bluuebunny/crossref_metadata_2025 huggingface dataset:
Postoperative Radiotherapy for Stage II or III Non–Small-Cell Lung Cancer Using the Surveillance, Epidemiology, and End Results Database
Authors: Lally Brian E. , Zelterman Daniel , Colasanto Joseph M. , Haffty Bruce G. , Detterbeck Frank C. , Wilson Lynn D.
Published: June 2006

Purpose

To investigate the association between survival and postoperative radiotherapy (PORT) in patients with resected non–small-cell lung cancer (NSCLC).

Patients and Methods

Within the Surveillance, Epidemiology, and End Results database, we selected patients with stage II or III NSCLC who underwent a lobectomy or pneumonectomy. Only those patients coded as receiving PORT or observation were included. To account for perioperative mortality, we excluded patients who survived less than 4 months. As a result of our inclusion criteria, we selected a total of 7,465 patients, with a median follow-up time of 3.5 years for patients still alive.

Results

Predictors for the use of PORT included age less than 50 years, higher American Joint Committee on Cancer stage, T3-4 tumor stage, larger tumor size, advanced node stage, greater number of lymph nodes involved, and a ratio of lymph nodes involved to lymph nodes sampled approaching 1.00. On multivariate analysis, older age, T3-4 tumor stage, N2 node stage, male sex, fewer sampled lymph nodes, and greater number of involved lymph nodes had a negative impact on survival. The use of PORT did not have a significant impact on survival. However, in subset analysis for patients with N2 nodal disease (hazard ratio [HR] = 0.855; 95% CI, 0.762 to 0.959; P = .0077), PORT was associated with a significant increase in survival. For patients with N0 (HR = 1.176; 95% CI, 1.005 to 1.376; P = .0435) and N1 (HR = 1.097; 95% CI, 1.015 to 1.186; P = .0196) nodal disease, PORT was associated with a significant decrease in survival.

Conclusion

In a population-based cohort, PORT use is associated with an increase in survival in patients with N2 nodal disease but not in patients with N1 and N0 nodal disease.
Targeted Inhibition of Farnesyltransferase in Locally Advanced Breast Cancer: A Phase I and II Trial of Tipifarnib Plus Dose-Dense Doxorubicin and Cyclophosphamide
Authors: Sparano Joseph A. , Moulder Stacy , Kazi Aslamuzzaman , Vahdat Linda , Li Tianhong , Pellegrino Christine , Munster Pam , Malafa Mokenge , Lee David , Hoschander Shira , Hopkins Una , Hershman Dawn , Wright John J. , Sebti Said M.
Published: June 2006

Purpose

To determine the recommended phase II dose (RPTD) of the farnesyltransferase (FTase) inhibitor tipifarnib when combined with doxorubicin and cyclophosphamide (AC) in patients with advanced breast cancer, the pathologic complete response (pCR) rate after preoperative treatment with four cycles of the combination in locally advanced breast cancer (LABC), and the effect of tipifarnib on primary tumor FTase enzyme activity in vivo.

Patients and Methods

Thirty-two patients with metastatic breast cancer (n = 11) or LABC (n = 21) received AC (doxorubicin 60 mg/m2 and cyclophosphamide 600 mg/m2) administered intravenously on day 1 plus tipifarnib (100, 200, or 300 mg bid for 6 to 14 days) without (n = 2) or with (n = 30) granulocyte colony-stimulating factor (G-CSF) for up to four cycles. Patients with LABC underwent surgery after up to four cycles of the combination.

Results

When combined with AC every 2 weeks plus G-CSF, the RPTD of tipifarnib was 200 mg bid administered on days 2 to 7. Seven (33%) of 21 patients (95% CI, 15% to 55%) with LABC treated with up to four cycles of the combination at the RPTD had a pCR in the breast at surgery. The five patients had serial biopsies that demonstrated at least 50% FTase enzyme inhibition in the primary tumor (median, 100%; range, 55% to 100%) after tipifarnib.

Conclusion

Tipifarnib may be safely combined with dose-dense AC using a dose and schedule that significantly inhibits FTase enzyme activity in human breast cancer in vivo and may enhance the pCR rate after four cycles of preoperative dose-dense AC.
Assessment of Disease Dissemination in Gastric Compared With Extragastric Mucosa-Associated Lymphoid Tissue Lymphoma Using Extensive Staging: A Single-Center Experience
Authors: Raderer Markus , Wöhrer Stefan , Streubel Berthold , Troch Marlene , Turetschek Karl , Jäger Ulrich , Skrabs Cathrin , Gaiger Alexander , Drach Johannes , Puespoek Andreas , Formanek Michael , Hoffmann Martha , Hauff Wolfgang , Chott Andreas
Published: June 2006

Purpose

Molecular data and preliminary clinical findings have suggested mucosa-associated lymphoid tissue (MALT) lymphoma as a multifocal disease in a high percentage of patients. We report our findings with an extensive staging routine applied in patients diagnosed with MALT lymphoma at our institution.

Patients and Methods

A total of 140 consecutive patients (61 with gastric and 79 with extragastric MALT lymphoma) underwent staging according to a standardized protocol. Staging included gastroscopy with multiple biopsies, endosonography of the upper GI tract, computed tomography of thorax and abdomen, lymph node sonography, colonoscopy with multiple biopsies, otorhinolaryngologic assessment, magnetic resonance imaging of salivary and lacrimal glands, and bone marrow biopsy. All lesions suggestive of lymphoma involvement were subjected to biopsy, if accessible, and biopsies were evaluated for MALT lymphoma–specific genetic aberrations by means of reverse transcriptase polymerase chain reaction and/or fluorescent in situ hybridization.

Results

Fifteen (25%) of 61 patients with gastric MALT lymphoma had multiorgan involvement, with dissemination beyond the GI tract in six patients. By contrast, significantly more patients with extragastric MALT lymphoma had dissemination to another MALT organ (37 of 79 patients, 46%; P = .045). Nine of these 37 patients had dissemination to the stomach. Only three (2%) of 140 patients had bone marrow involvement. Multifocality was significantly associated with t(11;18)(q21;q21) in gastric lymphomas (P = .045) and with trisomy 18 in extragastric lymphomas (P = .011).

