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Makoto Fujita

Publications and source records attributed to Makoto Fujita.

At least 19 recordsLinked to original sources
PubMed2025

Vinigrol Tricyclic Scaffold Biosynthesis Employs an Atypical Terpene Cyclase and a Multipotent Cyclization Cascade.

Vinigrol (1) is a fungal diterpenoid consisting of a decahydro-1,5-butanonaphthalene ring system with no analogs in nature. Despite immense efforts in synthetic studies, the vinigrol biosynthesis pathway remains largely unknown. Herein, we identified a biosynthetic gene cluster for 1 and fully elucidated the biosynthetic pathway. By employing an AlphaFold-generated model structure, we identified the possible catalytic residues of the noncanonical terpene cyclase and analyzed their function by site-directed mutagenesis. We found that the G340A mutation opened a cryptic pathway for an unprecedented tetracyclic diterpene, defined here as virgarene. Retro-biosynthetic theoretical analysis provided a solid foundation for the complex cyclization pathway for the vinigrol scaffold, its chemical transformation to a structurally distinct bonnadiene, and redirection of the enzymatic cyclization cascade to virgarene. Close inspection of the terpene cyclization pathway via integrated experimental and theoretical approaches would allow efficient exploration of novel terpenoid chemistries.

Cyclization↗
PubMed2007

Guest-dependent flexible coordination networks with fluorinated ligands.

Guest-dependent flexible coordination networks are formed from 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf), 4,4'-bis(4-pyridylmethyl)octafluorobiphenyl (bpfb), 2,6-bis(4-pyridylmethyl)hexafluoronaphthalene (2,6-bpfn), and 2,7-bis(4-pyridylmethyl)hexafluoronaphthalene (2,7-bpfn) with Cd(NO3)2 in the presence of various organic compounds. The reaction of bpf affords one-dimensional cyclic chains, two-dimensional rhombus grid sheets, and three-dimensional diamond frameworks with threefold interpenetration. The reaction of bpfb mainly affords two-dimensional rhombus grid sheets with twofold parallel interpenetration. The reaction of 2,6-bpfn affords a one-dimensional ladder and two-dimensional rhombus grid, twisted grid, and herringbone sheets. The reaction of 2,7-bpfn affords two-dimensional rhombus grid sheets and grid sheets with dumbbell-shaped cavities. This diversity of network topologies is induced by interactions between the guest molecules and the flexible ligand frameworks.

Journal Article↗
PubMed2006

Networking a hollow cage via guest coordination.

A hollow coordination cage with a highly symmetric cavity was successfully self-assembled to form a 2D-network having a less symmetric cavity via networking of disordered guests with a metal connector.

Journal Article↗
PubMed2006

Fluorous nanodroplets structurally confined in an organopalladium sphere.

The distinct properties of fluorous phases are practically useful for separation, purification, and reaction control in organic synthesis. Here, we report the formation of a liquid-like fluorous droplet, composed of 24 perfluoroalkyl chains confined in the interior of a 5-nanometer-sized, roughly spherical shell that spontaneously assembled in solution from 12 palladium ions and 24 bridging ligands. Crystallographic analysis confirmed the rigid shell framework and amorphous interior. Perfluoroalkanes can dissolve in this well-defined fluorous phase, whereas they can hardly dissolve in a surrounding polar organic solution, and their solubility (up to approximately eight perfluoroalkane molecules per spherical complex) can be finely controlled by tuning the length of perfluoroalkyl chains tethered to the shell.

Journal Article↗
PubMed2006

Folding of an Ala-Ala-Ala tripeptide into a beta-turn via hydrophobic encapsulation.

An Ac-Ala-Ala-Ala-NH2 tripeptide was folded into a beta-turn structure even in water through hydrophobic binding by a self-assembled porphyrin cage. The turn conformation of the bound peptide was fully assigned from NOESY measurements and was strongly supported by molecular dynamics simulation. Single mutation experiments and molecular modeling also suggested that CH-pi interactions between methyl groups of Ala residues and porphyrin ligands were important for the stabilization of the turn conformation. Furthermore, we observed the induction of a beta-hairpin structure by encapsulation of a heptapeptide, Ac-Gly-Gly-Ala-Ala-Ala-Gly-Gly-NH2, possessing Ala-Ala-Ala sequence at the middle.

Alanine↗
PubMed2006

Direct crystallographic observation of a coordinatively unsaturated transition-metal complex in situ generated within a self-assembled cage.

