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Dependence of NH3-SCR reaction rate on O2 partial pressure was investigated at 473 K over Cu ion-exchanged MOR, MFI, CHA and *BEA zeolites with varying “Cu density in micropores”. Among the zeolites, Cu–*BEA zeolite demonstrated promising potential as an effective catalyst for NH3-SCR over a wide range of O2 partial pressure.

Cu–zeolite catalysts are promising for the selective catalytic reduction of nitrogen oxides using ammonia as the reducing agent (NH3-SCR) but rational catalyst design requires a better understanding of the effect of zeolite topology on NH3-SCR activity at low temperatures. Herein, the catalytic activities of Cu–zeolites with different topologies (MOR, MFI, *BEA, and CHA) and various Cu ion-exchange levels for low-temperature NH3-SCR (at 473 K) were investigated. To allow comparisons of catalytic activities among Cu–zeolites with different topologies, the “cation density in micropores” of zeolites was defined, and a similar cation density in micropores was achieved for each topology by varying the Si/Al ratio. The dependence of the turnover frequencies at 473 K on the Cu density in micropores was strongly influenced by the parent zeolite, although the widely accepted reaction mechanism was independent of the zeolite topology. MOR zeolites showed low turnover frequencies irrespective of the Cu density in micropores. In contrast, *BEA zeolites exhibited extremely high turnover frequencies at a low Cu density in micropores, but the turnover frequencies did not increase considerably at higher Cu densities in micropores. Time-resolved UV-vis measurements were used to calculate the rate of the reduction–reoxidation cycle for Cu ions during model transient reactions over different zeolites. It was clearly demonstrated that the turnover frequency for NH3-SCR was dominated by the Cu+ to Cu2+ reoxidation cycle, regardless of the zeolite topology and the Cu density in micropores. The reoxidation of Cu ions on *BEA zeolites was rapid, even at low Cu densities in micropores, and the effect of increasing the mean Cu density in micropores was small. It was also suggested that Cu2+ interacted with zeolite framework oxygen, even under NH3 flow. Thus, it is likely that the local structure and distribution of ion-exchange sites for divalent ions affect the reoxidation cycle during NH3-SCR. It is proposed that development of Cu–zeolite catalysts that have both high reaction rates for NH3-SCR and low Cu volumetric densities can be achieved by considering the zeolite topology.

ERI zeolite is a small-pore zeolite that has been rarely explored as a catalyst in the selective catalytic reduction of NOx with ammonia (NH3-SCR) as the performance has been considered to be limited by its insufficient hydrothermal stability. We herein report that a fast-synthesized ERI zeolite, which can be synthesized in only 2 h at a high temperature (210 °C), shows much enhanced hydrothermal stability than the conventional ERI zeolite due to the presence of less silanol defects. The fast-synthesized ERI zeolite with an optimal copper loading (equaling a Cu/Al ratio of 0.20) is demonstrated to be highly active in the NH3-SCR, which even rivals Cu-SSZ-13 – the benchmark NH3-SCR catalyst. Various characterization techniques are employed to characterize the copper species in the fast-synthesized ERI zeolite in order to understand its high hydrothermal stability and NH3-SCR activity. The results indicate that the copper species sitting at different locations exhibit variant hydrothermal stability and NH3-SCR activity, suggesting the importance of the interplay between the copper species and the zeolite host. With a deep understanding into the structure-activity relationship, this work presents that the fast-synthesized ERI zeolite holds potential to emerge as a robust NH3-SCR catalyst for emission control.

Dependence of NH

A multiple templating strategy using both bulky and small organic structure-directing agents (SDAs) was adapted for AFX zeolite synthesis in order to control the distribution of aluminum and phosphorus. An AFX zeolite with an Si/Al ratio of 4.8 was obtained in the presence of a bulky and rigid SDA, N,N,N',N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium cation (TEBOP2+), and co-existing Na+ cations. The use of a tetramethylammonium cation (Me4N+) as the SDA instead of Na+ provided AFX zeolite with a middle Si/Al ratio of 7.9. Elemental analysis and 13C and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy suggested that TEBOP2+ existed in the wide aft cage in both AFX zeolites, while the higher Si/Al ratio was derived from the lower charge density of Me4N+ occupying the narrow gme cage. We also attempted to control the distribution of phosphorus in phosphorus-modified AFX zeolite. The large tetraethylphosphonium cation (Et4P+) and small tetramethylphosphonium cation (Me4P+) were selectively incorporated into aft and gme cages during the hydrothermal synthesis, respectively. As a result, phosphorus oxide with different polymerization degrees were formed by calcination treatment according to the size of the cage occupied by the phosphorus-modifying agents (P-MAs). This direct phosphorus modification using alkylphosphonium was characterized by elemental analysis and 13C, 27Al, and 31P MAS NMR and two-dimensional (2D) 31P–27Al heteronuclear correlation NMR spectroscopies.

