Regioselective Synthesis of 6-O-Acetyl Dieckol and Its Selective Cytotoxicity against Non-Small-Cell Lung Cancer Cells.

Dieckol, a phlorotannin from Ecklonia cava, has shown potential for use as an anticancer agent that selectively kills cancer cells. However, it is necessary to amplify its potency without damaging its inherent safety in order to develop it as a competitive chemotherapeutic. Here, we explored the controlled O-acylations of dieckol. Acyl groups could be consistently introduced to the 6-O position of dieckol with a high regioselectivity, which was confirmed by NOESY, HMBC and HSQC spectroscopies. In cytotoxicity studies on the newly synthesized 6-O-acetyl, 6-O-benzoyl dieckols and previously synthesized 6-O-alkyl dieckols against A549 vs. normal cells, all of the derivatives showed low cytotoxicity in normal cells with an IC50 of 481-719 µM, and highly structure-dependent cytotoxicity in A549 cells with an IC50 of 7.02 (acetyl)-842.26 (benzyl) µM. The selectivity index also showed a large structure dependency in the range of 0.67 (benzyl)-68.58 (acetyl). An analysis of the structure-activity relationship indicated that the activity was dramatically reduced in the presence of a benzene ring and was highly increased in the presence of small polar substituents. Conclusions: Controlled mono-O-modifications of dieckol could be a powerful tool to enhance the anticancer activity of dieckol, thus contributing to the development strategy for dieckol-based chemotherapeutics.

In Vitro Osteogenic Differentiation and Antibacterial Potentials of Chalcone Derivatives.

Chalcone derivatives have been investigated as therapeutic agents for the anticancer, antioxidant, and anti-inflammatory fields. In this study, we have synthesized four different types of chalcone derivatives and demonstrated in vitro bioactivities. We divided these derivatives into two groups of chalcones on the basis of similar substituents on the aromatic rings, and we tested cell viability and proliferation potentials, which indicated that the methoxy substituent on the A ring could enhance cytotoxicity and antiproliferation potential depending on the chalcone concentration. We also investigated osteogenic differentiation of C2C12 cells by ALP staining, the early marker for osteogenesis, which demonstrated that the chalcones could not only induce activity of BMP-2 but also inhibit the activity of noggin, a BMP antagonist. In addition, chalcone bearing hydroxyl groups at the 2-, 4-, and 6-position on the A ring inhibited treptococcus mutans growth, a major causative agent of dental caries. Therefore, we concluded that the chalcone derivatives synthesized in this research can be good candidates for therapeutic agents promoting bone differentiation, with an expectation of inhibiting S. mutans, in dentistry.

The effect of trunk stabilization circuit exercise using a rubber mat on the thickness and white area index of transverse abdominis in healthy young adults.

[Purpose] The purpose of this study was to investigate the effect of trunk stabilization circuit exercise using a rubber mat on the thickness and white area index of the transverse abdominis in college students in their 20's. [Subjects and Methods] The subjects were randomly assigned to the experimental group and the control group. Those exercises were provided to twenty eight healthy adults in their 20s for four weeks and the thickness of transverse abdominis was measured before study and after 4 weeks. [Results] There were significant differences in interaction between two groups. Paired t-test for thickness and white area index of transverse abdominis showed statistically significant differences to experimentals than controls. Independent t-test for white area index of transverse abdominis also showed statistically significant differences to experimentals than controls. [Conclusion] In conclusion, there was statistically significant difference between the effects of trunk stabilization circuit exercises on back muscles according to types of the surface, and it is expected that this result will be used as a basic data in studies of abdominal muscle stabilization in the future.

Impact of wearing a functional foot orthotic on the ankle joint angle of frontal surface of young adults with flatfoot.

[Purpose] This study investigated the effects of proprietary foot orthotics in young adults with flatfoot to determine changes in the ankle joint angle in the coronal plane during the midstance phase. [Subjects and Methods] The subjects were 15 college students diagnosed with flatfoot. Changes in the ankle joint angle in the coronal plane in the midstance phase were measured using the Vicon Motion System before and after use of the orthotic. The data were analyzed using Statistical Package for the Social Sciences Win 16.0. [Results] The subjects showed significant increases in left and right ankle joint angles in the coronal plane during the midstance phase of the gait cycle after use of the orthotics. However, the difference between the left and right ankle joint angles showed no significant change, even though the difference increased after use of the orthotics. [Conclusion] Young adults with flatfoot showed increased ankle joint angles after use of the orthotics. This suggests that orthotic footwear can shape the plantar arch and affect the ankle joint, and that constant use of orthotics would cause a dynamic change in normal walking.

Effects of wearing functional foot orthotic on pelvic angle among college students in their 20s with flatfoot.

