A macrocage molecule with a bridged phenylene rotor has been reported as a molecular gyrotop, because the rotor can rotate even in a crystalline state. Although the most stable cage structure of the molecular gyrotop in a crystal was folded and shrunken at low temperature, expansion of the cage was observed at high temperature due to rapid rotation of the phenylene in a crystal. This phenomenon is analogous to the deflation and inflation of a balloon. Moreover, the unusually large thermal expansion coefficient of the crystal was estimated in the temperature range in which the expansion of the cage was observed, indicating a new function of dynamic states of the molecules.

A novel organobismuth compound, 1-[(2-di-p-tolylbismuthanophenyl)diazenyl]pyrrolidine (4), which has 1-(phenyldiazenyl)pyrrolidine (1) substituent in a benzene ring of tri(p-tolyl)bismuthane (2), was synthesized and tested for biological activity toward human tumor cell lines. 4 had a potent anti-proliferative effect on human cancer cell lines, although both 1 and 2 exhibited only weak activity. The sensitivity of leukemic cell lines to 4 was relatively high; IC50 values for the human leukemia cell line NB4 and cervical cancer cell line HeLa were 0.88 μM and 5.36 μM, respectively. Treatment of NB4 cells with 4 induced apoptosis, loss of mitochondrial membrane potential (ΔΨmt) and the generation of cellular reactive oxygen species (ROS). 1 and 2 did not induce apoptosis and had only a marginal effect on ΔΨmt and the generation of ROS. N-acetyl cysteine (NAC) reduced the generation of ROS and conferred protection against 4-induced apoptosis, indicating a role for oxidative stress. 4 did not inhibit the polymerization of tubulin in vitro. 1-[2-(di-p-tolylstibanophenyl)diazenyl]pyrrolidine (3), which has the same chemical structure as 4 but contains antimony in place of bismuth, did not show any cytotoxic activity. The results suggest that the conjugated structure of the diazenylpyrrolidine moiety and bismuth center are key to the bioactivity of 4.A novel 1-[(2-di-p-tolylbismuthanophenyl)diazenyl]pyrrolidine(4), which has 1-(phenyldiazenyl)pyrrolidine substituent in a benzene ring of tri(p-tolyl)bismuthane, was synthesized and tested for biological activity toward human tumor cell lines.4 exhibited strong anti-leukemia activity in vitro via reactive oxygen species.Unexpectedly, 1-[(2-di-p-tolylstibanophenyl)diazenyl]pyrrolidine, the compound containing antimony in place of bismuth, showed no cytotoxic activity.Highlights► A novel organobismuth exhibited anti-leukemia activity via reactive oxygen species. ► Compound containing antimony in place of bismuth showed no cytotoxic activity. ► Diazenylpyrrolidine moiety and bismuth center are key to the bioactivity.

We have designed new cleavable cross-linkers for biomolecules containing the 2,6-bis(oxazolinyl)pyridine (pybox) lanthanum complex. These species can effectively donate multiple charges to afford cross-linker ions for target biomolecules. The cross-linkers are cleaved easily by adding water. Moreover, we were able to detect chain structures of target molecules, including biomolecules and carbon clusters, such as fullerene C60, by the addition of some MS ionic probes. Cold-spray ionization mass spectrometry demonstrated the applications of multiply charged ionic probes as cleavable cross-linkers and polymerization reagents.

Recently, functional organic materials have been put into practical use. The application of molecular motions has the potential to create new molecule-based materials. For this reason, considerable attention has been focused on the chemistry and properties of molecular machines in which mechanical motions of parts of the molecules are observed. In particular, phenylene rotation in the crystalline state has been investigated using framed molecular gyrotops having a phenylene rotor encased in three long alkyl spokes. In this study, we show thermal modulation of birefringence in a crystal due to the states of dynamic equilibrium of a novel molecular gyrotop. A macrocage molecule having a bridged phenylene rotor was synthesized as a novel molecular gyrotop. Rapid rotation of the phenylene rotor of the molecular gyrotop was confirmed by solid-state 2H NMR spectroscopy that showed changes in the optical properties of a single crystal, i.e., the thermal modulation of birefringence. These results are the first application of the dynamic states in a crystal causing an optical change. These phenomena were also confirmed by control experiments using a molecular gyrotop with a nonrotating xylene rotor. We anticipate our finding to be a starting point for the creation of a new field of material chemistry that will make use of the dynamic states of molecules.

An ionization method that uses metal-complex-based ionization probes, malonic acid 3-[2,6-bis(4,4-dimethyloxazolin-2-yl)pyridin-4-yloxy]propyl ethyl ester (EM-TMpybox) and potassium N-{3-[2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine-4-yloxy]propyl} aminoacetate (Sar-TMpybox), was developed for isotope ratio analysis and the effective ionization of unsubstituted carbon clusters. The preparation of Sar-TMpybox and EM-TMpybox and their applications in cold-spray ionization mass spectrometry are reported. A probe applicable to a substituted fullerene is also demonstrated.

An effective La-complex-based probe ionization method is reported. Novel stable isotopically labeled probes containing the 15N-labeled 2,6-bis(oxazolin-2-yl)pyridine (pybox) ligand, succinimide-tetramethylpybox (NHS-TMpybox), maleimide-tetramethylpybox (Mal-TMpybox), and 4-(tetramethylpybox)-butyl bromoacetate (BrAc-TMpybox), have been synthesized and their value in analyzing large complex molecules has been studied. The value of the 15N-labeled pybox-La complex in ionizing various compounds, including bioactive peptides by cold-spray ionization mass spectrometry is emphasized.

An ionization method that uses metal-complex-based ionization probes, malonic acid 3-[2,6-bis(4,4-dimethyloxazolin-2-yl)pyridin-4-yloxy]propyl ethyl ester (EM-TMpybox) and potassium N-{3-[2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine-4-yloxy]propyl} aminoacetate (Sar-TMpybox), was developed for isotope ratio analysis and the effective ionization of unsubstituted carbon clusters. The preparation of Sar-TMpybox and EM-TMpybox and their applications in cold-spray ionization mass spectrometry are reported. A probe applicable to a substituted fullerene is also demonstrated.

An effective La-complex-based probe ionization method is reported. Novel stable isotopically labeled probes containing the 15N-labeled 2,6-bis(oxazolin-2-yl)pyridine (pybox) ligand, succinimide-tetramethylpybox (NHS-TMpybox), maleimide-tetramethylpybox (Mal-TMpybox), and 4-(tetramethylpybox)-butyl bromoacetate (BrAc-TMpybox), have been synthesized and their value in analyzing large complex molecules has been studied. The value of the 15N-labeled pybox-La complex in ionizing various compounds, including bioactive peptides by cold-spray ionization mass spectrometry is emphasized.