Conclusion

Our findings suggest that MALT lymphoma frequently presents as a multifocal disease. Extragastric MALT lymphomas are significantly more prone to dissemination than gastric MALT lymphomas.
Effects of the Intrapellet Activity Profiles on the Selectivities in Consecutive Reactions : 1,3-Butadiene Hydrogenation over Pt/Al2O3
Authors: Komiyama Masaharu , Ohashi Kazumichi , Morioka Yoshio , Kobayashi Jun’ichi
Published: June 2006

Experimental examinations concerning the effect of the intrapellet activity profiles on a consecutive reaction were performed. The product selectivities in the liquid-phase hydrogenation of 1,3-butadiene over Pt/Al2O3 spheres were obtained for three types of intrapellet Pt distribution profiles: a uniform catalyst with an appreciable amount of Pt present throughout the support sphere, an eggshell catalyst with a Pt band deposited at the outer surface of the support sphere, and an inner-shell catalyst with a Pt band at the middle of its radius. In all of the three profiles a whole-pellet catalyst showed product distributions and activation energies very different from that of their respective powdered form. These results are interpreted and discussed in terms of the effect of diffusional limitations.
Molecular-Orientation Change in Langmuir Films of Stearic Acid and Cadmium Stearate upon Surface Compression, as Studied by Infrared External-Reflection Spectroscopy
Authors: Sakai Hiroshi , Umemura Junzo
Published: June 2006

For interpretating the various phases appearing in a two-dimensional system, we have recorded in situ polarized FT-IR external reflection spectra of Langmuir films of stearic acid and cadmium stearate on the water surface at various surface areas, and evaluated the molecular orientation angles quantitatively. In the stearic acid monolayer, the orientation angle of the hydrocarbon chain from the surface normal decreased from 20° to almost 0° upon monolayer compression. In the cadmium stearate monolayer, on the other hand, the orientation angle (near 0°) did not change upon monolayer compression, though it was widely scattered at large surface areas, because of the formation of a rigid crystalline island. These results correspond well to the π–A isotherms.
Phosphorescence Spectra of Two Rotational Isomers of m-Fluorobenzaldehyde
Authors: Uejoh Kazuya , Shimokozono Makoto , Koyanagi Motohiko
Published: June 2006

Phosphorescence spectra of m-fluorobenzaldehyde and its aldehyde deuterated derivative have been observed in the vapor phase at room temperature and in a methylcyclohexane matrix at 4.2 K. Paired band systems were detected for the vapor phase and for each of the two different crystallographic phases, α- and β-phases, and were attributed to two rotational isomers of the aldehyde group. Variable intensity changes between the two paired bands observed in the α-phase crystal are manifestations of the isomeric conversion in the ground state during crystallizations. An energy correlation of the rotational isomers between the lowest excited nπ* singlet and triplet states is given for the vapor phase and for the α-phase methylcyclohexane matrix.
PHOFEX Spectroscopy of HgNe and HgAr: Determination of the Dissociation Energies of the X1Σ+, A3Π0+, and B3Π1 States
Authors: Tasaka Tomoki , Onda Ken , Hishikawa Akiyoshi , Yamanouchi Kaoru
Published: June 2006

Photofragment excitation (PHOFEX) spectroscopy was applied to determine the dissociation energies of the B3Π1 states of HgAr and HgNe. The PHOFEX spectra were measured in the wavelength region where the laser-induced fluorescence spectrum of the B3Π1–X1Σ+ transition exhibits a continuum structure by probing the photolysis product of Hg(63P1) through the Hg(83S1–63P1) transition. By the spectral simulation of the threshold behavior of the high-resolution (Δν ≈ 0.08 cm−1) PHOFEX spectrum, the thresholds for the photodissociation reaction, HgRg → Hg(63P1) + Rg, were determined to be 39447.9(3) and 39536.0(5) cm−1 for Rg = Ne and Ar, respectively. From these thresholds, the dissociation energies, D0’s, of the B3Π1 states of HgNe and HgAr were determined to be D0(B3Π1; HgNe) = 9.8(3) and D0(B3π1; HgAr) = 61.8(5) cm−1, respectively. This direct determination of the dissociation energies of the B3Π1 states led to a determination of the D0’s for the X1Σ+ and A3Π0+ states; D0(X1Σ+; HgNe) = 35.6(3), D0(X1Σ+; HgAr) = 123.7(5), D0(A3Π0+; HgNe) = 68.7(3), and D0(A3Π0+; HgAr) = 348.8(6) cm−1. In addition, the (v′,0) vibronic bands of the B3Π1–X1Σ+ transition of HgAr were re-measured with high resolution for v′ = 0—8. From the transition wavenumbers of these vibronic bands, the Morse potential parameters were determined with high precision as ωe = 11.94(3) cm−1 and ωexe = 0.594(3) cm−1.
Polarity Effect of Organic Solvents on the Separation Factors across the Lanthanoid Series
Authors: Hasegawa Yuko , Takashima Keiko , Watanabe Fumie
Published: June 2006

The extraction constants (Kexn = [LnX3·nE]o/[Ln3+][X−]3[E]on, n = 3 and/or 4) were determined across the lanthanoid series, when lanthanoids(III) were extracted from a 1 M sodium thiocyanate (NaX) solution into benzene and chlorobenzene containing trioctylphosphine oxide (TOPO, E). The dominant species were LnX3·4E for light lanthanoids and LnX3·3E for heavy ones. Although both extraction constants increased along with the atomic number, the difference in the magnitude of log Kex4 from log Kex3 to a less-polar solvent, benzene, was larger than that to chlorobenzene. The separation factor was similar either in light lanthanoids or in heavy lanthanoids to both solvents, reflecting the similar variation of the constants across the series. However, in the middle of the series, it was smaller upon using less-polar solvents than polar solvents. One of the reasons was the larger proportion of LnX3·4E, of which extraction constant did not change much in the middle of the series. In addition, when the concentration of TOPO was not in a large excess of the lanthanoid(III) concentration it was due to a greater consumption of TOPO; that is, the heavier lanthanoid(III), which was extracted better, required more TOPO molecules to be combined with LnX3, and into less-polar solvents lanthanoids(III) were extracted better than into polar solvents. Consequently the separation factor when using less-polar solvents was smaller than expected from the extraction constants.
Intercalation of Methylene Blue into Layered Phosphates in the Presence of Butylamine and Function of Alkylamine in the Intercalation Reaction
Authors: Danjo Mayumi , Tsuhako Mitsutomo , Nakayama Hirokazu , Eguchi Taro , Nakamura Nobuo , Yamaguchi Shunro , Nariai Hiroyuki , Motooka Itaru
Published: June 2006