The direct decomposition of nitric oxide (NO) into nitrogen and oxygen was successfully catalyzed on copper- and iron-exchanged ZSM-5 zeolites through microwave (MW) rapid heating. Under the developed methodology, NO is first concentrated in the microcage of the zeolite structure and the adsorbed NO is subsequently decomposed by efficient energy irradiation of MWs without desorption of NO as intact molecules. Lower temperatures favor NO adsorption/concentration inside the zeolite cavities. Under the investigated conditions, the coexistence of oxygen and water vapor exert little adverse influence on the adsorption properties. Rapid and short-term heating of zeolite catalysts under MW irradiation allow the reaction to be repeated at higher temperatures without considerable deterioration of catalytic performance. With the optimization of the adsorption sequences at lower temperatures, heating, and the catalytic reaction for adequate duration, we expect the developed two-step NO decomposition process to find suitable practical applications.

This paper introduces a joint industries&ndash, academia&ndash, academia research project started by researchers in several automobile companies and universities working on a single theme. Our first target was to find a zeolite for NH3-SCR, that is, zeolite mining. Zeolite AFX, having the same topology of SSZ-16, was found to be the one of the zeolites. SSZ-16 can be synthesized by using an organic structure-directing agent such as 1,1&prime, tetramethylenebis(1-azonia-4-azabicyclo[2.2.2]octane, Dab-4, resulting in the formation of Al-rich SSZ-16 with Si/Al below five. We found that AFX crystallized by use of N,N,N&prime, N&prime, tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium ion, called TEBOP in this study, had the same analog as SSZ-16 having Si/Al around six and a smaller particle size than SSZ-16. The AFX demonstrated a high performance for NH3-SCR as the zeolitic support to load a large number of divalent Cu ionic species with high hydrothermal stability.

Selective catalytic reduction (SCR) of NOx with zeolite catalysts has been reported as the most promising technique for the removal of NOx from diesel engine exhaust. In this research, SSZ-13 zeolite doped with Cu species was synthesized by dry gel conversion (DGC) method and applied as a catalyst for NH3-SCR. The obtained Cu/SSZ-13 was characterized using X-ray diffraction (XRD), energy-dispersive X-ray (EDX), Scanning Electron Microscopy (SEM), NMR spectroscopy, ESR spectroscopy, nitrogen adsorption. Cu/SSZ-13 synthesized by DGC method has higher crystallinity and porosity than that synthesized by conventional hydrothermal synthesis (HTS) method. Due to its higher crystallinity and porosity, higher amount of Cu ions was introduced into SSZ-13 synthesized by DGC method, leading to a higher catalytic performance for the SCR of NOx compared with Cu/SSZ-13 prepared by HTS. In addition, Cu/SSZ-13 synthesized by DGC method showed higher hydrothermal stability.

Five 2-substituted 6/7-methoxy-l,4-benzodioxan-7/6-carbaldehydes and 6-methoxy-l,4-benzodioxan-7-carbaldehyde available for the syntheses of insecticidal neolignan analogs were prepared from 4/3-benzyloxy-3/4-hydroxybenzaldehydes and l,4-benzodioxan-6-carbaldehyde, respectively.