[Purpose] This study examined the impact of wearing a functional foot orthotic on the pelvic angle of young adults who have flatfoot. [Subjects and Methods] A total of 15 college students diagnosed with flatfoot were included in the study. Changes in the pelvic angle in the stance period during walking before and after orthotic use were measured using a VICON Motion System (VICON, Hansung, Korea). The data were analyzed using SPSS 12.0 for Windows. [Results] In the experimental group, the pelvic angle during the mid-stance and mid-swing periods of the gait cycle significantly decreased on the left and right sides after wearing the orthotic, compared to the measurements taken before orthotic usage. The pelvic angle change on the left and right sides also decreased after wearing the orthotic, though this difference was not significant. [Conclusion] The pelvic angle of college students with flatfoot decreased after they wore orthotics. This implies that wearing orthotic shoes can greatly benefit individuals during normal walking by promoting passive changes that decrease the pelvic angle.

The effects of inspiratory diaphragm breathing exercise and expiratory pursed-lip breathing exercise on chronic stroke patients' respiratory muscle activation.

[Purpose] The purpose of this study is to examine the effects of inspiratory diaphragm breathing exercise and expiratory pursed-lip breathing exercise on chronic stroke patients' respiratory muscle activation. [Subjects and Methods] All experimental subjects performed exercises five times per week for four weeks. Thirty chronic stroke patients were randomly assign to an experimental group of 15 patients and a control group of 15 patients. The experimental group underwent exercises consisting of basic exercise treatment for 15 minutes and inspiratory diaphragm breathing exercise and expiratory pursed-lip breathing exercise for 15 minutes and the control group underwent exercises consisting of basic exercise treatment for 15 minutes and auto-med exercise for 15 minutes. The activation levels of respiratory muscles were measured before and after the experiment using MP 150WSW to obtain the results of the experiment. [Results] In the present study, when the pulmonary functions of the experimental group and the control group before and after the experiment were compared, whereas the experimental group showed significant differences in all sections. In the verification of intergroup differences between the experimental group and the control group before and after the experiment. [Conclusion] The respiratory rehabilitation exercise is considered to be capable of inducing positive effects on stroke patients' respiratory muscles through diaphragm breathing exercise and lip puckering breathing exercise.

Electronic Activation of a DNA Nanodevice Using a Multilayer Nanofilm.

A method to control activation of a DNA nanodevice by supplying a complementary DNA (cDNA) strand from an electro-responsive nanoplatform is reported. To develop functional nanoplatform, hexalayer nanofilm is precisely designed by layer-by-layer assembly technique based on electrostatic interaction with four kinds of materials: Hydrolyzed poly(ß-amino ester) can help cDNA release from the film. A cDNA is used as a key building block to activate DNA nanodevice. Reduced graphene oxides (rGOs) and the conductive polymer provide conductivity. In particular, rGOs efficiently incorporate a cDNA in the film via several interactions and act as a barrier. Depending on the types of applied electronic stimuli (reductive and oxidative potentials), a cDNA released from the electrode can quantitatively control the activation of DNA nanodevice. From this report, a new system is successfully demonstrated to precisely control DNA release on demand. By applying more advanced form of DNA-based nanodevices into multilayer system, the electro-responsive nanoplatform will expand the availability of DNA nanotechnology allowing its improved application in areas such as diagnosis, biosensing, bioimaging, and drug delivery.

Effects of diaphragm respiration exercise on pulmonary function of male smokers in their twenties.

[Purpose] We investigated how diaphragm respiration exercises can affect pulmonary function in long-term male smokers in their twenties. [Subjects and Methods] Twenty-eight healthy males between 20 and 29 years of age were randomly divided into an experimental and a control group (14 members each). The experiment was conducted during 30 min sessions, 3 times a week for 4 weeks. The experimental group performed diaphragm respiration exercises and the control group performed exercises using MOTOmed. Pulmonary function (tidal volume, breathing capacity, inspiratory reserve volume, inspiratory capacity, and expiratory reserve volume) was evaluated and analyzed before and after the experiment. [Results] Our results revealed significant increases in tidal volume, inspiratory reserve volume, inspiratory capacity, and breathing capacity in the experimental group. These increases were greater in the experimental group than in the control group. [Conclusion] In our study, the experimental group which performed diaphragm respiration exercises showed a greater improvement in pulmonary function compared with the control group. It is hypothesized that greater improvement in pulmonary function is expected if diaphragm respiration exercises are implemented taking into account the age of the smokers.

The effects of stair gait training using proprioceptive neuromuscular facilitation on stroke patients' dynamic balance ability.

