Positive Synergy between the Helical Poly(phenylacetylene) Backbones and the Helical -Proline Oligopeptide Pendants for Enhanced Enantioseparation Properties.

A series of optically active helical poly(phenylacetylene)s (, , , , and ) bearing different chain lengths of -proline oligopeptide in the side chains were obtained by polymerizing the corresponding novel phenylacetylene monomers. The monomer adopted a -rich helix structure when the -proline oligopeptide chain length was longer, according to the optical activities and 2D-NMR analysis. The helical structure could be maintained and significantly influenced the polymers' helical conformation by introducing the -proline oligopeptide to the pendants.

Cellulose/amylose derivatives bearing bulky substituents as reversible fluorescent sensors for detection of Fe.

Two novel cellulose and amylose derivatives bearing bulky tris(2-benzothienylformate) pendants (Cel-3 and Amy-3) were expeditiously prepared by one-step esterification. The fluorescent sensing performance of six polysaccharide derivatives, including Cel-3/Amy-3, and other four previously prepared benzothienyl- or benzofuranyl-phenylcarbamates of cellulose and amylose (Cel-1/Amy-1, Cel-2/Amy-2), were carefully evaluated using eight metal ions, including Co, K, Na, Li, Hg, Ni, Ca and Fe. All six derivatives exhibited excellent fluorescence quenching property to Fe ions with high sensitivity and selectivity.

Synthesis of amylose and cellulose derivatives bearing bulky pendants for high-efficient chiral fluorescent sensing.

Three novel amylose and cellulose phenylcarbamate derivatives bearing bulky para-substituted benzothienyl or benzofuranyl pendants were successfully synthesized as chiral fluorescent sensors through carbamoylation followed by Suzuki-Miyaura coupling reactions. The bulky derivatives showed good enantioselective fluorescent sensing properties toward a total of eight chiral quenchers in this study. Especially, a high enantiomeric fluorescence difference ratio (ef = 164.

Hybridization of helical poly(phenylacetylene)s bearing L-proline tripeptide pendants into porous silica microspheres as a solvent-tolerable chiral stationary phase for liquid chromatography.

A novel one-handed helical copoly(phenylacetylene) (CPA) bearing L-proline tripeptide pendants and a few triethoxysilyl residues was synthesized and hybridized into SiO porous microspheres (PMSs) during microsphere growth through the hydrolytic polycondensation of ethoxysilyl groups. Nuclear magnetic resonance and Fourier transform infrared spectroscopy results verified the successful preparation of CPA and its hybrid product using SiO PMSs. The chiral recognition ability of the resulting CPA with a hybridized-type chiral stationary phase (HCSP) for high-performance liquid chromatography (HPLC) was investigated, revealing its high recognition ability for selected racemates.

Synthesis and application of chitosan thiourea derivatives as chiral stationary phases in HPLC.

Chitosan 2-thiourea derivatives with various substituents, including 3-(methylthio)propyl, phenyl, octyl and ethoxycarbonyl, at the 2-position of the glucosamine skeleton were prepared via isothiocyanates with the above substituents. The obtained chitosan 2-thiourea derivatives without ethoxycarbonyl were then esterified to develop a new series of chitosan 2-thiourea-3,6-diphenylcarbamate derivatives. The enantioseparation properties of the obtained chitosan derivatives were examined by high-performance liquid chromatography (HPLC).

Preparation of cellulose derivative bearing bulky 4-(2-benzothienyl)phenylcarbamate substituents as chiral stationary phase for enantioseparation.

A novel cellulose derivative bearing bulky 4-(2-benzothienyl)phenylcarbamate substituents (Cel-1) was readily synthesized by carbamoylation followed by Suzuki-Miyaura coupling reaction. The corresponding coated-type chiral stationary phase (CSP) was prepared on basis of the derivative, and its chiral recognition ability was then evaluated by high-performance liquid chromatography (HPLC). The chiral recognition ability of the cellulose derivative was greatly influenced by introduction of the bulky benzothienyl pendants on the aromatic moieties of phenylcarbamates, compared with its analog with smaller groups.

NK-cell post-transplant lymphoproliferative disease successfully treated by second allogenic hematopoietic stem cell transplantation in chronic active Epstein-Barr virus infection.

Chronic active Epstein-Barr virus infection (CAEBV) is a systemic T- or NK-lymphoproliferative disorder (LPD) caused by EBV. Allogenic hematopoietic stem cell transplantation (HSCT) is the only curative therapy for CAEBV, but relapse sometimes occurs. Relapse is generally attributed to proliferation of recipient-derived CAEBV cells.