金沢大学医薬保健研究域保健学系, Objective: Lymphoscintigraphy is an effective method for detecting sentinel lymph nodes (SLNs). However, the rate and degree of SLN detection is not uniform. We quantified SLNs detected with lymphoscintigraphy, and investigated correlations with factors that may influence detection. We then attempted to predict SLN metastasis from lymph node counts, comparing the predictions to subsequent biopsy results. Methods: We assessed lymph node counts in 100 breast cancer patients in whom a single SLN was detected with a fixed lymphoscintigraphy procedure. We examined correlations between the counts and factors known to influence lymphoscintigraphic SLN detection (age, body mass index, tumor size, and presence or absence of metastasis), and determined reference values (lymph node counts of 10.0, 19.4 and 53.0) which were used to predict SLN metastasis in 100 subsequent patients. The predictions were then compared with the SLN biopsy findings. Results: SLN counts correlated strongly with the presence or absence of metastasis, with metastasis-positive lymph nodes showing significantly lower counts than negative nodes (p < 0.001). Prediction of SLN metastasis achieved a 100% positive predictive value at a reference value of 10.0, and a 100% negative predictive value at a reference value of 53.0. At a reference value of 19.4, the sensitivity, specificity, and diagnostic accuracy were 77.8, 73.2, and 74.0%, respectively. Conclusions: The SLN counts detected with lymphoscintigraphy were significantly lower in metastasis-positive lymph nodes than in metastasis-negative lymph nodes. This suggests that prediction of SLN metastasis in breast cancer is possible using lymphoscintigraphy. © 2010 The Japanese Society of Nuclear Medicine.

Reactions of Mo(II)-tetraphosphine complex [MoCl2(κ4-P4)] (2; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with a series of small molecules have been investigated. Thus, treatment of 2 with alkynes RC CR′ (R = Ph, R′ = H; R = p-tolyl, R′ = H; R = Me, R′ = Ph) in benzene or toluene gave neutral mono(alkyne) complexes [MoCl2(RC CR′)(κ3-P4)] containing tridentate P4 ligand, which were converted to cationic complexes [MoCl(RC CR′)(κ4-P4)]Cl having tetradentate P4 ligand upon dissolution into CDCl3 or CD2Cl2. The latter complexes were available directly from the reactions of 2 with the alkynes in CH2Cl2. On the other hand, treatment of 2 with 1 equiv. of XyNC (Xy = 2,6-Me2C6H3) afforded a seven-coordinate mono(isocyanide) complex [MoCl2(XyNC)(κ4-P4)] (7), which reacted further with XyNC to give a cationic bis(isocyanide) complex [MoCl(XyNC)2(κ4-P4)]Cl (8). From the reaction of 2 with CO, a mono(carbonyl) complex [MoCl2(CO)(κ4-P4)] (9) was obtained as a sole isolable product. Reaction of 9 with XyNC afforded [MoCl(CO)(XyNC)(κ4-P4)]Cl (10a) having a pentagonal–bipyramidal geometry with axial CO and XyNC ligands, whereas that of 7 with CO resulted in the formation of a mixture of 10a and its isomer 10b containing axial CO and Cl ligands. Structures of 7 and 9 as well as [MoCl(XyNC)2(κ4-P4)][PF6](8′) and [MoCl(CO)(XyNC)(κ4-P4)][PF6] (10a′) derived by the anion metathesis from 8 and 10a, respectively, were determined in detail by the X-ray crystallography.

We evaluated the predictive value of bone marrow accumulation of technetium (Tc)-99m tetrofosmin in patients with breast cancer for distant metastases in comparison with conventional prognostic factors such as clinical stage, tumor size, axillary lymph node (Node) status, and estrogen receptor (ER) status.Bone marrow scans with Tc-99m tetrofosmin were performed on 64 patients with breast cancer who had no clinical evidence of distant metastases. Accumulation in the femoral marrow was classified into four patterns, no detectable, lower, higher, and intensively higher. Higher or intensively higher pattern was interpreted as abnormal. Thirty-six patients with abnormal accumulation (marrow-positive group) and 28 patients without abnormal accumulation (marrow-negative group) were enrolled in the follow-up study. The mean length of observation after scans was approximately 3 years. The predictive value of femoral marrow status and conventional prognostic factors for distant metastases was evaluated by statistical analysis.Univariate analysis showed a significantly higher incidence of subsequent bone metastases (36%4%; P0.005), and distant metastases (69%18%; P0.001) in the marrow-positive group when compared with the marrow-negative group. Conventional prognostic factors except tumor size were also significantly associated with the development of distant metastases; 77% in clinical stage 339% in clinical stages 1, 2, P0.05; 64% in Node-positive29% in Node-negative, P0.01; and 70% in ER negative27% in ER positive, P0.005. These conventional factors were not significantly associated with bone metastases. The Cox proportional hazard ratio for bone metastases was markedly higher in femoral marrow status (hazard ratio=11.07). The distant metastases-free survival was significantly reduced in ER negative (P0.0005), Node-positive (P=0.0215), and clinical stage 3 patients (P=0.0163). On the other hand, a more marked difference was observed in the femoral marrow status (P0.0001). The hazard ratio for distant metastases was 2.44 in clinical stage, 2.74 in tumor size, 2.74 in Node, and 3.68 in ER, which were each independent prognostic factors associated with distant metastases. However, femoral marrow status was markedly associated with distant metastases (hazard ratio=5.27).Bone marrow accumulation of Tc-99m tetrofosmin can be a promising prognostic factor independent of conventional prognostic factors for predicting development of not only bone metastases but also distant metastases in breast cancer.