[Purpose] This study aims to examine stroke patients' changes in dynamic balance ability through stair gait training where in proprioceptive neuromuscular facilitation (PNF) was applied. [Subjects and Methods] In total 30 stroke patients participated in this experiment and were randomly and equally allocated to an experimental group and a control group. The experimental group received exercise treatment for 30 min and stair gait training where in PNF was applied for 30 min and the control group received exercise treatment for 30 min and ground gait training where in PNF was applied for 30 min. For the four weeks of the experiment, each group received training three times per week, for 30 min each time. Berg Balance Scale (BBS) values were measured and a time up and go (TUG) test and a functional reach test (FRT) were performed for a comparison before and after the experiment. [Results] According to the result of the stroke patients' balance performance through stair gait training, the BBS and FRT results significantly increased and the TUG test result significantly decreased in the experimental group. On the contrary, BBS and FRT results did not significantly increase and the TUG test result did not significantly decrease in the control group. According to the result of comparing differences between before and after training in each group, there was a significant change in the BBS result of the experimental group only. [Conclusions] In conclusion, the gait training group to which PNF was applied saw improvements in their balance ability, and a good result is expected when neurological disease patients receive stair gait training applying PNF.

Effects of a functional foot orthosis on the knee angle in the sagittal plane of college students in their 20s with flatfoot.

[Purpose] The purpose of this study was to examine the effects of a functional foot orthosis on the knee angle in the sagittal plane of college students in their 20s who had flatfoot. [Subjects and Methods] The subjects of this study were 20 college students diagnosed as having flatfoot. The variations of their knee angle (Q-angle) in the sagittal plane during the stance phase were measured using the VICON Motion System (Vicon, Hansung, Korea) before and while wearing a foot orthosis. The experimental data were analyzed using SPSS 12.0 for Windows. [Results] The Q-angle in the test group during the stance phase showed statistically significant declines on the right and left sides while wearing the foot orthosis during the gait-phases of loading response and midstance. During initial contact, terminal stance, and preswing, the Q-angle also decreased on the right and left sides after wearing the foot orthosis, but the changes were not statistically significant. [Conclusion] The college students with flatfoot exhibited declines in the Q-angle in the sagittal plane while wearing a foot orthosis. In this regard, the application of active gait training using orthotic shoes for long hours is likely to help individuals with flatfoot to achieve normal gait.

The Effects on the Pain Index and Lumbar Flexibility of Obese Patients with Low Back Pain after PNF Scapular and PNF Pelvic Patterns.

[Purpose] The purpose of this study was to determine whether exercises using proprioceptive neuromuscular facilitation (PNF) scapular and pelvic patterns might decrease the pain index and increase the lumbar flexibility of obese patients with low back pain. [Subjects and Methods] Thirty obese patients with low back pain were randomly assigned to an experimetal group (n=15) and a control group (n=15). The exercise program of the experimental group consisted of scapular patterns (anterior depression - posterior elevation) and pelvic patterns (anterior elevation - posterior depression). The control group performed neutral back muscle strengthening exercises. Over the course of four weeks, the groups participated in PNF or performed strengthening exercises for 30 minutes, three times per week. Subjects were assessed a pre-test and post-test using measurements of pain and lumbar flexibility. [Results] The results show that lumbar flexion and lumbar extension significantly improved in the experimental group, had significant improvement and that the Oswestry Disability index (ODI) significantly decreased. However, there were no significant changes in the control group. The experimental group also showed significant differences in the pain index and lumbar flexibility from the control group. [Conclusion] This study showed that PNF can be used to improve pain index rating and lumbar flexibility. The findings indicate that the experimental group experienced greater improvement than the control group by participating in the PNF lumbar stabilization program.

Parallel and combinatorial liquid-phase synthesis of alkylbiphenyls using pentaerythritol support.

Unfunctionalized alkylbiphenyls were fabricated by a parallel and combinatorial synthesis using pentaerythritol as a tetrapodal soluble support for a sulfonate-based traceless multifunctional linker system. Nickel N-heterocyclic carbene-catalyzed reactions of pentaerythritol tetrakis(biphenylsulfonate)s with primary alkylmagnesium bromides generated the alkylbiphenyl derivatives by desulfitative cleavage/cross-coupling of the C-S bond without any "memory" of the attachment on the support. Though the reactions were completed with sufficient yields in 12 h at room temperature, even with only 1.5 equiv of nucleophiles, they still retained the benefits of facile isolation observed in polymer-supported reactions.

Solid-phase synthesis of unsymmetrical trans-stilbenes.

A small library of fluorescent and unsymmetrical trans-stilbene compounds was efficiently produced by a solid-phase synthetic approach using the sulfonate-based traceless linker system. Nickel(0)-catalyzed cleavage/cross-coupling of polymer-bound stilbenesulfonates with aryl Grignard reagents generated the desired trans-stilbenes at high yield by the multifunctional release facilitating the additional diversification of the library. The luminescent properties of trans-stilbenes are assessed, and the influence of alkyl substituents on their photophysical properties is discussed.

