New Development in Chemistry of Hypervalent Radicals Approach from the Gas-phase
气相高价自由基化学的新进展
基本信息
- 批准号:18350009
- 负责人:
- 金额:$ 10.25万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:2006
- 资助国家:日本
- 起止时间:2006 至 2007
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
In order to reveal the role of hypervalent radicals in chemical reactions including those in biological chemistry, we have studied on the following three subjects.1. The electronic structures of Na-2^-(H_2O)_n (n〓6), which have a similar loosely-bounded electron to NH_4 have been investigated by a photoelectron spectroscopy (PES) to examine the solvation of sodium aggregates in small water clusters, From the analysis of the PES bands for the transitions from the anion to the neutral ground and first excited states derived from Na_2 (1^1Σ_g^+) and Na_2(1^3Σ_u^+) it is found that the Na_2-Na^+(H_2O)_n^-type electronic state grows with increasing cluster size, which can be regarded as a sign of the solvation of Na_2 with ionization of the hydrated Na.2. Ionization potentials (IPs) of NR_4(CH_3OH)_m (NH_3)_n radicals produced by an ArF excimer laser photolysis of ammonia-methanol mixed clusters are determined by the photoionization threshold measurements. The observed IPs show the different evolutions with increasing the number of ammonia and methanol solvents. We have also examined the formation and relaxation dynamics of NH_4(CH_3OH)_m(NH_3)_n clusters produced by photolysis of ammonia-methanol mixed neutral clusters using a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ion, NH_4(CH_3OH)_m(NH_3)_n, the kinetic model is constructed.3. A photodissociation spectrometer, containing a spray ionization source and a temperature-variable multipoleion trap, has been constructed to examine the structure and reactivity of gas phase biological molecular ionsat various temperatures. Ultraviolet (UV) and infrared (IR) photodissociation spectra of protonatedalanyltryptophan (Ala-TrpH+) and tryptophanylglycine (Trp-GlyH+) have been investigated to examine the effect of proton on the electronic structure and reactivity of the dipeptides.
为了揭示高价自由基在包括生物化学在内的化学反应中的作用,我们对以下三个方面进行了研究。的电子结构Na-2 ^ - (H_2O) _n”(n〓6),有一个类似的松散的电子NH_4调查了光电子能谱(PES)检查钠的溶解水聚集在小集群,从分析PES乐队的转变从阴离子中性点接地和第一激发态源自Na_2(1 ^ 1Σ_g ^ +)和Na_2(1 ^ 3Σ_u ^ +)发现,Na_2-Na ^ + (H_2O) _n”^型电子态随着集群规模的不断扩大,这可以看作是Na_2的溶剂化与水合na的电离的标志。利用光电离阈值测定了ArF准分子激光光解氨-甲醇混合团簇所产生的NR_4(CH_3OH)_m (NH_3)_n自由基的电离势。随着氨溶剂和甲醇溶剂数量的增加,所观察到的IPs有不同的演化规律。我们还利用飞秒脉冲激光的时间分辨泵浦探测方法研究了氨-甲醇混合中性团簇光解产生的NH_4(CH_3OH)_m(NH_3)_n团簇的形成和弛豫动力学。通过对质子化簇离子NH_4(CH_3OH)_m(NH_3)_n的时间演化的详细分析,建立了动力学模型。利用喷雾电离源和变温多极阱组成的光解离谱仪,研究了气相生物分子离子在不同温度下的结构和反应性。利用紫外(UV)和红外(IR)光解光谱研究了质子对两种二肽的电子结构和反应活性的影响。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Microscopic solvation and reaction processes of metal atoms/ions in small gas-phase clusters
小气相团簇中金属原子/离子的微观溶剂化和反应过程
- DOI:
- 发表时间:2006
- 期刊:
- 影响因子:0
- 作者:Y. Kita;R. Maezono;M. Tachikawa;冨宅 喜代一
- 通讯作者:冨宅 喜代一
水クラスター中でのNa_2の溶解過程
Na_2在水团簇中的溶解过程
- DOI:
- 发表时间:2007
- 期刊:
- 影响因子:0
- 作者:Wakayama Sayaka;et al.;Akimasa Fujihara;藤原亮正;若山清香;藤原亮正;藤原亮正;若山清香;藤原亮正;前川亜耶子
- 通讯作者:前川亜耶子
Spectroscopy of cooled molecular ions in gas-phase
气相中冷却分子离子的光谱
- DOI:
- 发表时间:2007
- 期刊:
- 影响因子:0
- 作者:T. Udagawa;T. Ishimoto;H. Tokiwa;M. Tachikawa;U. Nagashima;冨宅喜代一
- 通讯作者:冨宅喜代一
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