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1.
Adv Ther ; 40(11): 4907-4918, 2023 11.
Article in English | MEDLINE | ID: mdl-37707675

ABSTRACT

INTRODUCTION: To report eyedrop instillation techniques and factors associated with instillation failure among glaucoma subjects in the Video-Recorded Assessment of Medication Skill and Questionnaire-based evaluation of Perception in Glaucoma Study. METHODS: In this cross-sectional observational study, subjects were 60 patients with glaucoma (mean ± standard deviation age, 68.4 ± 11.3 years; 30 men) who required ocular hypotensive medication(s). Subjects completed ophthalmologic examinations and the Mini-Cog cognitive function test; their typical eyedrop instillation technique was video-recorded. Subjects rated their technique as successes/failures by questionnaire and two examiners rated the successes/failures based on video assessment. Discrepancy between self-reported and video-assessed success/failure rates of instillation was the main outcome measures. Multivariate logistic regression identified factors in instillation failure. RESULTS: Of 48/56 (86%) self-reported successes, 27/48 (56%) failed based on video assessment; as a result, 32/56 (57%) were inconsistent between subjective and objective assessments. Overall, 30/56 (54%) failed based on video assessment. In the subject-based data model, older age [odds ratio (OR) 0.93/year, P = 0.025] and lower cognitive function score (OR 2.7/score, P = 0.025) were factors in failed instillations. In the eye-based data model, less myopic objective refractive error (OR 0.77/diopter, P = 0.016) and lower visual field foveal threshold (OR 1.1/decibel, P = 0.041) were factors in failures. CONCLUSION: In addition to older age, decreased cognitive function, hyperopia, and decreased foveal sensitivity are risks for failed eyedrop instillation. Treating physicians can screen patients who require guidance by checking the risk factors of instillation failure rather than by relying on patient reports.


Subject(s)
Glaucoma , Aged , Humans , Male , Middle Aged , Antihypertensive Agents/therapeutic use , Cross-Sectional Studies , Glaucoma/drug therapy , Intraocular Pressure , Medication Adherence , Ophthalmic Solutions/therapeutic use , Surveys and Questionnaires , Female
2.
Environ Res ; 160: 232-238, 2018 01.
Article in English | MEDLINE | ID: mdl-29028487

ABSTRACT

Ziram, a dithiocarbamate fungicide, protects various vegetables and fruits against infections by fungus. Recently, there have been increasing anxieties about the risks in the use of dithiocarbamate fungicides. Our previous studies showed that Zn2+ was a determinant of Ziram cytotoxicity. In addition, Zn2+ is linked to H2O2 cytotoxicity. Therefore, in this study, we aimed to test the hypothesis that Ziram could augment the cytotoxicity of H2O2 by examining the changes induced by Ziram in some cellular parameters in rat thymic lymphocytes subjected to H2O2-induced oxidative stress using flow-cytometric methods with fluorescent dyes. Ziram significantly attenuated H2O2-induced cell death at sublethal concentrations. However, in the cells under oxidative stress elicited by H2O2, Ziram promoted the changing over from intact cells to living cells with exposed phosphatidylserine (PS) on plasma membranes, whereas it inhibited the transition from PS-exposed living cells to dead cells. Ziram significantly augmented H2O2 actions, including reduction of cellular glutathione levels and elevation of intracellular Zn2+ concentrations. Conversely, it attenuated H2O2-induced depolarization of mitochondrial membrane potential. Ziram at sublethal concentrations seems to exhibit promotive and suppressive actions on the process of cell death caused by H2O2. Ziram increased the number of living cells with exposed PS, a phenomenon characteristic of early stages of apoptosis. Thus, it is concluded that Ziram exhibits pseudo-cytoprotective actions against H2O2-induced oxidative stress. Ziram at sublethal concentrations exerts promotive and suppressive actions on the process of cell death caused by oxidative stress.