The intercalation of methylene blue (MB) into layered phosphates was examined in the presence of butylamine (BA) in order to clarify the mechanism of this reaction and the function of alkylamine, such as BA in the intercalation reaction. MB was not directly intercalated into layered phosphates, but could be intercalated in the presence of BA. The intercalation of MB was strongly influenced by the amount of BA used; that is, it was accelerated by the presence of BA, but inhibited by the presence of too much BA. Moreover, in the procedure which BA was previously intercalated into layered phosphates, it was found that the intercalation of MB can be achieved by removing BA from the interlayer region when BA is formed a monolayer in the phase, and depends on the orientation of BA in the interlayer region when BA forms a bilayer.
Facile Chemical Dehydrogenation of α-Amino Acids Chelated to a Ruthenium(II) Ion: (α-Imino acidato)bis(1,10-phenanthroline)ruthenium(II) Complexes
Authors: Mori Tomonori , Yamamoto Tadayoshi , Yamaguchi Motowo , Yamagishi Takamichi
Published: June 2006

(α-Amino acidato)ruthenium(II) complexes were dehydrogenated to give (α-imino acidato)ruthenium(II) complexes by chemical oxidation. (α-Imino acidato)ruthenium(II) complexes, [RuII{N(R1)=C(R2)CO2}(phen)2]+ (R1 = H, Me, or Bn, R2 = H; R1 = H or Me, R2 = Me; R1, R2 = –(CH2)3–) were obtained from the (α-amino acidato)ruthenium(II) complexes (glycinato, N-Me-glycinato, N-Bn-glycinato, (S)-alaninato, N-Me-(S)-alaninato, and (S)-prolinato complexes) by using diammonium cerium(IV) nitrate (CAN) as an oxidizing reagent. On the other hand, in the presence of hydrogen peroxide, the α-imino acidato complexes were converted to the corresponding α-imino acidato complexes, except for the glycinato and (S)-alaninato complexes. In particular, the iminoacetatoruthenium(II) complex, [Ru(NH=CHCO2)(phen)2]+, was synthesized for the first time by this method using CAN as an oxidizing reagent. Dehydrogenation with CAN is more facile and versatile than any other method that we have ever examined.
Reducing Characteristics of Borohydride Exchange Resin–CuSO4 in Methanol
Authors: Sim Tae Bo , Yoon Nung Min
Published: June 2006

Reducing characteristics of borohydride exchange resin (BER)–CuSO4 (cat.) were studied in methanol at room temperature. Carbon–carbon double bonds conjugated with benzene or carbonyl group were more rapidly reduced than was the case with isolated double bonds. Carbonyl groups were readily reduced, whereas esters and amides were inert, and nitriles were slowly reduced. High chemoselectivity was also observed in halide reductions: p-bromochlorobenzene and p-bromoiodobenzene were reduced quantitatively to chlorobenzene and bromobenzene, respectively. Aliphatic epoxides were inert to this reagent; however, styrene oxide derivatives were readily reduced to the corresponding deoxygenated products. Aliphatic azides were reduced slowly during 6 h, whereas phenyl azide was transformed to aniline in 1 h. Nitrocyclohexane was reduced at room temperature, but nitrobenzene, nitrosobenzene, azobenzene, and azoxybenzene required an elevated temperature (65 °C) for rapid reductions (1 h). Similarly, N,N-dimethylaniline N-oxide was reduced at room temperature, whereas pyridine N-oxide required refluxing. Finally, among the sulfur compounds tested, only diphenyl disulfide was reduced readily, and sulfide, aliphatic disulfide, sulfoxide, sulfone, and tosylate were inert to this reducing system.
Interactions of Two Porphyrin Rings: Metal-Induced Structural Change of 5,5′-Ethylenebis(porphyrin)
Authors: Sugiura Ken-ichi , Ponomarev Gelii , Okubo Satoshi , Tajiri Akio , Sakata Yoshiteru
Published: June 2006

5,5′-Ethylenebis(octaethylporphyrin) 1 and its metallocomplexes with various combination of metals (Zn, Cu, and Ni) 2—10 were prepared. On the basis of 1H and 13C NMR as well as MCD spectra, it was concluded that interactions between the two intramolecular porphyrins become attractive when at least one of the two rings is converted to zinc porphyrin. The phenomenon was explained by dipole–dipole interaction arising from the large polarization in Zn complexes.
Synthesis and Photochemical Properties of Anthracene-Polyyne-Porphyrin Assemblies
Authors: Kawabata Shigeki , Yamazaki Iwao , Nishimura Yoshinobu
Published: June 2006

A series of anthrylpolyynes (α-anthryl-ω-(formylphenyl)polyynes) and anthrylpolyynylporphyrins (5-[(anthrylpolyynyl)phenyl]porphyrins) have been synthesized, and their photochemical properties and photoinitiated intramolecular excitation energy transfer from anthracene to porphyrin were studied by picosecond time-resolved fluorescence spectroscopy. Although anthrylpolyynes have strong fluorescence emission and fluorescence high quantum yield, anthrylpolyynylporphyrins, in which porphyrin links to the other side of polyyne, show only typical fluorescence emission of porphyrin and almost no fluorescence emission in the spectral region of anthrylpolyynes. The excitation of anthryl substituent brings about an increase in the fluorescence emission of porphyrin on the picosecond time scale. The mechanism of quantitative energy transfer from the anthryl moiety to the porphyrin is discussed on the basis of the photochemical properties of the component molecules.
Removal of a Palladium-Bound Tertiary Phosphine Ligand with Silver(I) Salts to Generate Cationic Monoorganopalladium(II) Complexes Having One Trimethylphosphine Ligand
Authors: Kayaki Yoshihito , Shimizu Isao , Yamamoto Akio
Published: June 2006

