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BackgroundThe purpose of this study was to develop a scale capable of measuring comprehensive quality of life (QOL) outcomes based on the concept of a good death for patients with advanced cancer.MethodsWe conducted an anonymous cross-sectional questionnaire survey on inpatients being treated at the Oncology Clinic in Saitama Medical University International Medical Center and seven palliative units throughout Japan.ResultsA total of 405 patients with cancer participated in this study. Factor analysis of scores on the Comprehensive Quality of Life Outcome (CoQoLo) inventory revealed 28 items and the following 10 subscales: physical and psychological comfort; staying in a favourite place; maintaining hope and pleasure; good relationships with medical staff; not being a burden to others; good relationships with family; independence; environmental comfort; being respected as an individual; and having a fulfilling life. The total CoQoLo score was moderately correlated with satisfaction (r=0.34) and overall QOL (r=0.34), and moderately correlated with feelings of support and security regarding cancer care (r=0.44). Cronbach's α and the intraclass correlation coefficient of the total score were 0.90 and 0.79, respectively. No significant correlation was found between the total CoQoLo score and self-reported Eastern Cooperative Oncology Group performance status (r=−0.01).ConclusionsThese results suggest that the CoQoLo has sufficient reliability and validity and therefore provides an accurate measure of QOL outcomes independent of the general physical condition of the patient.

Podoplanin is an endogenous ligand for C-type lectin-like receptor 2 (CLEC-2), which is expressed on platelets. Recent evidence indicates that this specific marker of lymphatic endothelial cells is also expressed by keratinocytes at the edge of wounds. However, whether podoplanin or platelets play a role in keratinocyte activity during wound healing remains unknown. We evaluated the effect of podoplanin expression levels on keratinocyte motility using cultured primary normal human epidermal keratinocytes (NHEKs). Down-regulation of podoplanin in NHEKs via transfection with podoplanin siRNA inhibited their migration, indicating that podoplanin plays a mandatory role in this process. In addition, down-regulation of podoplanin was correlated with up-regulation of E-cadherin, suggesting that podoplanin-mediated stimulation of keratinocyte migration is associated with a loss of E-cadherin. Both the addition of platelets and treatment with CLEC-2 inhibited the migration of NHEKs. The down-regulation of RhoA activity and the up-regulation of E-cadherin in keratinocytes were also induced by CLEC-2. In conclusion, these results suggest that podoplanin/CLEC-2 signaling regulates keratinocyte migration via modulating E-cadherin expression through RhoA signaling. Altering the regulation of keratinocyte migration by podoplanin might be a novel therapeutic approach to improve wound healing.

In order to realize a high conductive carbon nanotube (CNT) via structure, an accurate evaluation of electrical properties of CNTs and their metal contacts is essential. We succeeded in evaluating the resistance of CNTs and their contacts individually by using our proposed test method and test structure. The contact resistance of CNTs to metals was dependent on the types of contacting metals, which can be explained by the Gibbs energy of oxide formation and differences in work functions of each metal with CNTs and adhesion property. Ti and Pd had common chemical and mechanical characteristics and showed the lowest contact resistance with CNTs among contact metals we used.

We report on the electrical properties of carbon nanotube (CNT) via interconnects with improvement in contact formations between the CNT via and metal electrodes. For the improvement of the bottom contact formation, a TiN/TaN multilayer on a Cu bottom wiring layer is applied to suppress formation of a highly resistive oxide layer on the TaN barrier layer. The top electrode formation with good coverage on CNTs reduces contact resistance. The current--voltage characteristics of ultrafine CNT via interconnects exhibit ohmic behavior. The resistance of the CNT via interconnect is inversely proportional to the via area, indicating that the CNT bundles are grown with uniform quality and density in various-diameter via holes.

In the presence of metallic strontium, the Barbier-type alkylation of aldehydes with alkyl iodides proceeded smoothly at -15 °C under an argon atmosphere to afford the corresponding alkylated alcohols in moderate to good yields. The unusual addition reaction of ethyl benzoate with tert-butyl iodide took place to give the p-tert-butylated alkylated product (the 1,6-adduct of the benzoate) in 55% yield. Using strontium isopropoxide, the Meerwein–Ponndorf–Verley-type reduction of the aldehyde proceeded smoothly under reflux conditions in 2-propanol.

A convenient one pot allylation of aldehydes with allylic iodides prepared in situ from allylic alcohols by using trimethylsilyl chloride and sodium iodide proceeds smoothly in the presence of metallic bismuth to afford the corresponding homoallylic alcohols in good yields.

