New approach for designing single-chain magnets: organization of chains via hydrogen bonding between nucleobases

Two one-dimensional (1D) manganese complexes, [Mn(2)(naphtmen)(2)(L)](ClO(4))·2Et(2)O·2MeOH·H(2)O (1) and [Mn(2)(naphtmen)(2)(HL)](ClO(4))(2)·MeOH (2), were synthesized by using a bridging ligand with a nucleobase moiety, 6-amino-9-β-carboxyethylpurine, and a salen-type manganese(III) dinuclear complex, [Mn(2)(naphtmen)(2)(H(2)O)(2)](ClO(4))(2) (naphtmen(2-) = N,N'-(1,1,2,2-tetramethylethylene)bis(naphthylideneiminato) dianion). In 1 and 2, the carboxylate-bridged Mn(III) dinuclear units are alternately linked by two kinds of weak Mn···O interactions into 1D chains. As a result, canted antiferromagnetic and ferromagnetic interactions are alternately present along the chains, leading to a 1D chain with non-cancellation of anisotropic spins. Since the chains connected via H-bonds between nucleobase moieties are magnetically isolated, both 1 and 2 act as single-chain magnets (SCMs). More importantly, this result shows the smaller canting angles hinder long-range ordering in favor of SCM dynamics.     

Design strategy for a near-infrared fluorescence probe for matrix metalloproteinase utilizing highly cell permeable boron dipyrromethene

Near-infrared (NIR) fluorescence probes are especially useful for simple and noninvasive in vivo imaging inside the body because of low autofluorescence and high tissue transparency in the NIR region compared with other wavelength regions. However, existing NIR fluorescence probes for matrix metalloproteinases (MMPs), which are tumor, atherosclerosis, and inflammation markers, have various disadvantages, especially as regards sensitivity. Here, we report a novel design strategy to obtain a NIR fluorescence probe that is rapidly internalized by free diffusion and well retained intracellularly after activation by extracellular MMPs. We designed and synthesized four candidate probes, each consisting of a cell permeable or nonpermeable NIR fluorescent dye as a F?rster resonance energy transfer (FRET) donor linked to the NIR dark quencher BHQ-3 as a FRET acceptor via a MMP substrate peptide. We applied these probes for detection of the MMP activity of cultured HT-1080 cells, which express MMP2 and MT1-MMP, by fluorescence microscopy. Among them, the probe incorporating BODIPY650/665, BODIPY-MMP, clearly visualized the MMP activity as an increment of fluorescence inside the cells. We then applied this probe to a mouse xenograft tumor model prepared with HT-1080 cells. Following intratumoral injection of the probe, MMP activity could be visualized for much longer with BODIPY-MMP than with the probe containing SulfoCy5, which is cell impermeable and consequently readily washed out of the tissue. This simple design strategy should be applicable to develop a range of sensitive, rapidly responsive NIR fluorescence probes not only for MMP activity, but also for other proteases.     

On the semilinear Schrödinger equation with time dependent coefficients

We consider nonlinear Schrödinger equation with time dependent coefficients. Fanelli [5] found a transformation between solutions of the original equation and of the usual Schrödinger equation with power nonlinearity involving time dependent coefficients in some Lorentz spaces. In this paper we extend the results in [5] in space‐time integrability properties of solutions. Particularly, we prove that the existence and uniqueness of solutions can be described exclusively in terms of Lebesgue spaces (not Lorentz spaces as in [5]) as far as the space integrability of solutions. We also discuss the equation with coefficient of an explicit homogeneous function and describe the associated Strichartz estimate and contraction mapping argument.     

de Bruijn-type identity for systems with flux

We show that an information-theoretic relation called the de Bruijn-type identity can be reformulated in a physical context with probability currents. The time derivatives of relative entropies under the continuity equation are presented, which shows that the conservation of distance between a pair of distributions is generally not guaranteed. As an important implication of these results, we discuss and present a possible conceptual framework for the classical no-cloning (deleting) theorem and qualitatively assert that we can attribute the perfect performance of the operating machine to the openness (non-vanishing flow at boundaries between the processing machine and the system) during the process.     