Treatment of neutral monoorganobis(trimethylphosphine)palladium(II) halide complexes, trans-[PdR(X)(L)2] 1 (R = Me, Et, or Ph group, X = halide ligand, L = trimethylphosphine), with an equimolar amount of a silver salt such as AgBF4 usually gives cationic monoorganobis(trimethylphosphine) palladium(II) complexes, trans-[PdR(s)L2]BF4 (s = solvent) 2. But employment of an excess amount of the silver salt in the reaction with 1 or treatment of 2 with an additional amount of the silver salt yields a cationic monoorganopalladium(II) complex coordinated with one PMe3 ligand, cis-[PdR(L)(s)2]+3 by removing one of the PMe3 ligands in 2. The cationic mono-phosphine complex 3 can be also prepared by addition of an equimolar amount of a silver salt to the neutral dinuclear Cl-bridged, monophosphine complex [PdMe(μ-Cl)(PMe3)]25. The cis configuration of 3 was supported by comparison of the NMR spectra with those of cationic, cyclooctadiene (COD)-coordinated monomethylmono(trimethylphosphine)palladium complex, cis-[PdMe(PMe3)(cod)]BF4, 6. Complex 6 was prepared by two routes, by treatment of 3 with COD and by reaction of [PdMe(Cl)(cod)] 7 with an equimolar amount of AgBF4 followed by addition of an equimolar amount of PMe3. The cationic mono-phosphine complex 3 having one PMe3 ligand shows greater reactivity for the CO insertion than the bis-phosphine complex 2.
The First Syntheses of GLA-60 Positional Isomers and Their Biological Activities
Authors: Shiozaki Masao , Arai Masami , Macindoe Wallace M , Mochizuki Takashi , Wakabayashi Takanori , Kurakata Shin-ichi , Tatsuta Tohru , Maeda Hiroaki , Nishijima Masahiro
Published: June 2006

Six GLA-60 positional isomers (8, 14, 14′, 20, 26, and 26′) were synthesized to investigate their biological activities. Compound 8 exhibited potent agonistic activity, while compounds 26 and 26′ exhibited slight agonistic activity on TNFα production toward human monoblastic U937 cells. TNFα production (% control; 10 ng ml−1 of LPS = 100) of compound 8 in the concentration of 10 μM was 611, and that of lipid A in the same concentration was 651. In contrast, the difluorinated compounds 14, 14′, and 20 showed little agonistic activity on TNFα production. And neither compound 8 nor compounds 26 and 26′ showed antagonistic activity. On the other hand, the difluorinated compounds 14, 14′, and 20 showed potent antagonistic activity, and inhibited the LPS-induced TNFα production dose-dependently. Compound 14′ (10 μM) inhibited in excess of 80% of the LPS-induced TNFα production.
Gas-Phase Substituent Effects in Highly Electron-Deficient Systems. II. Stabilities of 1-Aryl-2,2,2-trifluoroethyl Cations Based on Chloride-Transfer Equilibria
Authors: Mishima Masaaki , Inoue Hiroki , Fujio Mizue , Tsuno Yuho
Published: June 2006

The relative stabilities of 1-aryl-2,2,2-trifluoroethyl cations were determined based on the chloride ion-transfer equilibria in the gas phase. An application of the Yukawa–Tsuno equation to this substituent effect on the equilibrium constants gave a remarkably larger r+ of 1.53 and a ρ of −10.6, supporting our previous conclusion that the highly electron-deficient benzylic carbocation systems are characterized by extremely high resonance demands. This r+ value, furthermore, conformed a linear relationship between the r+ value and the relative stability of the unsubstituted member of the respective benzylic carbocations, clearly demonstrating a continuous spectrum of varying resonance demands characteristic of the stabilities of carbocations. The π-delocalization of the positive charge into the aryl π-system increases with the destabilization of a carbocation by the α-substituent(s) linked to the central carbon. In addition, the r+ value of 1.53 for 1-aryl-2,2,2-trifluoroethyl cations was found to be in complete agreement with that for the solvolysis of 1-aryl-2,2,2-trifluoroethyl tosylates in 80% aq acetone. This reveals that the r+ value observed for this solvolysis must be the intrinsic resonance demand of a highly electron-deficient cationic transition state in the SN1 ionizing process. The identity of the r+ value was consistent with our previous observation for other benzylic carbocation systems, indicating that the degree of the π-delocalization of the positive charge is identical between the cationic transition state and an intermediate cation for all benzylic systems, which cover a wide range of reactivity and stability of the carbocation. This leads us to the conclusion that the geometry of the transition state in the ionizing process of the SN1 solvolysis, which is a highly endothermic reaction, closely resembles the high-energy product, an intermediate cation.
Mass-Spectrometric Study on Ion-Molecule Reactions of CF3+with PhX (X = F, Cl, Br, I) at Near-Thermal Energies
Authors: Tsuji Masaharu , Aizawa Masato , Oda Erika , Nishimura Yukio
Published: June 2006

The branching ratios of product ions for the reactions of CF3+ with PhX (X = F, Cl, Br, I) have been determined by using an ion-beam apparatus. The main reaction channels are electrophilic addition to a benzene ring, followed by HF and HX elimination, and X− abstraction reaction leading to phenyl cation. Charge transfer reaction leading to the parent cation was found only for PhI with the lowest ionization potential. Semi-empirical MNDO calculations of heats of formation of various intermediates and products were carried out to explore possible reaction mechanisms.
The Effect of Fused Rings on the Spectral and Electrochemical Properties of Bis-Fused 1,4-Diacetyl-1,4-dihydropyrazines
Authors: Kobayashi Tomoshige , Yamamoto Shin-ya , Kato Hiroshi
Published: June 2006

A series of 1,4-diacetyl-1,4-dihydropyrazines fused with two bornene, cyclopentene, and cyclohexene rings were prepared by the reduction of the corresponding pyrazines with zinc powder in the presence of acetic anhydride. Cyclic voltammetry measurements revealed that the oxidation potentials of the dihydropyrazines decrease in the order of cyclohexene-, bornene-, and cyclopentene-fused derivatives. This trend is in harmony with that of the bathochromic shifts in their UV absorptions.
Spectroscopy and Photophysics of O2 in the Neighborhood of the Dissociation Limit in Rare Gas Solids
Authors: Koda Seiichiro , Kajihara Hideo
Published: June 2006

