimed to inherit both antigen multivalency and antigen-specific immunostimulation properties, observed in reported self-adjuvanting vaccine candidates, by using self-assembly and adjuvant-conjugated antigens. Under vaccination concentrations, respective lipophilic adjuvants underwent co-assembly with lipidated CH401, which boosted the anti-CH401 IgG and IgM production. In particular, α-GalCer was responsible for the most significant immune activation. Therefore, the newly developed vaccine design enabled the optimization of adjuvants against the antigenic CH401 peptide in a simple preparatory manner. Overall, the co-assembling vaccine design opens the door for efficient and practical self-adjuvanting vaccine development.     

Total Synthesis and Stereochemical Revision of Iriomoteolide‐2a

Total syntheses of the proposed and correct structures of iriomoteolide‐2a, a cytotoxic marine macrolide natural product with an unusual 23‐membered macrolactone skeleton, have been accomplished for the first time. The synthesis of the correct structure involves an asymmetric epoxidation/diepoxide cyclization cascade for the construction of the bis(tetrahydrofuran) moiety, a Suzuki–Miyaura coupling for the fragment assembly, and a ring‐closing metathesis for the closure of the macrocyclic backbone. In addition, the original stereochemical assignment of iriomoteolide‐2a was revised.     

Prediction of the layered ink layout for 3D printers considering a desired skin color and line spread function

Optical Review - We propose a layout estimation method for multi-layered ink using a measurement of the line spread function (LSF) and machine learning. The three-dimensional printing market for...     

Synthesis and characterization of iron(III)-substituted, dimeric polyoxotungstates, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](n-) (n = 6, X = As(III), Sb(III); n = 4, X = Se(IV), Te(IV))

Interaction of the lacunary [alpha-XW(9)O(33)](9-) (X = As(III), Sb(III)) with Fe(3+) ions in acidic, aqueous medium leads to the formation of dimeric polyoxoanions, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](6-) (X = As(III), Sb(III)) in high yield. X-ray single-crystal analyses were carried out on Na(6)[Fe(4)(H(2)O)(10)(beta-AsW(9)O(33))(2)] x 32H(2)O, which crystallizes in the monoclinic system, space group C2/m, with a = 20.2493(18) A, b = 15.2678(13) A, c = 16.0689(14) A, beta = 95.766(2) degrees, and Z = 2; Na(6)[Fe(4)(H(2)O)(10)(beta-SbW(9)O(33))(2)] x 32H(2)O is isomorphous with a = 20.1542(18) A, b = 15.2204(13) A, c = 16.1469(14) A, and beta = 95.795(2) degrees. The selenium and tellurium analogues are also reported, [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](4-) (X = Se(IV), Te(IV)). They are synthesized from sodium tungstate and a source of the heteroatom as precursors. X-ray single-crystal analysis was carried out on Cs(4)[Fe(4)(H(2)O)(10)(beta-SeW(9)O(33))(2)] x 21H(2)O, which crystallizes in the triclinic system, space group P macro 1, with a = 12.6648(10) A, b = 12.8247(10) A, c = 16.1588(13) A, alpha = 75.6540(10) degrees, beta = 87.9550(10) degrees, gamma = 64.3610(10) gamma, and Z = 1. All title polyanions consist of two (beta-XW(9)O(33)) units joined by a central pair and a peripheral pair of Fe(3+) ions leading to a structure with idealized C(2h) symmetry. It was also possible to synthesize the Cr(III) derivatives [Cr(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](6-) (X = As(III), Sb(III)), the tungstoselenates(IV) [M(4)(H(2)O)(10)(beta-SeW(9)O(33))(2)]((16)(-)(4n)-) (M(n+) = Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), and Hg(2+)), and the tungstotellurates(IV) [M(4)(H(2)O)(10)(beta-TeW(9)O(33))(2)]((16-4n)-) (M(n+) = Cr(3+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Hg(2+)), as determined by FTIR. The electrochemical properties of the iron-containing species were also studied. Cyclic voltammetry and controlled potential coulometry aided in distinguishing between Fe(3+) and W(6+) waves. By variation of pH and scan rate, it was possible to observe the stepwise reduction of the Fe(3+) centers.     