Development of exploding wire ion source for intense pulsed heavy ion beam accelerator

A Novel exploding wire type ion source device is proposed as a metallic ion source of intense pulsed heavy ion beam (PHIB) accelerator. In the device, multiple shot operations are realized without breaking the vacuum. The basic characteristics of the device are evaluated experimentally with an aluminum wire of diameter 0.2 mm and length 25 mm. A capacitor bank of capacitance 3 μF and a charging voltage of 30 kV was used, and the wire was successfully exploded by a discharge current of 15 kA with a rise time of 5.3 μs. Plasma flux of ion current density around 70 A/cm² was obtained at 150 mm downstream from the device. The drift velocity of ions evaluated by a time-of-flight method was 2.7×10⁴ m/ s, which corresponds to the kinetic energy of 100 eV for aluminum ions. From the measurement of the ion current density distribution, the ion flow is found to be concentrated toward the direction where the ion acceleration gap is placed. From the experiment, the device is found to be acceptable for applying the PHIB accelerator.     

Broadband terahertz light source pumped by a 1 μm picosecond laser

We obtained a frequency tunable, low-coherence, picosecond, terahertz (THz) output with a high repetition rate from a picosecond Nd:YVO₄ bounce laser in combination with tandem periodically poled stoichiometric lithium tantalate and 4′-dimethylamino-N-methyl-4-stilbazolium tosylate crystals. The frequency of the THz output was tunable in the range 2.1–7.1 THz with a linewidth of ~3.5 THz at 2.2 THz. The THz output had a maximum peak power of ~180 mW and an average power of ~0.65 μW at 3.9 THz. This system has the potential to realize ultra-high speed, THz coherence tomography.     

Total Synthesis of (+)‐Dibromophakellin

Two members of a family of pyrrole–imidazole marine alkaloids, (+)‐dibromophakellin and the nonnatural congener (+)‐phakellin, were synthesized enantioselectively from 4‐hydroxy‐L ‐proline. The chiral aminal at C10 was constructed efficiently by means of an Overman‐type [3,3] sigmatropic rearrangement of an enamide (see scheme).

     

Photodynamic Activity of C70 Caged within Surface‐Cross‐Linked Liposomes

[70]Fullerene (C₇₀) encapsulated into a surface‐cross‐linked liposome, a so‐called cerasome, was prepared by an exchange reaction incorporating C₇₀?γ‐cyclodextrin complexes into lipid membranes. Fullerene exchange in a cerasome‐incorporated C₇₀ (CIC₇₀), as well as in a lipid‐membrane‐incorporated C₇₀ (LMIC₇₀), was completed within 1 min with stirring at 25 °C. CIC₇₀ was more resistant to lysis than LMIC₇₀ towards lysing agents such as surfactants. Furthermore, the photodynamic activity of CIC₇₀ in HeLa cells was similar to that of LMIC₇₀, indicating that C₇₀ can act as a photosensitizing drug (PS) without release from cerasome membranes. Thus, in contrast with general drug‐delivery systems (DDSs), which require the drug to be released from the interior of liposomes, carriers for PSs for use in photodynamic therapy (PDT) do not necessarily need to release the drug. These results indicate that DDSs with high morphological stability can increase the residence time in blood and achieves tumor‐selective drug delivery by the enhanced permeability and retention (EPR) effect.     

Pd/TEMPO-catalyzed electrooxidative synthesis of biaryls from arylboronic acids or arylboronic esters

A facile electrooxidative method for synthesizing biaryls from arylboronic acids or arylboronic esters is described. In the presence of a catalytic amount of Pd(OAc)₂ and TEMPO, the electrooxidation of arylboronic acids or arylboronates gave the corresponding biaryls in moderate to excellent yields.     

Synthetic studies toward miroestrols: trials for elongation of the methyl group of 5-substituted 2-methyl-2-cyclohexanone to 3-methyl-2-butenyl function

Toward total synthesis of miroestrols (miroestrol and deoxymiroestrol), 3-methyl-2-butenyl function (endo-C5 unit) on D ring as a carbon chain for C and E rings was prepared by elongation of the methyl group in α-methyl-α,β-unsaturated ketone unit, and 3,5-dinitrobenzoyl group was introduced as a potential leaving group for the construction of B ring. The former was accomplished through a sequence of epoxide ring-opening, microwave-irradiated siloxy-Cope rearrangement, and isomerization of 3-methyl-3-butenyl function (exo-C5 unit) to endo-C5 unit.