The energy levels, potentials and relaxation mechanism of O2 doped in rare gas (Ar, Kr) and N2 solids in the neighborhood of the dissociation limit have been studied by means of absorption and emission spectroscopy. The environmental effects of the solids on the energy level shift are not large, but the cage effect is important in considering the relaxation mechanism following the laser irradiation. The efficient cross-relaxation among nested Herzberg states and specific energy transfer dependent on the energy gap between relevant levels, in particular from A′ state to c state, have been found. Due to the very slow vibrational relaxation, vibrationally excited O2 molecules have been accumulated to a high concentration in the solid. Based on the B–X transition energy values from the vibrationally excited O2 molecules, the B state potential curve has been determined. This shows that the cage effect retards the atomic dissociation in the B state.
Reaction Kinetics in a Microemulsion Medium IV. Hexacyanoferrate(III)–Iodide Reaction in Water/Aerosol-OT/Heptane Microemulsion and Mixed Solvents
Authors: Mukherjee Kallol , Mukherjee Dulal Chandra , Moulik Satya Priya
Published: June 2006

The kinetics of the reaction between [Fe(CN)6]3− and I− was studied in a W/O microemulsion (Water/AOT/Heptane at different [Water]/[Amphiphile] mole ratios) and in mixed water–organic media (water–formamide, water–ethylene glycol, and water–dioxane). The pseudo-first-order rate constants were observed to radically increase in microemulsion media with a [Water]/[AOT] mole ratio below 6. At a mole ratio of 5.4, the rate constant was found to be about 20-fold greater than that in water. At a constant mole ratio, the rate constant was witnessed to be independent of [AOT]. In all mixed media, the rate decreased with increasing proportion of the nonaqueous solvent. The ionic-strength effect on the reaction did not obey either the modified Brønsted–Bjerrum or Brønsted–Bjerrum–Pitzer relations in the studied nonaqueous media, except for ethylene glycol. This disagreement is very prominent in the studied W/O microemulsion medium at [Water]/[AOT] ω = 9.1. The activation parameters for the pseudo-first-order reaction in all of the studied media suggested distinct difference of the microemulsion from other solvents. A reasonable compensation between ΔH‡ and ΔS‡ i.e., the isokinetic effect, was observed.
Active Control of the Relative Population of 3P0 Fine-State in the Glow Discharge of a Supersonic Ar Beam
Authors: Midorikawa Ryotaro , Ohoyama Hiroshi , Imura Kohei , Kasai Toshio
Published: June 2006

An active control for changing the relative population of the 3P0 fine-state of Ar* in a supersonic beam was investigated in a glow discharge by adding a small amount of foreign gases to pure Ar gas. The Ar* mean velocity was determined to be constant at major positions of the time profile, except for a rise and the decay of the beam for all gas mixtures, and also pure Ar. The relative population of 3P0 decreased with the discharge potential for the addition of ethylene, cyclohexane, and benzene. However, the addition of N2 and CH4 and pure Ar, did not show such a 3P0 decrease. These dissimilar behaviors of the foreign mixed gases could be interpreted based on a difference in the ionization potential of the molecules. A useful application of this population control is discussed.
Crystal and Molecular Structures of Hypervalent Thia/Selena-pentalenes
Authors: Iwasaki Fujiko , Manabe Noriko , Nishiyama Hideyuki , Takada Kiwamu , Yasui Masanori , Kusamiya Motoyuki , Matsumura Noboru
Published: June 2006

X-Ray structure analyses were performed on the 2,3,4,5-tetrahydro-3,4-dimethylene-2,5-bis(4-chlorophenylimino)-1,6,6aλ4-trithia-3,4-diazapentalene (5), 2,5-bis(4-chlorophenylimino)-6aλ4-thia-1,6-diselena-3,4-diazapentalene derivative (6) and 2,5-bis(phenylimino)-1,6-dithia-6aλ4-selena-3,4-diazapentalene derivative (7). The lengths of the S–S bonds (mean value of 2.401 Å) for 5 and those of the Se–S bonds (mean value of 2.501 Å) for 6 and 7 are longer than that of the normal S–S or Se–S single bond (2.08 and 2.21 Å for S–S and Se–S bonds, respectively) by about 15%, which shows the hypervalent character of these S–S or Se–S bonds. In molecule 5, a difference in the two S–S bonds (2.488 and 2.314 Å) is considered to be a reflection of the feature of a weak hypervalent bond, which is very liable with effects of the environment, such as substituents or packing. The same tendency was observed for molecule 6. The crystal structures of 5 and 6, both of which are p-Cl-phenylimino derivatives, are isomorphous with each other. The crystal structure of 7, a phenylimino derivative, is different from those of 5 and 6, and two Se–S bonds of 7 are almost similar. The diffraction intensities of 5 were measured by a Weissenberg-diffractometer with imaging-plates, because only very small crystals were obtained, the intensities of which could not be measured by a conventional four-circle diffractometer with a rotating anode generator.
Structures and Formation Mechanism of Novel Metal–Carbene Complexes Derived from Hypervalent Thiadiselenadiazapentalenes
Authors: Iwasaki Fujiko , Nishiyama Hideyuki , Yasui Masanori , Kusamiya Motoyuki , Matsumura Noboru
Published: June 2006

2,3,4,5-Tetrahydro-3,4-dimethylene-2,5-bis(4-chlorophenylimino)-6aλ4-thia-1,6-diselena-3,4-diazapentalene (6), which contains a hypervalent sulfur atom, has been found to give novel complexes by treating with [Pt(PPh3)4], [Pd(PPh3)4], and [RhCl(PPh3)3]. X-Ray investigations have revealed that the resultant complexes are novel metal–carbene complexes: {1,1′-(perhydroimidazole-1,3-diyl-κC2)bis[(4-chlorophenylimino)methaneselenolato-κ2SeSe′]}(triphenylphosphine)platinum(II) (8), {1,1′-(perhydroimidazole-1,3-diyl-κC2)bis[(4-chlorophenylimino)methaneselenolato-κ2SeSe′]}(triphenylphosphine)palladium(II) (9), and trans(P,P′)-(chloro){(perhydroimidazole-1,3-diyl-κC2)bis[(4-chrolophenylimino)methaneselenolato-κ2SeSe′]}bis(triphenylphosphine)rhodium(III) (10). The central sulfur atom in 6 was substituted by a metal atom to form metal–selenium bonds in the resultant metallapentalene framework. The structure of complex (11), obtained from thiatetraazapentalene-2,5-diselone with [Pd(PPh3)3], was also determined by an X-ray analysis. This complex was also a metal–carbene complex with a metallapentalene framework: {1,1′-(perhydropyrimidine-1,3-diyl-κC2)bis[(4-chlorophenylimino)methaneselenolato-κ2SeSe′]}(triphenylphosphine)palladium(II) (11). The final R values are 0.038, 0.034, 0.046, and 0.032 for the 4494, 4234, 3919, and 4451 observed reflections for 8, 9, 10, and 11, respectively. The fact that similar metal–carbene complexes with a metallapentalene framework were obtained from both thiadiselenadiazapentalenes and thiatetraazapentalene-2,5-dithione/diselones confirms the previously proposed formation mechanism of these metal–carbene complexes.
Acceleration of Deswelling of Poly(N-isopropylacrylamide) Hydrogel by the Treatment of a Freeze-Dry and Hydration Process
Authors: Kato Norihiro , Takahashi Fujio
Published: June 2006