Cobalt-containing silicotungstate sandwich dimer [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2]22-

The 6-cobalt-substituted [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2]22- has been characterized by IR and UV-vis spectroscopy, elemental analysis, magnetic studies, electrochemistry, and gel filtration chromatography. A single-crystal X-ray analysis was carried out on K10Na12[{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2].49H2O (KNa-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a=19.9466(8) A, b=24.6607(10) A, c=34.0978(13) A, beta=102.175(1) degrees, and Z=2. Polyanion 1 represents a novel class of asymmetric sandwich-type polyanions. It contains three cobalt ions, which are encapsulated between an unprecedented (B-beta-SiW9O34) fragment and a (B-beta-SiW8O31) unit. Polyanion 1 is composed of two sandwich species via two Co-O-W bridges in the solid state and almost certainly in solution as well based on gel filtration chromatography. UV-visible spectroscopy and cyclic voltammetry also confirmed its stability. Two well-separated groups of waves appeared in the voltammetric pattern: the wave observed in the negative potential range versus a saturated calomel electrode features the redox processes of WVI centers; the two reversible redox couples observed in the positive potential domain are attributed to the redox processes of Co2+ centers and indicated that the two types of Co2+ centers in the structure are oxidized in separate waves. Such reversibility of Co2+ centers within multi-Co-substituted polyoxometalates is uncommon. The magnetic properties of KNa-1 are also discussed. The ferromagnetic ground state has been studied by magnetic susceptibility and magnetization measurements and fitted according to an anisotropic exchange model.     

Catalytic Asymmetric Total Synthesis of Exiguolide

The catalytic asymmetric total synthesis of (−)-exiguolide, a complex 20-membered macrolide embedded with a bis(tetrahydropyran) motif, is reported. The convergent synthesis involves the construction of the C1–C11 tetrahydropyran segment via catalytic asymmetric allylation and Prins cyclization, and the formation of the C12–C21 phosphonate segment via catalytic asymmetric cyclocondensation reaction and Johnson–Claisen rearrangement. The synthesis of 15-epi-exiguolide is also described.     

Direct Carboxylation of Electron-Rich Heteroarenes Promoted by LiO-tBu with CsF and [18]Crown-6

We herein demonstrate that the combination of LiO-tBu, CsF, and [18]crown-6 efficiently promotes the direct C−H carboxylation of electron-rich heteroarenes (benzothiophene, thiophene, benzofuran, and furan derivatives). A variety of functional groups, including methyl, methoxy, halo, cyano, amide, and keto moieties, are compatible with this system. The reaction proceeds via the formation of a tert-butyl carbonate species.     

Synthesis and characteristics of hyperbranched polymer with phosphonic acid groups for high-temperature fuel cells

Two different molecular weight hyperbranched polymers (HBP(L)-(PA)₂ and HBP(H)-(PA)₂) with two phosphonic acid groups as a functional group at the periphery and a low molecular weight hyperbranched polymer (HBP(L)-(PA)₂-Ac) with both two phosphonic acid groups and an acryloyl group as a cross-linker at the periphery were successfully synthesized as thermally stable proton-conducting electrolytes. A cross-linked electrolyte membrane (CL-HBP(L)-(PA)₂) was prepared by thermal polymerization of the HBP(L)-(PA)₂-Ac using benzoyl peroxide. Ionic conductivities of the HBP(L)-(PA)₂, the HBP(H)-(PA)₂, and the CL-HBP(L)-(PA)₂ under dry condition and their thermal properties were investigated, and also, the effect of the phosphonic acid group number on them was discussed. Ionic conductivities of the HBP(L)-(PA)₂ and the HBP(H)-(PA)₂ were found to be 1.5?×?10^?5 S cm^?1 at 150 °C and 3.6?×?10^?6 S cm^?1 at 143 °C, respectively, under dry condition, and showed the Vogel–Tamman–Fulcher type temperature dependence. The hyperbranched polymers and the cross-linked electrolyte membrane were thermally stable up to 300 °C, and the cross-linked electrolyte membrane (CL-HBP-(PA)₂) had suitable thermal stability as an electrolyte membrane for the high-temperature fuel cells under dry condition. Fuel cell measurement using a single membrane electrode assembly cell with the cross-linked membrane was performed.