In situ crystallographic observation of an extremely labile coordinatively unsaturated transition-metal complex, Cp'Mn(CO)2 (Cp' = methylcyclopentadienyl), was achieved by generating and trapping it within the confined cavity of a self-assembled cage in the crystalline state at a low temperature. The labile target Cp'Mn(CO)2 was formed by the photodissociation of the CO ligand from stable Cp'Mn(CO)3, which was accommodated within the cavity of the coordination cage. Being trapped in the cage at a low temperature, Cp'Mn(CO)2 showed sufficient stability to be analyzed by X-ray crystallography. The diffraction study revealed that the 16-electron unsaturated Mn complex adopted a pyramidal geometry rather than a planar geometry.

Journal Article↗
PubMed2006

2D hydrogen-bonded square-grid coordination networks with a substitution-active metal site.

Reported here is the preparation and property of 2D coordination networks composed of rodlike ligands with ethylene glycol side chains (1). Two 2D coordination networks, [[Co(1)2(H2O)2](NO3)2.1.5H2O]n and [[Ni(1)2(H(2)O)2](NO3)2.1.5H2O]n, have been synthesized and characterized by single-crystal X-ray diffraction, TG, DSC, UV-vis spectroscopy, and magnetic measurements. The structural analyses clarified that infinite 1D hydrogen-bond arrays composed of ethylene glycol chains contribute to the stabilization of 2D coordination frameworks, keeping the environment of substitution-active metal sites unchanged. They are more stable than a similar square-grid coordination network that does not possess an ethylene glycol chain on the ligand. We also succeeded in the direct observation of a reversible apical-ligand-exchange reaction at the cobalt(II) and nickel(II) ions in a single-crystal-to-single-crystal fashion because of the considerable stability as well as moderate flexibility of the framework. The cobalt-containing coordination network crystal showed chromic behavior depending on temperatures. Crystallographic and spectroscopic studies revealed that the color change of the crystal was attributed to the ligand-exchange process between H2O and a NO3 anion on the cobalt metal. Magnetic measurements indicated weak antiferromagnetic nearest-neighbor spin coupling between cobalt(II) ions.

Journal Article↗
PubMed2006

Control of molecular interactions by the hollow of coordination cages.

Coordination self-assembly entities have been demonstrated to be useful and powerful alternatives for the construction of predefined and well-organized architectures. Self-assembled coordination cages, which possess an inner hydrophobic cavity, can be utilized to move substrates closer by encapsulation so enabling their interaction with each other and exhibiting of non-classical physical properties.

Journal Article↗
PubMed2006

Diels-alder in aqueous molecular hosts: unusual regioselectivity and efficient catalysis.

Self-assembled, hollow molecular structures are appealing as synthetic hosts for mediating chemical reactions. However, product binding has inhibited catalytic turnover in such systems, and selectivity has rarely approached the levels observed in more structurally elaborate natural enzymes. We found that an aqueous organopalladium cage induces highly unusual regioselectivity in the Diels-Alder coupling of anthracene and phthalimide guests, promoting reaction at a terminal rather than central anthracene ring. Moreover, a similar bowl-shaped host attains efficient catalytic turnover in coupling the same substrates (although with the conventional regiochemistry), most likely because the product geometry inhibits the aromatic stacking interactions that attract the planar reagents to the host.

Journal Article↗
PubMed2006

Peptide recognition: encapsulation and alpha-helical folding of a nine-residue peptide within a hydrophobic dimeric capsule of a bowl-shaped host.

A dimeric capsule of coordination bowl 1 encapsulated a nine-residue peptide (Trp-Ala-Glu-Ala-Ala-Ala-Glu-Ala-Trp; 2) within the large hydrophobic cavity in water, and stabilized the alpha-helical conformation of bound 2. An NMR titration experiment revealed that monomeric bowl 1 recognized two Trp residues at the both terminals of 2 through 1/2 = 1:1 to 2:1 complexation. The 1:1 and 2:1 species exist in equilibrium even in the presence of excess 1. It was found that the formation of the 2:1 complex, in which two bowls of 1 wrapped the whole of 2, became dominant by the addition of NaNO3 due to the fact that the enhanced ion strength increased the hydrophobic interaction between Trp residues and the cavity of 1. The alpha-helical conformation of 2 within the dimeric capsule of 1 was elucidated from detailed NOESY analysis.

Dimerization↗
PubMed2006

Noncontact vital sign monitoring system for isolation unit (casualty care system).