The deswelling rate of a thermally-sensitive gel consisting of poly(N-isopropylacrylamide) crosslinked by 4% N,N′-methylenebisacrylamide (MBA) was accelerated at above the lower critical solution temperature (LCST) by the treatment of a freeze-dry and hydration process (freeze-dry treatment); it was roughly 102 times faster than the gel without a freeze-dry treatment. The values of the apparent activation energy (Ea’s) for the conventional gel crosslinked by 2 and 4% MBA was roughly 140 kJ mol−1 each, and those for freeze-dry treated gel crosslinked by 2, 4, and 10% MBA were 24, 25, and 12 kJ mol−1, respectively. An SEM photomicrograph showed that the freeze-dry treatment made the gel porous. The freeze-dry treated gel exhibited a weaker shrinking force, and showed easy expansion compared with the conventional gel. An expansion of the diffusion area of water and a decrease of the thickness of the surface layer for a macroporous gel could be the reason for the increase in the deswelling rate.
Determination of the Acid Strength of Binary Oxide Catalysts Using Temperature-Programmed Desorption of Pyridine
Authors: Satsuma Atsushi , Westi Yenni , Kamiya Yuichi , Hattori Tadashi , Murakami Yuichi
Published: June 2006

The temperature-programmed desorption of pyridine (Py-TPD) was performed for measuring the acid strength and acid amount of binary oxide catalysts. First, the optimum measurement conditions were determined by comparing the TPD spectra with the infrared spectra of adsorbed pyridine measured under the same conditions in order to minimize the shift in the desorption temperature and contribution of physically absorbed and/or weakly held pyridine. The following conditions were found to be optimum: purging at 423 K for 2 h, W/F (W, sample weight; F, flow rate of the carrier) of 100 mg/150 cm 3 min −1, and a heating rate of 5 K min−1. This method was applied then to a series of binary mixed oxide catalysts. The amount of desorbed pyridine was 15—24% of the full coverage of pyridine on the catalyst surface with few exceptions. The highest acid strength, determined from the Py-TPD spectra, was well-correlated to that determined from a color change of Hammett indicators. The potential of the Py-TPD for determining the acid strength and the acid amount on binary oxide catalysts is discussed.
Excitation Energy Dependence of Transient Absorptions of [N,N′-o-Phenylenebis(salicylideneaminato)]cobalt(II) in Dmf Solution
Authors: Ohashi Yukako
Published: June 2006

[N,N′-o-Phenylenebis(salicylideneaminato)]cobalt(II), [Co(saloph)], forms two solvated complexes in the dmf solution; that is [Co(saloph)]·dmf at higher temperature and [Co(saloph)]·2dmf at lower temperature. The transient absorptions of the two species were measured in the present work with irradiation of the 532 nm- and 355 nm-light. For [Co(saloph)]·2dmf, the intensity change of the transient absorption induced by the 532 nm-excitation was ca. 5 times larger than that induced by the 355 nm-excitation, although the spectra was the same. By contrast, for the transient absorption of [Co(saloph)]·dmf, no dependence on the excitation wavelength was found with respect to the spectra, the absorption intensity or the decay rates. A quantum calculation of the electronic excited states was carried out by ZINDO model. Taking into consideration the calculated results, the observed differences between the excitation-wavelength dependence of the transient absorptions are discussed.
Mechanism of Isotopic Exchange for Cs+/*Cs+, Sr2+/*Sr2+, and Co2+/*Co2+ on Cerium(IV) and Tin(IV) Antimonates Particles
Authors: El-Naggar Ibrahim Mohamed , Zakaria Essam Saleh , Aly Hisham Fouad
Published: June 2006

Self-diffusion coefficients () for Cs+, Sr2+, and Co2+ ions in cerium(IV) antimonate and tin(IV) antimonate have been investigated under conditions of particle diffusion and the limited batch technique for these ions in solutions of different acidity. The effect of heat treatment on the rate of isotopic exchange reactions on both materials was also studied. Values for the diffusion coefficients, activation energy, and entropy of activation have been evaluated. The data obtained have been compared with those reported for other organic and inorganic exchangers, which give some information regarding the mechanism of ion exchange on the surface of the ion exchange materials.
Spectral Studies and In Vitro Antimicrobial Activity of New Organotin(IV) Complexes of Schiff Bases Derived from Amino Acids
Authors: Nath Mala , Yadav Rakesh
Published: June 2006

Some new di- and triphenyltin(IV) complexes of the general formulae Ph2SnL and Ph3SnL′, where H2L/HL′ = Schiff bases derived from the condensation of 2-hydroxy-1-naphthaldehyde (H2L) and benzaldehyde (HL′) with glycine (H2L-1/HL′-1), Dl-α-alanine (H2L-2/HL′-2), l-methionine (H2L-3/HL′-3), Dl-valine (H2L-4/HL′-4), d-phenylalanine (H2L-5/HL′-5), 2-aminobutyric acid (H2L-6/HL′-6), and l-leucine (H2L-7/HL′-7), have been synthesized and characterized by elemental analyses, molar conductance, electronic, infrared and far-infrared, multinuclear magnetic resonance (1H, 13C, and 117Sn), and 119Sn Mössbauer studies. Thermal decomposition of a few complexes using TG, DTG, and DTA techniques indicates the formation of SnO2 as a residue. The complexes have also been tested in vitro against bacteria [Streptococcus faecalis, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus Penicillin resistance (2500 units)] and fungi [Candida albicans, Cryptococcus neoformans, Sporotrichum schenckii, Trichophyton mentagrophytes, and Aspergillus fumigatus]. All of the complexes show remarkable activity.
Fluorescent Sensors for Molecules. Guest-Responsive Monomer and Excimer Fluorescence of 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-Bis(2-naphthylsulfonyl)-γ-cyclodextrins
Authors: Hamada Fumio , Minato Shingo , Osa Tetsuo , Ueno Akihiko
Published: June 2006