Subject(s)
Fungicides, Industrial/toxicity , Oxidative Stress/drug effects , Thymocytes/drug effects , Ziram/toxicity , Animals , Calcium/metabolism , Hydrogen Peroxide , Primary Cell Culture , Rats , Sulfhydryl Compounds/metabolism , Thymocytes/metabolism , Zinc/metabolism
3.
Toxicol Res (Camb) ; 6(4): 499-504, 2017 Jul 01.
Article in English | MEDLINE | ID: mdl-30090518

ABSTRACT

Ziram, one of the dithiocarbamate fungicides, is widely applied to agriculture because this agent protects various crops from fungal infections. Risks of dithiocarbamate biocide use are of concern. It was previously reported that Ziram increased the intracellular concentration of Zn2+. Therefore, we cytometrically studied the mechanism of Zn2+-dependent lethal actions of Ziram on rat lymphocytes at environmentally relevant Zn2+ levels. Membrane and cellular parameters of rat lymphocytes were estimated by flow-cytometric techniques with appropriate fluorescent probes. The Ziram-induced increase in cell lethality was completely attenuated by Zn2+ chelators. A significant increase of cell lethality was found on the simultaneous application of Ziram at a sublethal concentration and ZnCl2. The combination of Ziram and ZnCl2 increased the cellular superoxide anion content and decreased the cellular GSH content, which possibly caused the increase in cell lethality. The zinc concentrations under the present experimental conditions were comparable to the environmentally relevant concentrations found in rivers. Therefore, the environmental level of zinc may be critical in estimating the toxicity of Ziram to wild animals.

4.
Dalton Trans ; 44(41): 18276-83, 2015 Nov 07.
Article in English | MEDLINE | ID: mdl-26435181

ABSTRACT

Four isostructural LnZn2 trinuclear complexes, [Ln(NO3){Zn(L)(SCN)}2] (H2L is a Schiff base ligand derived from o-vanillin and ethylenediamine), were synthesized, which include light lanthanide ions as spin carriers (Ln = Ce 1, Pr 2, Nd 3, and Sm 4). These complexes involve a linear Zn(ii)-Ln(iii)-Zn(ii) array, which leads to an axially stressed ligand field and can also cause single-moleluce magnet (SMM) behavior in oblate-type electronic distributions of ground sublevels found in Ce(iii), Pr(iii), and Nd(iii). Slow magnetic relaxation behavior was observed in 1 and 3 under an applied bias dc field of 1000 Oe, whereas such a slow relaxation was not observed in 2 and 4. The appearance of field-induced SMM behavior in 1 and 3 was correlated with the even-numbered Jz sublevels of Ce(iii) and Nd(iii) ions known as the Kramers system.


Subject(s)
Coordination Complexes/chemistry , Lanthanoid Series Elements/chemistry , Magnets/chemistry , Zinc/chemistry , Benzaldehydes/chemistry , Crystallography, X-Ray , Ethylenediamines/chemistry , Models, Molecular , Schiff Bases/chemistry
5.
Dalton Trans ; 44(41): 18038-48, 2015 Nov 07.
Article in English | MEDLINE | ID: mdl-26411298

ABSTRACT

Five LnZn2 trinuclear complexes, [Ln(NO3){Zn(L)(SCN)}2] (H2L is a Schiff base ligand derived from o-vanillin and ethylenediamine; Ln = Tb 1, Dy 2, La 3, Tb0.14La0.864, and Dy0.21La0.795), were synthesised in which the Zn(II)-Ln(III)-Zn(II) array exhibits two slightly different arrangements: 1 and 2 exhibited slightly bent arrangements, whereas 3-5 exhibited more linear arrangements. These differences in the arrangements lead to a slightly different coordination geometry around Ln(III). From the detailed studies of dynamic susceptibility, 1 and 2 were found to be paramagnetic, whereas 4 and 5 were SMMs with barriers for the flipping of magnetisation with a height of 41.2(4) K and 156(4) K, respectively.