Identification of an asymptomatic Shwachman-Bodian-Diamond syndrome mutation in a patient with acute myeloid leukemia.

Shwachman-Diamond syndrome (SDS) is an autosomal recessive inherited disorder characterized by bone marrow failure, exocrine pancreatic dysfunction, and skeletal abnormalities. SDS is typically caused by a pathogenic mutation in the Shwachman-Bodian-Diamond Syndrome (SBDS) gene. Patients with SDS have an increased risk of developing acute myeloid leukemia (AML) and myelodysplastic syndromes.

The expression of human testis-specific actin capping protein predicts in vitro fertilization outcomes: A novel biomarker of sperm function for assisted reproductive technology.

Purpose: Sperm function tests do not adequately assess fertilization potential, and new indices are required. We have previously reported that human testis-specific actin capping proteins may be involved in both sperm morphology and function. This study aimed to determine whether testis-specific actin capping proteins can be a predictive marker of IVF success.

Acquired hypofibrinogenemia in a patient with multiple myeloma.

We report a case of acquired hypofibrinogenemia with multiple myeloma presenting λ-type IgG monoclonal protein. The patient had anemia and renal deficiency, and also developed bleeding tendency due to severe coagulopathy. Her fibrinogen level was under the detectable limits in a functional assay.

Influence of the substituents on phenyl groups on enantioseparation property of amylose phenylcarbamates.

A series of amylose phenylcarbamate derivatives bearing different chloro- or/and methyl- substituents on the phenyl groups were synthesized and their enantioseparation properties were examined by high-performance liquid chromatography. The enantioseparation power considerably altered due to the substituents on the phenyl units. The amylose derivative bearing 3-chloro-5-methyl disubstituents seemed to possess much higher chiral resolution power.

Enantioseparation using chitosan 2-isopropylthiourea-3,6-dicarbamate derivatives as chiral stationary phases for high-performance liquid chromatography.

A new class of chitosan derivatives with an isopropylthiourea at the 2-position and various carbamates at the 3,6-positions of the glucosamine skeleton was synthesized by the selective thiocarbamoylation of the 2-amino group. The chiral stationary phases (CSPs) were then prepared by coating the obtained chitosan 2-isopropylthiourea-3,6-dicarbamate derivatives onto silica gel. The enantioseparation property of the chitosan-based CSPs was assessed with twelve racemates by high-performance liquid chromatography (HPLC).

Efficacy of salvage therapy with MTX-HOPE for elderly patients with heavily pretreated non-Hodgkin's lymphoma.

Methotrexate, hydrocortisone, vincristine, sobuzoxane, and etoposide (MTX-HOPE) chemotherapy was originally reported in 2007 as a salvage regimen for relapsed or refractory non-Hodgkin's lymphoma. To clarify the safety and efficacy of this regimen, we retrospectively analyzed patients at our institute. We analyzed 18 patients, including 16 with diffuse large B-cell lymphoma (DLBCL), one with follicular lymphoma (FL), and one with T-cell lymphoma.

Synthesis of poly(phenylacetylene)s containing chiral phenylethyl carbamate residues as coated-type CSPs with high solvent tolerability.

Two novel helical poly(phenylacetylene) derivatives containing chiral phenylethyl carbamate residues in the end of each side chain (PPA-S and PPA-R) were synthesized by polymerization of the corresponding phenylacetylene monomers using Rh(nbd)BPh as a catalyst in DMF. The enantioseparation properties of the polymers were evaluated as coated-type chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). Under the same chromatographic conditions, PPA-S and PPA-R showed different enantioseparation properties, indicating that the different interactions between the analytes and the polymers, which result from the different chiral phenylethyl carbamate groups in the end of each side chains.

[Essential thrombocythemia correctly diagnosed through the guidance of comprehensive genomic profiling].

In 2003, a 60-year-old man presenting with thrombocytosis was referred to our hospital. Laboratory tests revealed normal white blood cell count and hemoglobin level. Bone marrow examination showed an increased number of megakaryocytes with dysplasia.

[MYC gene amplification attributed to double minutes in a patient with atypical chronic myeloid leukemia].

A 61-year-old man was admitted to our hospital with fever and massive leukocytosis. A bone marrow smear revealed an increased density of myeloid cells in various stages of maturation as well as dysplasia in the neutrophils. There was no proliferation of blasts, eosinophils, or basophils.

Chiral recognition ability of amylose derivatives bearing regioselectively different carbamate pendants at 2,3- and 6-positions.