Flexible hosts, 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-bis(2-naphthylsulfonyl)-γ-cyclodextrins (γ-1, γ-2, γ-3, and γ-4, respectively) were used as fluorescent sensors with which a variety of organic compounds were detected by naphthalene excimer and monomer emissions. In a 10 vol% ethylene glycol aqueous solution, γ-1 exhibits almost pure monomer fluorescence while γ-2, γ-3, and γ-4 exhibit both monomer and excimer emissions. The intensities of the emissions changed upon addition of guest species, particularly in the case of γ-2 and γ-3, and the guest-induced intensity variations were used as sensitivity factors of the sensors. When (−)-borneol (5), cyclohexanol (6), cyclododecanol (7), and 1-adamantanecarboxylic acid (8) were added to each host solution, γ-2, γ-3, and γ-4 increased the excimer emission intensity but decreased the monomer one, the absolute intensity variations being 6 < 5 ≈ 8 < 7. When geraniol (9), nerol (10), and (−)-menthol (11) were added, the hosts decreased intensities in both monomer and excimer emissions for 9 and 10 while their emission variations for 11 were similar to those of 5. For steroids such as cholic acid (12), deoxycholic acid (13), chenodeoxycholic acid (14), and ursodeoxycholic acid (15), γ-4 showed depression in the excimer emission and enhancement in the monomer one while γ-2 and γ-3 showed complicated features in which the excimer emission was enhanced with the order of 15 < 14 < 13 ≈ 12 but the monomer one was depressed or enhanced depending on the hosts. All these data demonstrate that the hosts can be used as sensors for molecular recognition.
Kinetics and Mechanism for the Formation and Dissociation Reactions of 21-(4-Nitrobenzyl)-5,10,15,20-tetrakis(4-sulfonatophenyl)-23H-porphyrinatozinc(II) and -cadmium(II)
Authors: Tabata Masaaki , Ishimi Hiroaki
Published: June 2006

The incorporation reaction of zinc(II) and cadmium(II) into 21-(4-nitrobenzyl)-5,10,15,20-tetrakis(4-sulfonatophenyl)-23H-porphyrin (NO2Bz(Htpps)4−; HP4−) and the dissociation reaction of the metalloporphyrins ([MP]3−) have been studied spectrophotometrically at I = 0.1 mol dm−3 (NaNO3). The formation rate of the metalloporphyrins is expressed by the following equation: d[MP3−]/dt = kfM[M2+][HP4−]+kfMOH[MOH+][HP4−]-kdMP[MP3−][H+]. The rate constants and the activation parameters of the reaction were found to be kfZn = (4.86 ± 0.06) × 102 mol−1 dm3 s−1 (25 °C), ΔH‡ = 62.1 ± 1.6 kJ mol−1, and ΔS‡ = 14.8 ± 5.3 J mol−1 K−1; kfZnOH = (6.39 ± 0.14) × 103 mol−1 dm3 s−1 (25 °C), ΔH‡ = 22.8 ± 0.9 kJ mol−1, and ΔS‡ = −90.2 ± 3.1 J mol−1 K−1; kdZnP = 122.3 ± 2.3 mol−1 dm3 s−1 (25 °C), ΔH‡ = 19.8 ± 2.2kJ mol−1, and ΔS‡ = −139 ± 18 J mol−1 K−1 for zinc(II) and kfCd = (1.17 ± 0.02) × 105 mol−1 dm3 s−1 (25 °C), ΔH‡ = 42.5 ± 1.3 kJ mol−1, and ΔS‡ = −5.3 ± 4.2 J mol−1 K−1; kdCdP = (2.51 ± 0.04) × 107 mol−1 dm3 s−1 (25 °C), ΔH‡ = 14.6 ± 0.5 kJ mol−1, and ΔS‡ = −54.3 ± 1.7 J mol−1 K−1 for cadmium(II).

Nitrobenzyl group lowers the basicity of porphyrin. The effect of the lowered basicity appeared strongly in the following order for the formation rate and equilibrium constants of the metalloporphyrins: Cd2+ < Zn2+ < [ZnOH]+. A hydrogen-bond formation between [ZnOH]+ and the pyrrole proton in NO2Bz(Htpps)4− is proposed for the reaction based on the larger rate constant than the water-exchange rate constant enhanced by the hydroxide ion bound to zinc(II), the small activation enthalpy, the negative activation entropy, and the dependence of porphyrin basicity.
Polarographic Study on the Stabilization of Copper(I) State by Macrocyclic Triamine with an Aid of Monodentate π-Ligand
Authors: Kodama Mutsuo
Published: June 2006

Formation equilibria of ternary copper(I)-macrocyclic triamine ([11]aneN3, [12]aneN3, iso[12]aneN3, and [12]aneN3S) complexes with monodentate π-ligand (SCN−, CH3CN, or imidazole) were studied by the polarographic method. The copper(I)-macrocyclic triamine complexes in solutions containing an excess monodentate π-ligand were found to produce a polarogram consisting of two separate reduction steps of equal height. The chemical equilibria for the formation of the 1 : 1 : 1 ratio copper(I) mixed ligand complexes including macrocyclic triamine and π-ligand were determined by studying the effects of solution pH and concentrations of macrocyclic triamine and π-ligand on the half-wave potential of the 2nd reduction step, which appears at more negative potentials. The eleven-membered macrocyclic triamine, [11]aneN3, forms the most thermodynamically stable copper(I) mixed ligand complex, [CuIL(A)]1−b. The formation constants for 1 : 1 : 1 ratio copper(II), macrocyclic triamine, and monodentate π-ligand were determined potentiometrically by studying the effects of SCN−, CH3CN, or imidazole concentration on the formation equilibrium of copper(II)-macrocyclic triamine complexes.
Synthesis and Characterization of Water-Soluble, All-Inorganic Composition, Dawson-Type Trisubstituted Heteropolytungstates. Effect of Alkali Metal Countercations (Li, Na, K, and Cs) on the P2W15Nb3O629− Polyoxoanion
Authors: Nomiya Kenji , Nozaki Chika , Miyazawa Kohji , Shimizu Yasushi , Takayama Toshio , Nomura Keiichi
Published: June 2006