Nickel N-heterocyclic carbene catalyst for cross-coupling of neopentyl arenesulfonates with methyl and primary alkyl grignard reagents.

Nickel N-heterocyclic carbene (NHC) catalytic system prepared in situ by the reaction of Ni(acac)(2) with NHC precursor efficiently catalyzed the cross-coupling reaction of alkoxysulfonylarenes with methyl, neopentyl, and benzyl Grignard reagents at ambient temperature.

Manganese peroxidase-catalyzed oxidative degradation of vanillylacetone.

When 4-(4-hydroxy-3-methoxy-phenyl)-2-butanone (vanillylacetone) was tested for manganese peroxidase (MnP)-catalyzed oxidation, it was found to be degraded with the cleavage of an aromatic ring. Among numerous products of vanillylacetone oxidation, four major ones were purified by thin-layer chromatography and identified using mass spectroscopy (MS) and nuclear magnetic resonance (NMR) analysis. Three of them maintained the aromatic ring structure and were identified as 4-[6,2'-dihydroxy-5,3'-dimethoxy-5'-(3-oxo-butyl)-biphenyl]-butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one, and 4-[6,2'-dihydroxy-5,3'-dimethoxy-5'-(3-oxo-butyl)-biphenyl]-3-buten-2-one. Even though the fourth product could not be purified to a single compound, data from infrared spectroscopy showed that it did not have a benzene ring. From MS and NMR analysis, 3-(3-oxo-butyl)-hexa-2,4-dienedioic acid-1-methyl ester was tentatively suggested as the dominant species. The reaction mechanism was suggested on the basis of the structural information of these products. To our knowledge, this paper is the first report on aromatic ring cleavage of the phenolic compound by MnP.

(E)-1-(4-Bromo-phen-yl)-2-(4-tert-butyl-phen-yl)-1-phenyl-ethene.

In the structure of the title compound, C(24)H(23)Br, the configuration about the double bond is E. The dihedral angles between the tert-butyl-substituted benzene ring and the unsubstituted and Br-substituted rings are 57.1 (2) and 78.2 (2)°, respectively. The methyl groups are disordered over two positions; the site occupancy factors are ca 0.8 and 0.2.

Traceless liquid-phase synthesis of biphenyls and terphenyls using pentaerythritol as a tetrapodal soluble support.

Application of a novel sulfonate-based traceless multifunctional linker system using pentaerythritol as a tetrapodal soluble support was demonstrated using liquid-phase parallel and combinatorial preparation of biphenyl and terphenyl compounds. Nickel-catalyzed reactions of pentaerythritol tetrakis(arenesulfonate)s with arylmagnesium bromides generated the desired products in sufficient yields through reductive cleavage/cross-coupling of the C-S bond. Homogeneous pentaerythritol-supported reactions could be accomplished using less nucleophile with shorter reaction periods than could the corresponding heterogeneous polymer-supported reactions. This liquid-phase approach using a small polyfunctionalized support combines advantages of solution-phase and solid-phase syntheses by allowing high reactivity, high atom economy, simple isolation, and real-time monitoring of the reaction progress.

Nickel-catalyzed cross-coupling of neopentyl arenesulfonates with methyl and primary alkylmagnesium bromides.

[reaction: see text] Neopentyl arenesulfonates were reacted with methyl and primary alkylmagnesium bromides in the presence of dppeNiCl(2), via the nucleophilic aromatic substitution of neopentyloxysulfonyl groups by the primary alkyl nucleophiles, to produce the corresponding alkylarenes in good yields. This result shows that the alkyloxysulfonyl group might be a suitable alternative to halides and triflate in some circumstances.

Nickel 0-catalyzed cross-coupling of alkyl arenesulfonates with aryl Grignard reagents.

The nickel-catalyzed cross-coupling reactions of neopentyl arenesulfonates with arylmagnesium bromides, involving nucleophilic aromatic substitution of alkyloxysulfonyl groups by aryl nucleophiles, take place in high yields. Optimal efficiencies are obtained by adding 3 + 2 equiv of the Grignard reagent to a mixture of dppfNiCl(2) and the sulfonate in refluxing THF. Neopentyl arenesulfonates are useful sources of the electrophilic aryl groups in these transition metal-catalyzed cross-coupling reactions. Aryl sulfonates are inappropriate due to their ambident reactivity under the reaction conditions. This new cross-coupling reaction can be used for the creative elimination of alkyloxysulfonyl groups from aromatic compounds and for the preparation of unsymmetric terphenyls and oligophenyls.