Seven amylose derivatives bearing two regioselective carbamate pendants at 2,3- and 6-positions of a glucose unit were synthesized through protection and deprotection at the 6-position. The chiral recognition abilities of the obtained derivatives were evaluated as the chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). Each derivative had its own characteristic recognition ability depending on the arrangement of carbamate pendants at the three positions.

Synthesis of cellulose carbamates bearing regioselective substituents at 2,3- and 6-positions for efficient chromatographic enantioseparation.

Nine cellulose derivatives bearing two different carbamate substituents at 2,3- and 6-positions of a glucose unit were synthesized by a sequential process based on the regioselective protection at 6-position. Their chiral recognition abilities were then evaluated as the chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) after coating them onto the macroporous silica gel. The introduction of two different phenylcarbamates at 2,3- and 6-positions of glucose unit was comparatively more attractive than that of one phenylcarbamate and one cyclohexylcarbamate to enhance the chiral recognition ability of these cellulose derivatives.

Temperature-Triggered Switchable Helix-Helix Inversion of Poly(phenylacetylene) Bearing l-Valine Ethyl Ester Pendants and Its Chiral Recognition Ability.

A phenylacetylene containing the l-valine ethyl ester pendant (PAA-Val) was synthesized and polymerized by an organorhodium catalyst (Rh(nbd)BPh₄) to produce the corresponding one-handed helical -poly(phenylacetylene) (PPAA-Val). PPAA-Val showed a unique temperature-triggered switchable helix-sense in chloroform, while it was not observed in highly polar solvents, such as ,'-dimethylformamide (DMF). By heating the solution of PPAA-Val in chloroform, the sign of the CD absorption became reversed, but recovered after cooling the solution to room temperature.

Enantioseparation Using Cellulose Tris(3,5-dimethylphenylcarbamate) as Chiral Stationary Phase for HPLC: Influence of Molecular Weight of Cellulose.

The cellulose oligomers with different degrees of polymerization (DP), 7, 11, 18, 24, 26, 40 and 52, were prepared by hydrolysis of microcrystalline cellulose with phosphoric acid. These oligomers including the starting microcrystalline cellulose (DP 124) were converted to tris(3,5-dimethylphenylcarbamate) (CDMPC) derivatives by the reaction with an excess of 3,5-dimethylphenyl isocyanate to be used as the chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). The structures of the CDMPC derivatives were investigated by infrared spectroscopy (IR), ¹H-NMR, circular dichroism (CD) and size exclusion chromatography (SEC), and the DPs of the derivatives estimated by SEC agreed with those estimated by ¹H-NMR.

Synthesis and chiral recognition of amylose derivatives bearing regioselective phenylcarbamate substituents at 2,6- and 3-positions for high-performance liquid chromatography.

Eighteen novel amylose derivatives bearing different phenylcarbamate substituents at 2,6- and 3-positions of a glucose ring were synthesized through the regioselective protection at 2- and 6-positions using a bulky trialkylsilyl chloride. Their chiral recognition abilities were then evaluated as the chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) after coating them on the surface of macroporous silica gel. The chiral recognition abilities of these CSPs intricately depended on the nature, position and number of the substituents on the phenyl moieties.

[Preparation and chiral recognition ability of chiral stationary phase based on immobilized polyacrylamide derivative].

High performance liquid chromatography (HPLC) has been widely considered as the most effective way for the separation and preparation of optically pure enantiomers. In the resolution by HPLC, the separation ability of a column strongly depends on the properties of a chiral stationary phase (CSP). Among many CSPs, the immobilized CSPs, which are becoming one of the most important kinds of CSPs, have the advantages of good solvent durability and enormous method flexibility.

[Preparation and enantioseparation property of novel amylose-based chiral stationary phases for high performance liquid chromatography].

Five new amylose derivatives, namely amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3,5-dimethylphenylcarbamate), amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3, 5-dichlorophenylcarbamate), amylose 2-benzoate-3, 6-bis (4-chlorophenylcarbamate), amylose 2-(4-chlorobenzoate)-3, 6-bis (4-chlorophenylcarbamate) and amylose 2-(4-chlorobenzoate)-3,6-biscyclohexylcarbamate, were synthesized by a series of regioselective process. These derivatives were then coated on the surface of aminopropyl silica gels, and used as chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC). These derivatives were characterized by 1H-nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FT-IR) spectroscopies, and their chiral recognition abilities were evaluated using nine racemates by HPLC.