6.
Chem Biol Interact ; 237: 80-6, 2015 Jul 25.
Article in English | MEDLINE | ID: mdl-26026913

ABSTRACT

Dithiocarbamate fungicides are used as alternative antifouling agents to highly toxic organotin antifouling agents, such as tri-n-butyltin and triphenyltin. There are some concerns regarding their environmental and health risks. It has been shown that tri-n-butyltin increases intracellular Zn(2+) levels of mammalian lymphocytes. Therefore, we examined the effects of dithiocarbamate fungicides (Ziram, Thiram, and Zineb) on rat thymic lymphocytes using a flow-cytometric technique to elucidate how these fungicides affect intracellular Zn(2+) levels. We further determined whether the agents increase intracellular Zn(2+) and/or Ca(2+), because both Zn(2+) and Ca(2+) are intracellular signals in lymphocytes, and excessive increases in their intracellular concentrations can have adverse effects. Dithiocarbamate fungicides increased intracellular Zn(2+) levels, without affecting intracellular Ca(2+) levels. Ziram was the most potent compound, increasing intracellular Zn(2+) levels via Zn(2+) influx. Ziram (1µM) greatly decreased the cellular nonprotein thiol content, and Zn(2+) chelators attenuated the Ziram-induced decrease. Ziram increased the population of annexin V-positive cells in a Zn(2+)-dependent manner. Therefore, we propose that dithiocarbamate fungicides induce Zn(2+) influx, resulting in an excessive elevation of intracellular Zn(2+) levels, leading to the induction of apoptosis. This study gives a basic insight into the mechanisms of dithiocarbamate fungicide-induced adverse events.


Subject(s)
Fungicides, Industrial/pharmacology , Lymphocytes/drug effects , Thymus Gland/drug effects , Zinc/metabolism , Ziram/pharmacology , Animals , Apoptosis/drug effects , Fluorescence , Ion Transport , Lymphocytes/metabolism , Rats , Thymus Gland/cytology , Thymus Gland/metabolism
7.
Int J Biometeorol ; 58(5): 999-1005, 2014 Jul.
Article in English | MEDLINE | ID: mdl-23756607

ABSTRACT

To reduce the risks of Japanese-style bathing, half-body bathing (HBLB) has been recommended in Japan, but discomfort due to the cold environment in winter prevents its widespread adoption. The development of the mist sauna, which causes a gradual core temperature rise with sufficient thermal comfort, has reduced the demerits of HBLB. We examined head-out 42 °C mist bathing with 38 °C HBLB up to the navel to see if it could improve thermal comfort without detracting from the merits of HBLB, with and without the effects of facial fanning (FF). The subjects were seven healthy males aged 22-25 years. The following bathing styles were provided: (1) HBLB-head-out half-body low bathing of 38 °C up to the navel (20 min); (2) HOMB-head-out mist bathing of 42 °C and HBLB of 38 °C (20 min); and (3) HOMBFF-HOMB with FF (20 min). HOMB raised the core temperature gradually. HOMBFF suppressed the core temperature rise in a similar fashion to HOMB. Increases in blood pressure and heart rate usually observed in Japanese traditional-style bathing were less marked in HOMBs with no significant difference with and without FF. The greatest body weight loss was observed after Japanese traditional-style bathing, with only one-third of this amount lost after mist bathing, and one-sixth after HBLB. HOMB increased thermal sensation, and FF also enhanced post-bathing invigoration. We conclude that HOMB reduces the risks of Japanese traditional style bathing by mitigating marked changes in the core temperature and hemodynamics, and FF provides thermal comfort and invigoration.


Subject(s)
Baths/methods , Body Temperature , Thermosensing , Adult , Blood Pressure , Head , Heart Rate , Humans , Japan , Male , Pilot Projects , Regional Blood Flow , Skin/blood supply , Steam Bath , Sweating , Urine , Water , Young Adult
8.
Dalton Trans ; 42(6): 1987-90, 2013 Feb 14.
Article in English | MEDLINE | ID: mdl-23283217

ABSTRACT

An assemblage of a Tb(III) ion and two mononuclear [Zn(II)(L)] complexes as antenna chromophores (H(2)L: Schiff base ligand) afforded a luminescent single-molecule magnet. The f-f emission spectrum had partially resolved fine structure which provides detailed information on the magnetic anisotropy of the (7)F(6) ground multiplet of the Tb(III) ion.