Reactions of a sulfido- and thiolato-bridged diiridium complex [(Cp∗Ir)2(μ-S)(μ-SCH2CH2CN)2] (Cp∗ = η5-C5Me5) with [(Cp∗MCl)2(μ-Cl)2] (M = Ir, Rh) afforded the sulfido- and thiolato-bridged trinuclear clusters [(Cp∗M)(Cp∗Ir)2(μ3-S)(μ2-SCH2CH2CN)2(μ2-Cl)]Cl (4: M = Ir, 5: M = Rh). Upon treatment with XyNC (Xy = 2,6-Me2C6H3) in the presence of KPF6 at 60 °C, 4 was converted into a mixture of a mononuclear XyNC complex [Cp∗Ir(SCH2CH2CN)(CNXy)2][PF6] (6) and a dinuclear XyNC complex [{Cp∗Ir(CNXy)}2(μ-S)(μ-SCH2CH2CN)][PF6] (7). On the other hand, reactions of 4 and 5 with methyl propiolate in the presence of KPF6 at 60 °C resulted in the formation of a cyclic trimer of the alkyne 1,3,5-C6H3(COOMe)3 as the sole detectable organic product. The reactions proceeded catalytically with retention of the cluster cores of 4 and 5, whereby the activity of the former was much higher than that of the latter.

Crystallization and structure formation of poly(ethylene oxide)–poly(ɛ-caprolactone) block copolymers (PEG–PCL) in which the melting temperatures of the components are close to each other were elucidated using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. The diblock copolymers with 33, 46 and 59 wt% of PEG composition formed ordinary single spherulites similar to those of PCL homopolymers, while concentric double-circled spherulites appeared for the PCL–PEG–PCL triblock copolymer with 66 wt% PEG composition as observed previously. For the diblock copolymers, despite of the ordinary appearance of the single spherulites, the DSC thermograms and the WAXD patterns indicated the crystallization of PEG as well as PCL. The time-resolved SAXS profiles for the diblock copolymers showed that long spacings of the crystal lamellae decreased stepwise in the crystallization process. Synthesizing these results for the single spherulites, it was concluded that PCL crystallized first followed by the crystallization of PEG with preservation of the PCL crystal lamellar structure. This means that PEG must crystallize within confined space between the formerly formed PCL crystal lamellae. Such confined crystallization of PEG caused the suppressed melting temperature, crystallinity and crystallization rate especially in the smaller PEG compositions. In the melting process of the diblock copolymers, it was observed that the PEG component first melted with a stepwise increase in the long spacing.

A Mo(0) complex containing a new tetraphosphine ligand [Mo( P 4 )(dppe)] ( 1 ; P 4 = meso-o -C 6 H 4 (PPhCH 2 CH 2 PPh 2 ) 2 , dppe = Ph 2 PCH 2 CH 2 PPh 2 ) reacted with CO 2 (1 atm) at 60 °C in benzene to give a Mo(0) carbonyl complex fac -[Mo(CO)(η 3 - P 4 O)(dppe)] ( 2 ), where the O abstraction from CO 2 by one terminal P atom in P 4 takes place to give the dangling P( O)Ph 2 moiety together with the coordinated CO. On the other hand, reaction of 1 with TolNCS (Tol = m -MeC 6 H 4 ) in benzene at 60 °C resulted in the incorporation of three TolNCS molecules to the Mo center, forming a Mo(0) isocyanide–isothiocyanate complex trans , mer -[Mo(TolNC) 2 (η 2 -TolNCS)(η 3 - P 4 S)] ( 4 ), where the S abstraction occurs from two TolNCS molecules by P 4 and dppe to give the η 3 - P 4 S ligand and free dppe S, respectively, together with two coordinated TolNC molecules. The remaining site of the Mo center is occupied by the third TolNCS ligating at the C S bond in an η 2 -manner. The X-ray analysis has been undertaken to determine the detailed structures for 2 and 4 .

