A novel silica-based column packing for reversed-phase HPLC of basic compounds

A novel bonded phase for reversed-phase HPLC was synthesized in two steps. Octylamine was first reacted with beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (beta -ECTS) and then the intermediate product was coupled onto porous silica. The prepared packing was characterized by elemental analysis, solid-state C-13 NMR and Fourier transform infrared (FT-IR). Chromatographic evaluations were carried out by using a mixture of organic compounds including acidic, basic and neutral analytes and methanol-water as binary mobile phase. The results showed that the stationary phase has excellent chromatographic properties and is resistant to hydrolysis between pH = 2 similar to 8. It can be used efficiently for the separation of basic compounds.

Epoxidation of propylene on NaCl-modified silver catalysts with air as the oxidant

Propylene epoxidation by air was carried out on NaCl-modified silver (NaCl/Ag) catalysts, and the catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The effects of NaCl loadings, propylene to oxygen ratio, and the reaction time on the catalytic performance were investigated. It was found that the addition of NaCl to silver significantly increases the propylene oxide (PO) selectivity. The PO yield has a maximum when the NaCl loading is about 10 wt.%. Also 12.4% conversion of propylene and 31.6% selectivity to PO are obtained on the NaCl/Ag (10 wt.%) catalyst at 350 degreesC, space velocity 1.8 x 10(4) h(-1) and C3H6:O-2 = 1:2. XPS and XRD characterizations show that AgCl formed on the silver catalyst was favorable to propylene epoxidation. A compound with highly oxidized Ag ion was also found, which may be effective for the reaction. (C) 2002 Elsevier Science B.V. All rights reserved.

Ammonia synthesis over Ru/C catalysts with different carbon supports promoted by barium and potassium compounds

Ammonia synthesis over ruthenium catalysts supported on different carbon materials using Ba or K compounds as promoters has been investigated. Ba(NO3)(2), KOH, and KNO3 are used as the promoter or promoter precursor, and activated carbon (AC), activated carbon fiber (ACF). and carbon molecular sieve (CMS) are used as the support. The activity measurement for ammonia synthesis was carried out in a flow micro-reactor under mild conditions: 350-450 degreesC and 3.0 MPa. Results show that KOH promoter was more effective than KNO3. and that Ba(NO3)(2) was the most effective promoter among the three. The roles of promoters can be divided into the electronic modification of ruthenium, the neutralization of surface functional groups on the carbon support and the ruthenium precursor. The catalyst with AC as the support gave the highest ammonia concentration in the effluent among the supports used, while the catalyst with ACF as the support showed the highest turnover-frequency (TOF) value. It seems that the larger particles of Ru on the carbon supports are more active for ammonia synthesis in terms of TOF value. (C) 2001 Elsevier Science B.V. All rights reserved.

A two-stage process with temperature-shift for enhanced anthocyanin production in strawberry cell suspension cultures

A two-stage process with temperature-shift has been developed to enhance the anthocyanin yield in suspension cultures of strawberry cells. The effect of the temperature-shift interval and the shift-time point was investigated for the optimization of this strategy. In this process, strawberry cells were grown at 30 degrees C (the optimum temperature for cell growth) for a certain period as the first stage, with the temperature shifted to a lower temperature for the second stage. In response to the temperature shift-down, anthocyanin synthesis was stimulated and a higher content could be achieved than that at both boundary temperatures but cell growth was suppressed. When the lower boundary temperature was decreased, cell growth was lowered and a delayed, sustained maximum anthocyanin content was achieved. Anthocyanin synthesis was strongly influenced by the shift-time point but cell growth was not. Consequently, the maximum anthocyanin content of 2.7 mg.g-fresh cell(-1) was obtained on day 9 by a temperature-shift from 30 degrees C, after 3-d culture, to 15 degrees C. The highest anthocyanin yield of 318 mg.L-1 on day 12 was achieved when the temperature was shifted from 30 degrees C, after 5-d culture, to 20 degrees C. For a global optimization of both the yield and productivity, the optimum anthocyanin yield and productivity of 272 mg.L-1 and 30.2 mg.L-1.d(-1) on day 9 were achieved by a two-stage culture with a temperature-shift from 30 degrees C after 3 d to 20 degrees C.