9.
Dalton Trans ; 42(8): 2683-6, 2013 Feb 28.
Article in English | MEDLINE | ID: mdl-23303168

ABSTRACT

Linear Zn(II)-Ce(III)-Zn(II) complex, which involves only one 4f electron as a spin source, behaves as an SMM. Easy-axis magnetic anisotropy for the ground (2)F(5/2) state of Ce(III) was achieved by a uni-axial crystal field, which is formed with four phenoxo oxygens as axial donors with the other five oxygens as equatorial donors.

10.
Dalton Trans ; 41(44): 13640-8, 2012 Nov 28.
Article in English | MEDLINE | ID: mdl-22898750

ABSTRACT

Six linear trinuclear [Ln{Zn(L)(AcO)}(2)]BPh(4) complexes (H(2)L denotes the Schiff-base ligand formed by a condensation reaction between ethylenediamine and two equivalents of o-vanillin), including Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5) and Yb (6) were synthesized and were confirmed to be isostructural via X-ray crystallographic analyses. The Ln(III) ion in each complex is deca-coordinated by four equatorial oxygen donors from the methoxo groups of the Schiff-base ligands, two oxygen donors from the acetate anions and four axial oxygen donors from the phenoxo groups of the Schiff-base ligands. AC susceptibility measurements, with an oscillating frequency of 10 to 10,000 Hz, revealed that 1, 2, 4 and 6 show slow magnetic relaxation under a 1000 Oe DC bias field, which occurs via a single process, as confirmed by the semi-circular Cole-Cole plots. These complexes are considered to be field-induced single-molecule magnets under these conditions. The presence or absence of the slow magnetic relaxation process is discussed by correlating the characteristic magnetic anisotropy of each Ln(III) ion with the ligand field anisotropy.

11.
Bioorg Med Chem Lett ; 22(16): 5218-21, 2012 Aug 15.
Article in English | MEDLINE | ID: mdl-22801645

ABSTRACT

Self-aggregates of a synthetic zinc porphyrin worked as a light absorber and photoexcited energy donor, transferred the collected energy to a small amount of 3-acetyl-(bacterio)chlorin monomer, and induced near-infrared fluorescence from the acceptors in aqueous micellar solution. These artificial supramolecular systems are novel models of the main light-harvesting antennas of green photosynthetic bacteria, chlorosomes.


Subject(s)
Bacteria/metabolism , Metalloporphyrins/chemistry , Porphyrins/chemistry , Energy Transfer , Light-Harvesting Protein Complexes/metabolism , Models, Biological , Porphyrins/metabolism , Spectrometry, Fluorescence
12.
Photosynth Res ; 111(1-2): 1-8, 2012 Mar.
Article in English | MEDLINE | ID: mdl-21253859

ABSTRACT

Methyl pheophorbide-a/a' derivatives covalently linked with oligomethylene chains at the 3-CH(2)OCO- and 13(2)-COO- moieties in a molecule were prepared by modifying chlorophyll-a through intramolecular ring-closing metathesis of vinyl groups. At least, a C10-length between the 3(3)- and 13(4)-positions was necessary for the cyclization and connection of a C12-strap was the most suitable to achieve the highest closure yield. The oligomethylene chain in 13(2) R-epimers derived from methyl pheophorbide-a covered the α-face of the chlorin π-plane and the strap in the corresponding 13(2) S-epimers protected the ß-face. Synthetic 13(2) R-epimer with a dodecamethylene chain gave a flat chlorin π-plane, while the decamethylene chain in the 13(2) R-epimer distorted the π-system due to its shorter linkage. The distortion by strapping in the 13(2) R-epimer induced a slight blue-shift of Qy peak in dichloromethane. CD spectra of the 13(2) R-epimers were similarly dependent on the chain length, i.e., the distortion of π-plane. Visible absorption and CD spectra of all the strapped 13(2) S-epimers were almost identical and only slightly different from those of the unstrapped. The strapping in the 13(2) S-epimers shifted the Qy peak bathochromically.