Direct decomposition of nitric oxide (NO) into nitrogen and oxygen was catalyzed on a copper-loaded zeolite catalyst with high conversion (>80%) by a newly proposed microwave pulsatile heating system, even in the presence of water vapor, while no reaction took place in a conventional reactor using an electric furnace under the same reaction conditions.

New preparation procedures of Ru-Sn/Y zeolite catalysts for acetic acid (methyl acetate) formation from methanol alone in the heterogeneous gas–solid phase were investigated. The catalysts were prepared with the following three procedures: (i) the evacuation of [Ru(NH3)6]3+/Y to form Ru-metal particles in the zeolite cavities; (ii) the reaction of Cl2 gas and Ru-metal particles to form RuCln species in the cavities; and (iii) introducing SnCl2 as a vapor. The methanol conversion at 473 K gave methyl acetate and hydrogen after a characteristic induction period. Stationary activity was sustained with a slight decrease until 200 h from the reaction start. The yield of methyl acetate was dependent on the conditions of the Cl2 and Sn treatment, and reached up to 10.9% with the catalyst prepared under the optimum condition. The characterization results of the catalyst at each preparation and reaction stage suggested that the active species were formed during the induction period in the supercages of the zeolites and were Rum-Snn species.

The addition of methanol to allyl alcohol was investigated with metal oxides and zeolites catalysts in the liquid phase. 3-Methoxy-1-propanol was selectively formed with MgO, ZrO2 and Al2O3, while zeolites gave 2-methoxy-1-propanol. This feature suggests that the generation of a methoxide ion on basic sites is an important step. The highest yield, 23.6%, was obtained with MgO treated in a hydrogen flow.

A Ru/mordenite (Ru/M) catalyst with catalytically-active ruthenium species retained in the mordenite pores has been prepared by the ion-exchange of Na-mordenite with [Ru(NH 3 ) 6 ] 3+ , followed by a very mild thermal treatment. While extended X-ray absorption fine structure (EXAFS) analysis showed the presence of both Ru–N and Ru–Ru bonds, HRTEM photographs evidenced the absence of metal particles larger than the diameter of a mordenite pore. The remaining NH 3 ligand was also observed from the characteristic IR bands appearing at 1640 and 1356 cm −1 ; the IR spectrum of adsorbed CO indicated the presence of multicarbonyl-type surface species (such as Ru n + (CO) 3 ), consistent with the well-dispersed or coordinatively-unsaturated nature of ruthenium species. After the complete preparation procedure, a high degree of crystallinity was maintained for mordenite (XRD), and the decrease of S BET from 362 to 313 m 2 g −1 ensured the existence of ruthenium species in the mordenite pores. It was demonstrated that, by using this catalyst, N -methylation of melamine with methanol was able to proceed in a moderately shape-selective manner (suppression of the formation of N,N ′ ,N ″-tri-methylated melamine ( 3 ) as compared to that of N -methylated or N,N ′-di-methylated melamine ( 1 or 2 )), which is in harmony with the sizes of relevant molecules relative to the size of a mordenite pore.

Vertebral artery dissection and thrombosis propagation causing neurologic sequelae is a rare complication of minor neck injury. Partial fracture of the transverse foramen of the third cervical vertebral body (C3) is uncommon. The authors report a case of vertebral artery injury and delayed midbrain infarction after an unusual fracture of only the upper half of the transverse foramen of C3, noted initially by bone scintigraphy. No other fracture was noted. A minor penetrating skin wound of the neck was not thought to be related to the fracture of the transverse foramen. The right lateral inferior edge of C2 was believed to have compressed the upper half of the transverse foramen of C3 by lateral hyperflexion. Innate laxity of the cervical spine at the level of C2 with respect to C3 in pediatric patients supports this belief.

We describe a patient with acute aortic dissection involving the right iliac artery and causing right lower leg ischemia that was successfully treated by Wallstent placement. Emergent endovascular treatment may be the treatment of choice in the patient with acute leg ischemia caused by the involvement of the iliac artery by aortic dissection.