For measuring the vital signs of casualties inside an isolation unit, we developed a noncontact vital sign monitoring system using a microwave radar. The system was tested on eight healthy volunteers ranging in age from 30 to 48 years. The heart and respiratory rates derived by the microwave radar correlated with the heart and respiratory rates determined by electrocardiogram and respiratory sensor (r = 0.98, p < 0.0001 for heart rate; r = 0.84, p < 0.01 for respiratory rate). The exhaled CO and CO2, as a measure of trauma injury, were measured using an exhaled gas analyzer. The CO and CO2 concentrations were found to average 3.8 +/- 4.3 ppm and 2.9 +/- 0.4%, respectively. The expired air temperature and body temperature, as indicators of hemorrhagic hypothermia, averaged 31.8 +/- 1.7 degrees C and 36.2 +/- 0.4 degrees C, respectively. The results show that our system is promising for future prehospital application in determining casualty conditions for fluid infusions by the Casualty Care System intravenous lines.

Adult↗
PubMed2006

[Hepatic arterial infusion chemotherapy for advanced hepatocellular carcinoma providing a good QOL].

We report a case of advanced hepatocellular carcinoma (HCC). A 73-year-old man with positive HBV and HCV underwent a partial hepatectomy (S6 and S5) twice and transcatheter arterial (chemo) embolization (TAE) four times, thereafter. During these treatments, HCC became intractable and the patient complained of general fatigue. The liver function was Child's classification A, and serum AFP was 6,737 ng/ml. Abdominal CT scan revealed recurrent lesions in the right hepatic lobe and left adrenal gland. The catheter for hepatic arterial infusion chemotherapy was inserted from the left femoral artery. Arterial chemotherapy with 5-fluorouracil (5-FU 750 mg) and cisplatin (CDDP 10 mg) was performed every two weeks. During 6 courses of this regimen, a significant side effect did not appear. Abdominal CT revealed no change in size, but serum AFP decreased up to 794 ng/ml and the general fatigue subsided. After 2 months, serum AFP began to increase and became 1454 ng/ml. The regimen of arterial chemotherapy was changed to epirubicin (EPI 40 mg every two weeks) and UFT-E (300 mg/day for four weeks), followed by a week off. An appetite loss (grade 2) appeared, but it could be well controlled. Serum AFP decreased again, up to 54 ng/ml. A good QOL was kept for about one year after the initiation of hepatic arterial infusion chemotherapy.

Aged↗
PubMed2005

Highly blue luminescent triazine-amine conjugated oligomers.

[Reaction: see text]. The novel synthetic strategy and optical properties of highly fluorescent, triazine-amine conjugated oligomers are described herein. Under basic conditions, aromatic dinitrile compounds, NC-C6H4-X-C6H4-CN (X = NMe, O, CH2), underwent cyclic trimerization of the cyano groups at both ends to give a series of triazine-containing oligomers. The oligomers can be expressed as (2n + 1) mer, where n represents the number of triazine rings in the oligomer. The absorption maximum of an amine-conjugated trimer (X = NMe, n = 1) was outstandingly red-shifted as compared with those of the other trimers (X = CH2, O). In acidic media, the amine-conjugated trimer showed two-step bathochromic shifts caused by protonation. The absorption maxima of the amine-conjugated (2n + 1) mers (X = NMe, n = 1-4) did not depend on n; instead, shoulder peaks appeared in the long-wavelength region when n 2. The oligomers involving alternate conjugation of triazines and NMe groups through phenylene groups showed strong fluorescence in chloroform. In particular, the pentamer was the most efficient blue emitter (PhiF = 0.82). The other triazine-containing oligomers (X = CH2, O) did not show fluorescence at all. Therefore, it is concluded that the emission properties are due to the strong electron-donating and accepting abilities of the NMe and triazine moieties, respectively.

Journal Article↗
PubMed2005

Room-temperature and solution-state observation of the mixed-valence cation radical dimer of tetrathiafulvalene, [(TTF)2]+*, within a self-assembled cage.

A mixed-valence state of the cation radical tetrathiafulvalene dimer, [(TTF)2]+*, is generated by the electrochemical oxidation of a stacked TTF dimer accommodated within an organic-pillared coordination cage. This mixed-valence species is remarkably stable (t1/2 = approximately 1 day at room temperature in aqueous solution under air) and clearly characterized by cyclic voltammogram and electronic absorption spectroscopy.

Journal Article↗