Subject(s)
Chlorophyll/analogs & derivatives , Spirulina/chemistry , Chlorophyll/chemical synthesis , Chlorophyll/chemistry , Chlorophyll A , Circular Dichroism , Models, Molecular , Molecular Conformation , Optics and Photonics , Solutions , Spectrophotometry, Atomic , Stereoisomerism
13.
Dev Growth Differ ; 51(9): 841-50, 2009 Dec.
Article in English | MEDLINE | ID: mdl-19951326

ABSTRACT

The acetylcholinesterase-encoding gene in the ascidian Ciona intestinalis (Ci-AChE) is expressed in tail muscle cells from the gastrula stage. When the embryo was continuously treated with aphidicolin from the 32-cell stage, Ci-AChE was not expressed even when control embryos reached the tailbud stage. This result suggests that Ci-AChE acquires the competence to be transcribed after passing through a certain number of DNA replication cycles. A lacZ reporter gene containing the 5' flanking region of Ci-AChE was expressed in the tail muscle cells. Aphidicolin treatment from the 32-cell stage affected, but did not completely suppress, the expression of lacZ. A bisulfite sequencing analysis was carried out to examine the methylation status of four regions within the 5' flanking sequence and the first exon. However, all of these regions remained unmethylated from the 16-cell to 110-cell stages. The results suggested that the DNA of the Ci-AChE locus is not responsible for counting the rounds of replication. We examined the expression of the C. intestinalis MyoD (Ci-MyoD), a transcription factor that activates Ci-AChE. Aphidicolin treatment from the 32-cell stage suppressed the expression of Ci-MyoD, even when control embryos reached the gastrula stage. These results suggest that a lack of Ci-MyoD is critical to the suppression of Ci-AChE in aphidicolin-treated embryos.


Subject(s)
Acetylcholinesterase/genetics , Ciona intestinalis/embryology , Ciona intestinalis/genetics , DNA Replication/physiology , Transcriptional Activation , Animals , Animals, Genetically Modified , Anti-Bacterial Agents/pharmacology , Aphidicolin/pharmacology , Azacitidine/analogs & derivatives , Azacitidine/pharmacology , Base Sequence , DNA Methylation , Decitabine , Embryo, Nonmammalian/drug effects , Embryo, Nonmammalian/metabolism , Models, Biological , Molecular Sequence Data , MyoD Protein/genetics , MyoD Protein/metabolism , Transcriptional Activation/genetics
14.
J Nanosci Nanotechnol ; 9(1): 655-7, 2009 Jan.
Article in English | MEDLINE | ID: mdl-19441364

ABSTRACT

Three kinds of protein-metal complexes were developed as pH sensing devices in the aqueous solutions. Biological transferrin and lactoferrin proteins formed stable Tb3+ complexes, which exhibited long-lived and green luminescence signals. They showed pH-dependent luminescence changes around neutral pH, coupled with their Tb3+ complexation/decomplexation. Since fluorescein-labeled transferrin-Fe3+ complex exhibited fluorescence changes at lower pH, these three protein complexes covered wide pH-responsive ranges. The immobilized biotinylated transferrin-Tb3+ complexes on the micrometer-scaled bead also operated as a pH-responsive luminescent indicator. Since the transferrin ligand had rapid Tb3+ complexation/decomplexation process, its Tb3+ complex exhibited pH-responsive luminescence signals even in the presence of Fe3+ cation. A new series of tunable luminescent pH sensing devices were developed by combination of biological protein and luminescent lanthanide center.

15.
Dalton Trans ; (30): 4038-43, 2008 Aug 14.
Article in English | MEDLINE | ID: mdl-18648708

ABSTRACT

A series of oligopyridine ligands were derived from amino acid amides in which amide oxygen and ternary nitrogen atoms were combined with pyridine moieties. 1H NMR and circular dichroism spectroscopic characterizations revealed that they formed stable Zn2+ complexes in neutral aqueous solutions and caused Zn2+ deficiency in the hepatic stellate cell systems. Since collagen synthesis was effectively promoted in the cells, the present oligopyridine derivatives worked as biocompatible ligands for Zn2+ complexation and cell activation.