Single-step conversion of methanol into acetic acid (methyl acetate) has been found possible by use of Ru(II)-Sn(II) hetero-bimetallic catalysts. By analyzing the homogeneous solution reactions, reaction paths are elucidated. Applications of lacunary heteropolyanions as model oxide ligands and of Y-type zeolite as a unique support for the gas-phase reaction are presented.

Mechanistic studies have been made of the unique one-pot conversion of methanol into acetic acid (and/or methyl acetate due to rapid esterification) with [Ru(SnCl 3 ) 5 (PPh 3 )] 3- as catalyst. Addition of Cl - ion promoted the formation of methyl formate relative to methyl acetate, but scarcely changed their total rate of formation. Further, the activation energies for their formation were virtually identical (≈76 kJ mol -1 ). No 13 C was incorporated into methyl acetate even when the reaction was performed under a 13 CO atmosphere, indicating that the conversion of methanol into methyl acetate does not involve carbonylation. The effect of the addition of Cl - ion on the reaction of formaldehyde was similar to that when using methanol as substrate, but quite different activation energies were obtained for the formation of methyl acetate (27.9 kJ mol -1 ) and methyl formate (40.6 kJ mol -1 ). The results are in accord with rate-determining dehydrogenation of methanol to formaldehyde (as a common intermediate), which is then converted competitively into acetic acid and methyl formate with different activation energies. The effect of added free Cl - ion for both substrates suggests the presence of a pre-equilibrium dissociation of Cl - from the co-ordinated SnCl 3 - , which is required for the formation of acetic acid but not for methyl formate. A possible reaction scheme is presented, in which reductive elimination of methyl formate is competitive with that of acetic acid.

Studies of methanol dehydrogenation in the liquid phase with Cu-based solid catalysts have shown (i) the product (methylal) is totally different from that in the gas-solid phase reaction (methyl formate) even using the same catalyst, and (ii) the differences in the calcination atmosphere of the catalyst (N2 versus dry air) have a marked effect on the product selectivity (methylal versus methyl formate). These results are in contrast to the gas-phase reaction (com-monly methyl formate). he results are discussed on the basis of surface species characterized with XPS and XRD.

The Ru II -Sn II heteronuclear cluster complex [Ru(SnCl 3 ) 5 (PPh 3 )] 3− has been found to be catalytically active for the isomerization of methyl formate to acetic acid. The initial reaction rate showed a first order dependence on the catalyst concentration, and showed a saturation curve for the reactant concentration in its high-concentration region. Extra addition of PPh 3 and Cl − ion considerably retarded the reaction with almost linear relationships between the reciprocal of initial rates and the concentration of additives. A rate equation derived from these kinetic data indicates the presence of a pre-equilibrium of dual ligand dissociation from the catalyst (PPh 3 from Ru II and Cl − from Sn II ) to form the catalyst-reactant complex, where the relatively soft Ru II and the hard Sn II interact simultaneously with the soft CO group and hard OCH 3 group of methyl formate, respectively. It is postulated that such a multi-center interaction in this cluster system facilitates the overall rearrangement of CH 3 group (from O atom to C atom) to realize the isomerization of methyl formate to acetic acid without CO atmosphere or iodide promoter, but with an activation energy comparable to that for Rh or Ni catalyst which requires both of them.

We report on a patient with bilateral stress fractures of the tibia who subsequently showed classic biochemical features of oncogenic osteomalacia. Conventional radiographs were normal. MR imaging revealed symmetric, bilateral, band-like low-signal lesions perpendicular to the medial cortex of the tibiae and corresponding to the only lesions subsequently seen on the bone scan. A maxillary sinus lesion was subsequently detected and surgically removed resulting in prompt alleviation of symptoms and normalization of hypophosphatemia and low 1,25-(OH)2 vitamin D3. The lesion was pathologically diagnosed as a hemangiopericytoma-like tumor. Patients with oncogenic osteomalacia may present with stress fractures limited to the tibia, as seen in athletes. The clue to the real diagnosis lies in paying close attention to the serum phosphate levels, especially in patients suffering generalized symptoms of weakness and not given to unusual physical activity.