Aldehydes are reduced chemoselectively by using tributyltin hydride in methanol, aqueous organic solvents, or water to provide the corresponding alcohols in high yields. No additional catalyst is required.

Silyl enol ethers react with dialkylboron halides or dialkylboron triflates to give the corresponding boron enolates quantitatively under mild conditions. Boron enolates thus generated are effectively used to afford cross aldol products with benzaldehyde.

To investigate the relationship between morphological plasticity of the spinal cord and neurological outcome after surgery for compressive lesions, we correlated the transverse area of the cervical spinal cord measured by transaxial magnetic resonance imaging (MRI) obtained during the early postoperative period (1–6 months) with neurological function assessed at a median postoperative follow-up period of 2.5 years. Measurements on MRI in 56 patients (35 men and 21 women) included evaluation of the cross-sectional area of the cervical cord and the subarachnoidal space at the level of decompression. The transverse area of the cervical cord increased by 30 to 62% postoperatively and that of the subarachnoidal space by 57 to 95%. Neurological improvement was noted in all patients and averaged 63% in our assessment scale. Expansion of the cervical cord during the early postoperative period correlated significantly with the late postoperative neurological status (P= 0.009). Our results suggest that an increase in the cross-sectional area of the cervical spinal cord, representing spinal cord morphological plasticity, is a significant factor in determining the late neurological improvement following decompressive surgery.

α-Hydroxy ketones (acyloins) were reduced to the corresponding ketones in good yields via pyridinium salts by the successive treatment with 1-methyl-2-fluoropyridinium p-toluenesulfonate and sodium hydrosulfite.

3-Methoxy-1-phenylthio-1-propene (3), obtained by the reaction of 1-phenylthio-2,3-epoxypropane (1) with sodium hydride in tetrahydrofuran (THF) and successive treatment with methyl iodide, was lithiated with lithium diisopropylamide at −78°C. The lithio derivative reacted with alkyl halides regioselectively at the α-position of sulfur atom, and hydrolysis of the products at room temperature in the presence of mercuric chloride afforded the corresponding α,β-unsaturated aldehydes in good yields.

The allylation of aldehydes with allylic bromides proceeded smoothly in a Mg / BiCl 3bimetal system even in THF-H 2O to afford the corresponding homoallylic alcohols in good yields. © 1997 Elsevier Science Ltd.

Bismuth bromide was found to work efficiently as a versatile catalyst for the cyanation and allylation of carbonyl compounds and acetals with organosilicon reagents, affording the corresponding alcohols and ethers in high yields.

It was established that the antibiotic and anti-leukemic agent botryodiplodin (VIIIa) is synthesized in good yield from cis-a-methyl ß-acetyl-?-butyrolactone, produced by the reaction of of a-methyl-a-angelicalactone with formaldehyde.

In order to elucidate the absolute configuration of C-15 in natural hyptol, methyl (15S)-12,16-dihydroxy-8,11,13-abietatrien-18-oate and its (15R)-epimer were transformed into (15S)-12,16-epoxy-11,14-dihydroxy-8,11,13-abietatrien-7-one (1a) and its (15R)-epimer (1b), respectively. The synthetic 1aw as identical to natural hyptol. Thus, the stereochemistry of C-15 in the natural compound was conclusively assigned as S-configuration.

In the presence of a catalytic amount of bismuth(III) trichloride (5 mol%), silyl enol ethers react with aldehydes at room temperature in dichloromethane to give the corresponding aldols in good yields. Silyl enol ethers also have been found to react with α,β-unsaturated ketones at room temperature in dichloromethane to afford the corresponding 1,5-dicarbonyl compounds, the Michael adducts in good yields. The intermediate adducts of the aldol reaction (the silyl ethers) and the Michael reaction (the silyl enol ethers) were also obtained in good yields.

An efficient method is described for the synthesis of ethyl 1-(2-oxoalkyl)-1,2-dihydroisoquinoline-2-carboxylates by C–C bond formation between 2-ethoxycarbonylisoquinolinium chloride and trimethylsilyl enol ethers. The products were treated with a few bases to afford the corresponding pyrido [2,1-a] isoquinoline derivatives.