汉字形音义加工时间进程的事件相关电位（ERP）研究

The time-courses of orthographic, phonological and semantic processing of Chinese characters were investigated systematically with multi-channel event-related potentials (ERPs). New evidences concerning whether phonology or semantics is processed first and whether phonology mediates semantic access were obtained, supporting and developing the new concept of repetition, overlapping, and alternating processing in Chinese character recognition. Statistic parameter mapping based on physiological double dissociation has been developed. Seven experiments were conducted: I) deciding which type of structure, left-right or non-left-right, the character displayed on the screen was; 2) deciding whether or not there was a vowel/a/in the pronunciation of the character; 3) deciding which classification, natural object or non-natural object, the character was; 4) deciding which color, red or green, the character was; 5) deciding which color, red or green, the non-character was; 6) fixing on the non-character; 7) fixing on the crosslet. The main results are: 1. N240 and P240:N240 and P240 localized at occipital and prefrontal respectively were found in experiments 1, 2, 3, and 4, but not in experiments 5, 6, or 7. The difference between the former 4 and the latter 3 experiments was only their stimuli: the former's were true Chinese characters while the latter's were non-characters or crosslet. Thus Chinese characters were related to these two components, which reflected unique processing of Chinese characters peaking at about 240 msec. 2. Basic visual feature analysis: In comparison with experiment 7 there was a common cognitive process in experiments 1, 2, 4, and 6 - basic visual feature analysis. The corresponding ERP amplitude increase in most sites started from about 60 msec. 3. Orthography: The ERP differences located at the main processing area of orthography (occipital) between experiments 1, 2, 3, 4 and experiment 5 started from about 130 msec. This was the category difference between Chinese characters and non-characters, which revealed that orthographic processing started from about 130 msec. The ERP differences between the experiments 1, 2, 3 and the experiment 4 occurred in 210-250, 230-240, and 190-250 msec respectively, suggesting orthography was processed again. These were the differences between language and non-language tasks, which revealed a higher level processing than that in the above mentioned 130 msec. All the phenomena imply that the orthographic processing does not finished in one time of processing; the second time of processing is not a simple repetition, but a higher level one. 4. Phonology: The ERPs of experiment 2 (phonological task) were significantly stronger than those of experiment 3 (semantic task) at the main processing areas of phonology (temporal and left prefrontal) starting from about 270 msec, which revealed phonologic processing. The ERP differences at left frontal between experiment 2 and experiment 1 (orthographic task) started from about 250 msec. When comparing phonological task with experiment 4 (character color decision), the ERP differences at left temporal and prefrontal started from about 220 msec. Thus phonological processing may start before 220 msec. 5. Semantic: The ERPs of experiment 3 (semantic task) were significantly stronger than those of experiment 2 (phonological task) at the main processing areas of semantics (parietal and occipital) starting from about 290 msec, which revealed semantic processing. The ERP differences at these areas between experiment 3 and experiment 4 (character color decision) started from about 270 msec. The ERP differences between experiment 3 and experiment 1 (orthographic task) started from about 260 msec. Thus semantic processing may start before 260 msec. 6. Overlapping of phonological and semantic processing: From about 270 to 350 msec, the ERPs of experiment 2 (phonological task) were significantly larger than those of experiment 3 (semantic task) at the main processing areas of phonology (temporal and left prefrontal); while from about 290-360 msec, the ERPs of experiment 3 were significantly larger than those of experiment 2 at the main processing areas of semantics (frontal, parietal, and occipital). Thus phonological processing may start earlier than semantic and their time-courses may alternate, which reveals parallel processing. 7. Semantic processing needs part phonology: When experiment 1 (orthographic task) served as baseline, the ERPs of experiment 2 and 3 (phonological and semantic tasks) significantly increased at the main processing areas of phonology (left temporal and frontal) starting from about 250 msec. The ERPs of experiment 3, besides, increased significantly at the main processing areas of semantics (parietal and frontal) starting from about 260 msec. When experiment 4 (character color decision) served as baseline, the ERPs of experiment 2 and 3 significantly increased at phonological areas (left temporal and frontal) starting from about 220 msec. The ERPs of experiment 3, similarly, increased significantly at semantic areas (parietal and frontal) starting from about270 msec. Hence, before semantic processing, a part of phonological information may be required. The conclusion could be got from above results in the present experimental conditions: 1. The basic visual feature processing starts from about 60 msec; 2. Orthographic processing starts from about 130 msec, and repeats at about 240 msec. The second processing is not simple repetition of the first one, but a higher level processing; 3. Phonological processing begins earlier than semantic, and their time-courses overlap; 4. Before semantic processing, a part of phonological information may be required; 5. The repetition, overlapping, and alternating of the orthographic, phonological and semantic processing of Chinese characters could exist in cognition. Thus the problem of whether phonology mediates semantics access is not a simple, but a complicated issue.