New Mo and W tetraphosphine-dihalide complexes [MX2(kappa4-P4)] (2, MX=MoCl, MoBr, WBr; P4=meso-o-C6H4(PPhCH2CH2PPh2)2) with uncommon trigonal-prismatic geometries have been prepared. Treatment of ethyl diazoacetate with 2 (MX=MoCl) resulted in catalytic carbenoid-group coupling to give diethyl maleate and fumarate, whereas reactions of 2 with trimethylsilyldiazoalkane formed the diazoalkane complexes trans-[MX(NN=CHSiMe3)-(kappa4-P4)]+ (3+) and cis,mer-[MoCl2(NN=CHSiMe3)(kappa3-P4)]. The molecular structures of 2 (MX=MoCl) and 3[PF6] (MX=WBr) were crystallographically determined.

Purpose To perform the largest in vivo dosimetry study for interstitial brachytherapy yet to be undertaken using a new radiophotoluminescence glass dosimeter (RPLGD) in patients with pelvic malignancy and to study the limits of contemporary planning software based on the results. Patients and Methods Sixty-six patients with pelvic malignancy were treated with high-dose-rate interstitial brachytherapy, including prostate ( n = 26), gynecological ( n = 35), and miscellaneous ( n = 5). Doses for a total of 1004 points were measured by RPLGDs and calculated with planning software in the following locations: rectum ( n = 549), urethra ( n = 415), vagina ( n = 25), and perineum ( n = 15). Compatibility (measured dose/calculated dose) was analyzed according to dosimeter location. Results The compatibility for all dosimeters was 0.98 ± 0.23, stratified by location: rectum, 0.99 ± 0.20; urethra, 0.96 ± 0.26; vagina, 0.91 ± 0.08; and perineum, 1.25 ± 0.32. Conclusions Deviations between measured and calculated doses for the rectum and urethra were greater than 20%, which is attributable to the independent movements of these organs and the applicators. Missing corrections for inhomogeneity are responsible for the 9% negative shift near the vaginal cylinder (specific gravity=1.24), whereas neglect of transit dose contributes to the 25% positive shift in the perineal dose. Dose deviation of >20% for nontarget organs should be taken into account in the planning process. Further development of planning software and a real-time dosimetry system are necessary to use the current findings and to achieve adaptive dose delivery.

The largest in vivo dosimetry study for interstitial brachytherapy yet examined was performed using new radiophotoluminescence glass dosimeters (RPLGDs). Based on the results, a dose prescription technique achieving high reproducibility and eliminating large hyperdose sleeves was studied.For 61 head-and-neck cancer patients who underwent high-dose-rate interstitial brachytherapy, new RPLGDs were used for an in vivo study. The Paris System was used for implant. An arbitrary isodose surface was selected for dose prescription. Locations of 83 dosimeters were categorized as on target (n = 52) or on nontarget organ (n = 31) and were also scaled according to % basal dose isodose surface (% BDIS). Compatibility (measured dose/calculated dose) was analyzed according to location. The hyperdose sleeve was assessed in terms of prescription surface expressed in % BDIS.The spread of compatibilities was larger for on nontarget organ (1.06 +/- 0.32) than for on target (0.87 +/- 0.17, p = 0.01). Within on target RPLGDs, compatibility on95% BDIS (0.95 +/- 0.10) was better than onor =95% BDIS (0.84 +/- 0.18, p = 0.02). The number of patients with diameter of hyperdose sleeveor =10 mm was increased with a dose prescription to77% BDIS (p = 0.046). For nontarget organs, the maximal positive deviation was 84% of the calculated dose.Dose prescription is recommended to77% and95% BDIS for reproducibility and elimination of excessive hyperdose sleeve. For organs at risk, radioprotection should be considered even when calculated dose seems sufficiently low. Further development of planning software is necessary to prevent overestimation.