Allylic 3-phenylthio-2-propen-1-yl ethers(3) underwent [2,3]-sigmatropic (Wittig-type) rearrangement by treatment of n-butyllithium in tetrahydrofuran (THF) at −40 ∼ −50°C to give the corresponding allylic alcohols (7). On the other hand, the allylic ethers 3were treated with potassium tert-but oxide in tert-butyl alcohol-N,N-dimethylformamide (DMF) at room temperature to give the corresponding allylic enol ethers (12), which isomerized to the corresponding aldehydes (13) on heating in xylene by the Claisen rearrangement.

The reagent formed by the reaction of diethyl azodicarboxylate (1) and triphenylphosphine (2) reacted with alcohols and ethyl cyanoacetate (6) to give alkylated products in 30–80% yields. When ethyl acetoacetate, 1,3-cyclopentanedione, or 1,3-cyclohexanedione was used in place of 6, the corresponding O-alkylated products were obtained. The reaction of either (S)-(−)-ethyl lactate or (S)-(−)-ethyl 2-hydroxy-3-phenylpropionate with 1, 2, and 6, followed by hydrolysis resulted in the formation of (S)-(−)-methylsuccinic acid or (S)-(−)-benzylsuccinic acid. The results indicate that nearly complete inversion of the configuration takes place in the alkylation step.

RCu·BF3reacted with 1-ethoxycarbonylpyridinium chloride at the 4-position with almost complete regio-selectivity (>99%) to afford the corresponding 1,4-dihydropyridine derivatives in high yields (81–94%). The dihydropyridines were oxidized by oxygen to give 4-alkyl(aryl)pyridines (38–68%). Grignard reagents also reacted with 1-t-butyldimethylsilylpyridinium triflate with almost complete regioselectivity (>99%) to afford the corresponding 1,4-dihydropyridines, which were easily oxidized by oxygen to give 4-substituted pyridines in higher yields than above (58–70%).

Salvinolone, saprorthoquinone, and 4-hydroxysapriparaquinone isolated from the roots of Salvia prionitisHance. were synthesized starting from (+)-dehydroabietic acid via 11,12-dimethoxyabieta-8,11,13-trien-7-one and 12-methoxyabieta-8, 11,13-triene.

In the presence of metallic bismuth, bismuth(III) chloride–metallic zinc, or bismuth(III) chloride–metallic iron, allylic halides have been found to react with aldehydes under mild conditions to give the corresponding homoallylic alcohols in high yields with high chemo-, regio-, and stereoselectivity. Allylic halides have been also found to react with aldehydes at room temperature in tetrahydrofuran–water by using bismuth(III) chloride–metallic aluminium to afford the expected homoallylic alcohols in high yields.

1,4-Dihydropyridines were successfully photooxidized to corresponding pyridines under suitable conditions. The substituents of the dihydropyridines, reaction mediums, and atmospheres affect the course of the reactions. When diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (1a), diethyl 1,4-dihydropyridine-3,5-dicar-boxylate (1b), 2,6-dimethyl-3,5-diacetyl-1,4-dihydropyridine (1c), and 3,5-diacetyl-1,4-dihydropyridine (1d) were irradiated by a super high pressure mercury lamp with filter in ethanol under air or oxygen, corresponding pyridines, diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (2a), diethyl pyridine-3,5-dicarboxylate (2b), 2,6-dimethyl-3,5-diacethylpyridine (2c), and 3,5-diacetylpyridine (2d) were formed in good yields. Irradiation of 1a, 1c, and 1din acetonitrile afforded 2a, 2c, and 2dirrespective of their atomosphere, oxygen or nitrogen. On the other hand, photolysis of 1bby the same lamp and filter in ethanol or acetonitrile in an atmosphere of nitrogen resulted in the formation of photodimer (3) which on irradiation by low pressure mercury lamp in acetonitrile dissociated to 1bfollowed by photooxidation giving 2b. Diethyl l-acetyl-1,4-dihydropyridine-3,5-dicarbolxyate (4e) and 1,3,5-triacetyl-1,4-dihydropyridine (4f) afforded 2band 2din fairly good yields when the photolyses were carried out in an atmosphere of air in ethanol or acetonitrile.

We fabricate planarized carbon nanotube (CNT) via interconnects using chemical mechanical polishing (CMP). The selective growth of CNT bundles in via holes and the filling of spin-on-glass into the space among the CNTs are performed, followed by a CMP process. The via resistance is reduced by post-CMP treatment and post-annealing due to the improvement in the top contact formation. The measured CNT via resistance is higher than the CNT bundle resistance estimated from the measured resistance of an individual CNT. This indicates that contact resistance is higher than the CNT resistance in the CNT via interconnect.