The water-soluble form of the Dawson-type trisubstituted tungstoheteropolyanion, B-α-P2W15Nb3O629−, was synthesized as its nona alkali-metal salts of Li, K, and Cs. Analytically pure compounds, obtained as homogeneous colorless solids, had nonahydrate for the nonalithium (Li9) salt, tetrahydrate for the nonasodium (Na9) salt, trihydrate for the nonapotassium (K9) salt and trihydrate for the nonacaesium (Cs9) salt, respectively, after each was dried overnight at room temperature under 10−3—10−4 Torr. TG/DTA analyses show that they can be made with 25 water for the Li9 salt, 23 water for the Na9 salt, 9 water for the K9 salt, and 8 water for the Cs9 salt under atmospheric conditions. A compositional characterization was accomplished by complete elemental analyses and TG/DTA, and structural characterization was achieved by a combination of FT-IR and variable-temperature solid-state 31P NMR and by both 31P and 183W NMR measurements at room temperature in D2O and DMSO-d6 solutions. The amount of hydrated waters, solubility in solvents and ease of crystallization were significantly influenced by the alkali-metal countercations. These cation-dependent properties are useful for selecting polyoxoanion precursor favorable to the crystallization of P2W15Nb3O629−-supported organometallic complexes. The effects of the cations (Li, K, Na, and Cs) on the P2W15Nb3O629− were observed as different hydrated structures of the polyoxoanion and its cation-dependent thermal stability in the solid state by a combination of TG/DTA and FT-IR measurements, and also as a spectral change of the downfiled 31P signal due to interactions of the polyoxoanion with the countercations and/or with hydrated waters by variable-temperature (VT) solid-state GHD/MAS 31P NMR spectroscopy.
Solvent Extraction of Several Divalent Metal Ions with 4-Isopropyltropolone into Chloroform in the Absence and Presence of Trioctylphosphine Oxide
Authors: Sekine Tatsuya , Ninomiya Ichiro , Tebakari Masayuki , Noro Junji
Published: June 2006

The solvent extraction of divalent metal ions, manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), and cadmium(II) in aqueous 0.1 mol dm−3 sodium nitrate solutions with 2-hydroxy-4-(1-methylethyl)-2,4,6-cycloheptatrien-1-one (4-isopropyltropolone; Hipt) into chloroform was studied in the absence and presence of trioctylphosphine oxide (TOPO). When the concentration of metal ions (M2+) was 1 × 10−5 to 1 × 10−4 mol dm−3 in the initial aqueous solutions, the extracted species of the metal ions in the absence of TOPO were only the mononuclear complex, M(ipt)2, with copper(II); these species were both the mononuclear complex, M(ipt)2, and the mononuclear self-adduct complex, M(ipt)2·Hipt, with zinc(II); they were both the mononuclear complex, M(ipt)2, and the dinuclear complex, M2(ipt)4, with cobalt(II) and cadmium(II); and they were predominantly the dinuclear complex, M2(ipt)4, with nickel(II) and manganese(II). It was also found that the extraction of manganese(II), cobalt(II), nickel(II), zinc(II), and cadmiun(II) was enhanced when TOPO was added into the organic phase. This was explained in terms of the formation of mononuclear adduct complex, M(ipt)2TOPO, from M(ipt)2, M(ipt)2·Hipt, and/or M2(ipt)4. The extraction constants for those species were determined. The extractability and the tendency to form dinuclear complexes are discussed.
Asymmetric Synthesis of Organosilicon Compounds Using a C2 Chiral Auxiliary
Authors: Kobayashi Kimiko , Kato Takayuki , Unno Masafumi , Masuda Shinji
Published: June 2006

Optically active silanes were synthesized by a novel asymmetric synthesis which involved the diastereoselective ring-opening reaction of 1,3-dioxa-2-silacycloheptanes bearing a C2 chiral auxiliary with Grignard reagents, followed by a lithium aluminum hydride (LiAlH4) reduction. (R)-Ethylmethylphenylsilane and (R)-methylphenylpropylsilane were derived in 93%ee and 98%ee, respectively. The preparation of the other optical silanes is also described. The maximum rotations of some of them have been determined by 1H NMR and/or capillary GC methods. A mechanism for a diastereoselective ring-opening reaction is proposed based on the stereochemical results.
Substituent Effects on the Solvolysis of 1,1-Diphenyl-2,2,2-trifluoroethyl Tosylates: Comparison between Symmetrically Disubstituted and Monosubstituted Systems
Authors: Fujio Mizue , Morimoto Hiroshi , Kim Hyun-Joong , Tsuno Yuho
Published: June 2006

The solvolysis rates of 1-(substituted phenyl)-1-phenyl-2,2,2-trifluoroethyl and 1,1-bis(substituted phenyl)-2,2,2-trifluoroethyl tosylates or bromides were conductimetrically measured at 25.0 °C in 80% aqueous ethanol. The substituent effects on these solvolyses were analyzed on the basis of the Yukawa–Tsuno equation. The former monosubstituted diphenyl system did not show a single linear Yukawa–Tsuno correlation; a bilinear correlation was observed with ρ = −4.33 and r = 1.26 for substituents more deactivating than p-methyl, and ρ = −6.08 and r = 1.45 for the substituent range more reactive than 3,4-dimethyl. The bilinear correlation was explicable in terms of the changing coplanarity of the respective benzene rings.

On the other hand, the symmetrically disubstituted diphenyl substrates gave an excellent linear Yukawa–Tsuno correlation for the whole substituent range with a ρ value of −8.3/2 and an r value of 1.19. The substituent effect correlation leads to the conclusion that the two aryl rings in this symmetrical system remain in the equivalent propeller-shape conformation with respect to deviations from coplanarity with the carbenium ion center in the transition state.