A series of Ru/mordenite (Ru/M) catalysts have been prepared by the ionexchange of Na-mordenite with [Ru(NH3)6]3+, followed by a mild thermal treatment for various periods. XRD measurement of each catalyst ensured that a high degree of crystallinity of mordenite was maintained, and that no formation of crystalline metallic ruthenium occurred. The trend of H/Ru value determined from chemisorption of H2 suggests that the reduction-aggregation took place progressively during the calcination, where the latter process preceded the former. Actually, in EXAFS spectra, the intensity of the peak for Ru-Ru bond became gradually stronger relative to that for Ru-N bond, and SBET value was decreased in the same order. Since HR-TEM photographs gave no metal particles comparable to or larger than the diameter of a mordenite pore, the extent of aggregation is not so large, which is consistent with the lack of crystalline metallic ruthenium. By use of Ru/M catalysts, moderate shape selectivty was observed in the N-methylation of melamine with methanol (suppression of the formation of N,N′, N″-tri-methylated melamine as compared to that of N-methylated or N,N′-di-methylated melamine), which is in harmony with the sizes of relevant molecules relative to the size of a mordenite pore. As the calcination condition became severe, catalytic activity decreased steeply. This fact suggests that molecular or quite high dispersion is demanded for the catalytic site, and that grown metallic ruthenium would prevent the motion and the reaction of melamine in the pores. The reactions with diols (ethylene glycol, diethylene glycol) were slower, and were accompanied by considerable side reactions. The trend of reactivity among the three substrates implies the importance of steric factors, and appreciable formation of N,N′, N″-tri-alkylated melamine for ethylene glycol suggests that the catalytic sites on the external surface contribute more than for methanol.

The Fuel Reprocessing Test Plant at JAERI was operated during the period of 1968-1969 to gain experiences of the fuel reprocessing.Fuel elements reprocessed were irradiated in the JRR-3 reactor up to about 700MWD/ton and cooled for 87-300 days.The purpose of this paper is to discribe the measured results of airborne radioiodine released in each stage of chemical processing and discuss collection efficiency of the charcoal impregnated filter paper for radioiodine in the presence of process off gas such as NO, NO2, NH3, HNO3 and solvent encountered during the fuel reprocessing.

The Fuel Reprocessing Test Plant at JAERI was operated during the period of 1968-1969 to gain experiences of the fuel reprocessing.Fuel elements reprocessed were irradiated in the JRR-3 reactor up to about 700MWD/ton and cooled for 87-300 days. Therefore, krypton-85 is the most dominant radionuclide in the long lived gaseous fission products and the major part of krypton-85 in the fuel is discharged from the stack to atmosphere in the process of uranium dissolution.The purpouse of the paper is to describe the measured results of gaseous krypton-85 released in each chemical processing and also to discuss the performance of krypton-85 gas monitor, in particular the relationship of counting rate and the inner pressure of the krypton-85 sampler. The measured activity of krypton-85 released was in fairly good agreement with the calculated inventory.

Transient thermal stresses of weld heat-affected zones were evaluated by a rigid frame apparatus as shown in Fig. 1. Round bar specimens set into the rigid frame were put to thermal cycles by induction heating and transient thermal stresses were recorded on the oscillograph connected to the loadcell. Four kinds of steel of different mechanical and metallurgical properties were used. The types of applied thermal cycle were single thermal cycle, multi thermal cycles of constant peak temperature type, increasing- or decreasing- peak temperature type (see Figs. 11 a, b).Test results of the transient thermal stress as a function of temperature are shown in Figs. 6 thru 9, Figs. 12 thru 16, Figs. 18 and 19. Residual stresses as a function of peak temperature applied are shown in Fig. 10 for single thermal cycles and in Fig. 17 for multi thermal cycles. The transient thermal stresses and residual stresses are influenced by the mechanical and metallurgical properties of steels used.Analysis of mechanical strains during thermal cycles was made using a connected bar-spring model as illustrated in Fig.2 b and a long rectangular plate as in Fig. 23 on they-axis of which an instantaneous plane heat source was applied. The analysis revealed the difference in mechanical strains between the model and the rectangular plate. The transient thermal stresses or elastic strains in plastic zones of the rectangular plate were approximately estimated by both-ends-fixed bar analogy.

The Fuel Reprocessing Test Plant in JAERI was operated during the period of 1968-1969 to gain experiences of the fuel reprocessing. The fuel elements reprocessed were irradiated in the JRR-3 up to about 700MWD/ton and cooled for 87-300 days.Tritium is produced by ternary fission and is one of the important nuclides to be monitored during the reprocessing of the highly irradiated fuels, because it is easily released into the off-gas line and difficult to be trapped before discharging to the atmosphere.In this paper, the results of tritium monitoring at the stack are described. It was found that tritium discharged from the stack during the reprocessing was about 1% of the total inventory and its concentration in air was about 1×10-8μCi/cm3.