The chemistry of an alkylstrontium halide analogue was examined. In the presence of metallic strontium, the Barbier-type alkylation of esters with alkyl iodides proceeded smoothly at room temperature, under argon, to afford the corresponding dialkylated alcohols in good yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

In the presence of BiCl3–Zn(0), nearly equimolar amounts of allyl bromide reacted with carbonyl compounds containing a carboxyl group to afford the corresponding homoallylic alcohols having a carboxyl group or the intramolecular dehydrated lactones in good yields.

The reaction of diphenylacetothioanilide with diethyl azodicarboxylate and triphenylphosphine gave rise to the formation of diphenylketene(N-phenyl)imine. Similarly, the reaction of N-(p-tolyl)diphenylacetothioamide gave diphenylketene(N-p-tolyl)imine. On treatment with diethyl azodicarboxylate in the presence of sodium ethoxide, diphenylacetothioanilide afforded bis(N-phenylbenzalimidoyl) disulfide in a good yield. The intermediate of the formation of the ketenimines is also discussed.

Functional selectivity and stereospecificity of the intermolecular dehydration between alcohols and phthalimide (III) by means of diethyl azodicarboxylate (I) and triphenylphosphine (II) was examined. The reaction of allyl alcohol, 2-chloroethanol or (±)-ethyl lactate with I, II, and III led to the formation of corresponding N-alkylphthalimide. The reaction was further applied to the synthesis of esters of N-phthaloyl-a-amino acid. (S)-(-)-ethyl 2-hydroxy-3-phenylpropionate was converted into (R)-(+)-N-phthaloylphenylalanine ethyl ester with high stereospecificity.

Various esters reacted with metallic strontium and alkyl iodides to give dialkylated products, followed by adding acid chlorides or acid anhydrides to afford the corresponding bulky tert-alcohol esters in good yields.

Aromatic carboxylic acids reacted with metallic strontium and alkyl iodides to give para alkylated products preferentially in moderate to good yields.

Aromatic aldimines reacted with Sr in the presence of a catalytic amount of iodine to give self-coupling products in good yields, whereas aromatic and aliphatic aldehydes underwent a similar reaction effected by the combined use of Sr and Al(OEt)3.

Carboxylic acids reacted with metallic strontium and methyl iodide to give methyl ketones preferentially in moderate to good yields.

The chemistry of alkylstrontium halide analogues was examined. In the presence of metallic strontium, the Barbier-type alkylation of imines with alkyl iodides proceeded smoothly at room temperature under an argon atmosphere to afford the corresponding alkylated amines in good yields.

A new solvent-free procedure for the synthesis of ß-amino carbonyl compounds in generally moderate to excellent yields has been developed. Three-component Mannich-type couplings between aldehydes (aromatic, aliphatic, alicyclic, and heterocyclic), aromatic amines and silyl enol equivalents proceeded smoothly on a conveniently prepared and reusable phosphoric acid-silica gel solid support.

Imines generated in situ from aldehydes and aniline can be reduced using tributyltin hydride on silica gel under solvent-free conditions to provide the corresponding amines in good yields.

Some water-tolerant allylating agents prepared in situfrom allylmagnesium chloride and bismuth trichloride, tin tetrachloride, tin dichloride, antimony trichloride, indium trichloride, or nickel dichloride reacted with aldehydes in THF–H2O to afford the desired homoallylic alcohols in good yields. The present reaction proceeded more smoothly than that under non-aqueous media.

The reductive homocoupling of a carbonyl compound and heterocoupling of a carbonyl compound with a non-protected alcohol were both effected smoothly at room temperature with triethylsilane in the presence of a catalytic amount of bismuth trichloride to afford the corresponding ethers in good yields.

In the presence of bismuth trichloride and metallic zinc, α-diketones react with aldehydes in THF under reflux to afford the corresponding α,β-dihydroxyketones in moderate to good yields. It was also found that the present reaction proceeds smoothly by using a catalytic amount of bismuth trichloride to give the corresponding adducts. The present reaction takes place even in aqueous media.

We explored the characteristic behavior of low-temperature graphene growth on catalytic metal films. The results suggested that graphene growth originates from the crystalline facets with specific angles with respect to the crystalline orientation of the catalytic metals at low temperatures, which is different from the conventional growth models. The G/D ratio of the Raman spectrum of the graphene film was affected by both the number of specific facets and the width of the terrace. Because of this behavior, it is important to prepare the surface conditions with a smaller number of facets and a wider terrace for high-quality graphene growth at low temperatures.