Subject(s)
Amino Acids/chemistry , Hepatocytes/drug effects , Organometallic Compounds/chemical synthesis , Pyridines/chemistry , Zinc/chemistry , Amides/chemistry , Amino Acids/pharmacology , Animals , Cells, Cultured , Circular Dichroism , Collagen Type I/biosynthesis , Computer Simulation , Hepatocytes/metabolism , Ligands , Magnetic Resonance Spectroscopy , Male , Molecular Structure , Organometallic Compounds/chemistry , Pyridines/chemical synthesis , Pyridines/pharmacology , Rats , Rats, Wistar , Water/chemistry , Zinc/pharmacology
16.
Chemistry ; 14(17): 5258-66, 2008.
Article in English | MEDLINE | ID: mdl-18446910

ABSTRACT

A new series of tripods were designed to form anion-responsive, luminescent lanthanide complexes. These tripods contain pyridine, thiazole, pyrazine, or quinoline chromophores combined with amide carbonyl oxygen and tertiary nitrogen atoms. Crystallographic and EXAFS studies of the 10-coordinated tripod-La(NO(3))(3) complexes revealed that each La(3+) cation was cooperatively coordinated by one tetradentate tripod and three bidentate NO(3)(-) anions in the crystal and in CH(3)CN. Quantum chemical calculations indicated that the aromatic nitrogen plays a significant role in lanthanide complexation. The experimentally determined stability constants of complexes of the tripod with La(NO(3))(3), Eu(NO(3))(3), and Tb(NO(3))(3) were in good agreement with the theoretically calculated interaction energies. Complexation of each tripod with lanthanide triflate gave a mixture of several lanthanide complex species. Interestingly, the addition of a coordinative NO(3)(-) or Cl(-) anion to the mixture significantly influenced the lanthanide complexation profiles. The particular combination of tripod and a luminescent Eu(3+) center gave anion-selective luminescence enhancements. Pyridine-containing tripods exhibited the highest NO(3)(-) anion-selective luminescence and thus permit naked-eye detection of the NO(3)(-) anion.


Subject(s)
Heterocyclic Compounds/chemistry , Lanthanoid Series Elements/chemistry , Luminescence , Acetonitriles/chemistry , Anions/chemistry , Crystallography, X-Ray , Ligands , Magnetic Resonance Spectroscopy , Spectrophotometry, Ultraviolet
17.
Chem Commun (Camb) ; (24): 2533-5, 2007 Jun 28.
Article in English | MEDLINE | ID: mdl-17563820

ABSTRACT

A new dendrimer-type ligand dynamically switched the lanthanide complexation and luminescence profiles in response to external anions.

18.
Dalton Trans ; (26): 2784-91, 2007 Jul 14.
Article in English | MEDLINE | ID: mdl-17592595

ABSTRACT

A new series of N3,O-mixed donor tripods was prepared for luminescent Eu3+ complexes, in which the soft quinoline nitrogen, tertiary amine nitrogen, and hard amide oxygen donors were cooperatively involved. The mixed donor tripods formed more stable 1 : 1 complexes with Eu(NO3)3, La(NO3)3 and Tb(NO3)3 than the corresponding N4 donor tripods, and their Eu3+ complexes particularly exhibited anion-responsive luminescence properties. NMR, UV, and luminescence spectroscopic characterizations revealed that -CH3 substitution on the tripod skeleton remarkably altered the preferred stoichiometry of the "tripod-Eu3+-anion" ternary complex and gave anion-dependent europium luminescence. Although the disubstituted tripod preferred to form non-luminescent 2 : 1 (tripod : Eu3+) complexes with Eu(NO3)3 and other salts, it formed a luminescent 1 : 1 complex with EuCl3. Thus, this type of tripod offered Cl- anion-selective luminescence enhancement that was easily observed by the naked eye.


Subject(s)
Chlorides/analysis , Europium/chemistry , Fluorescent Dyes/chemistry , Organometallic Compounds/chemistry , Anions/analysis , Fluorescent Dyes/chemical synthesis , Ligands , Luminescence , Magnetic Resonance Spectroscopy , Nitrogen/chemistry , Organometallic Compounds/chemical synthesis , Oxygen/chemistry , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet
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