Effect of variations in acid properties of HZSM-5 on the coking behavior and reaction stability in butene aromatization

In order to investigate the effect of acid properties on the coke behavior and stability of butene aromatization, we prepared the AHZSM-5 samples with various acid properties by the methods of hydrothernial treatment and K addition. The reaction of butene aromatization was carried out at 350 degrees C and 0.5 MPa in a continuous flow fixed bed. The characterization of the fresh/coked catalysts with NH3-TPD, N-2 adsorption-desorption measurement, and TG techniques has shown that a large amount of acid sites (high acid density) of the AHZMS-5 catalyst can cause a large quantity of coke deposit and serious channel blockage, and so result in a rapid loss of aromatization activity. On the contrary, after a great reduction in strong acid sites of AHZSM-5 catalyst resulting from some K-modification, the presence of only many weak acid sites also could not lessen the formation of coke nor improve the reaction stability of butene aromatization. Interestingly, the simultaneous reduction in the strong and weak acid sites to a desirable level by hydrothermal treating the AHZSM-5 catalyst at a proper temperature can effectively suppress the coke formation and channel blockage, and thus improve its olefin aromatization stability. (c) 2005 Elsevier B.V. All rights reserved.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 Elsevier B.V. All rights reserved.

Determination of heat capacities and thermodynamic properties of 2-(chloromethylthio)benzothiazole by an adiabatic calorimeter

The molar heat capacities of 2-(chloromethylthio)benzothiazole (molecular formula C8H6ClNS2, CA registry no. 28908-00-1) were measured with an adiabatic calorimeter in the temperature range between (80 and 350) K. The construction and procedures of the calorimeter were described in detail. The performance of the calorimetric apparatus was evaluated by heat capacity measurements on alpha-Al2O3. The deviation of experiment heat capacities from the corresponding smoothed values lies within 0.3%, whereas the uncertainty is within +/-0.5%, compared with that of the recommended reference data over the whole experimental temperature range. A fusion transition was found from the C-p-T curve of 2-(chloromethylthio)benzothiazole. The melting temperature and the molar enthalpy and entropy of fusion of the compound were determined to be T-m = (315.11 +/- 0.04) K, Delta(fus)H(m) = (17.02 +/- 0.03) kJ(.)mol(-1), and Delta(fus)S(m) = (54.04 +/- 0.05) J(.)mol(-1.)K(-1), respectively. The thermodynamic functions (H-T - H-298.15) and (S-T - S-298.15) were also derived from the heat capacity data. The molar fraction purity of the 2-(chloromethylthio)benzothiazole sample used in the present calorimetric study was determined to be 99.21 by fraction melting.

New route for light olefins production from chloromethane over HSAPO-34 molecular sieve

HSAPO-34 molecular sieve was employed in chloromethane conversion and showed high performance in activity and selectivity in production of light olefins. Our detailed IR investigation allowed the identification of the active sites and the adsorbed species and demonstrated that the conversion started from 350 degrees C with alkoxy group as the intermediate. The fixed-bed catalytic testing evidenced that in the range of 350-500 degrees C, 70-80% of chloromethane was transferred to ethylene, propylene and butenes. Increasing reaction temperature favors the conversion and enhances the yield of lighter olefins. A very important reversible phenomenon, the breaking of Al-O-P bonds upon adsorption of HCl, a main product of reaction to generate a large amount of P-OH groups and the recovery of Al-O-P upon removal of HCI was revealed. (c) 2005 Elsevier B.V. All rights reserved.