清华的铊盐类型

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crystal_ice

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Aug 21, 2006, 11:31:04 PM8/21/06
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这是Ai-Jun Tong 他们的PAPER的摘要。

Solid-substrate and micellar-stabilized room temperature
phosphorescence of two anilinonaphthalenesulfonates
Ai-Jun Tong * , Ying-Guang Wu, Long-Di Li

Departmat of Chemistry, Ts~~~h~U niversity. Be&kg Iooo84C,h ina
Received 16 August 1995; revised 3 November 1995; accepted 12 November
1995
Abstract

Room temperature phosphorimetric studies were made on two important
fluorescent probes: 8-~linonaph~~ene-lsulfonate
(ANS) and 6-toluidinylnaphthalene-2-sulfonate (TNS). The two dyes gave
proper RTP signals using solid-substrate
room temperatnre phosphorimetry (SS-RTP) and micellar-stabilized room
temperature phosphorimetry (MS-RTP) under the
experimental conditions described in this article. The SS-RTP signals
are observed on filter paper using thallium(I) nitrate as
a heavy atom. The MS-RTP emission of the compounds is also measurable
in sodium dodecyl sulfate (SDS) micelles by
applying sodium sulfite as an oxygen scavenger and ~al~urn(I) nitrate
as a heavy atom. Light irradiation for a certain period
of time could increase the RTP intensities of ANS and TNS solutions.
Our results provide some useful information for the
RTP studies of derivatized macromolecules using ANS or TNS as
phosphorescent probes.
Keywords: 8-Anilinonaphthalene-I-sulfonate;
6-Toluidinylnaphthalene-2-sulfonateP; hosphorimetry;R oom temperaturep
hosphorimetr

crystal_ice

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Aug 21, 2006, 11:34:31 PM8/21/06
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我找到了这篇论文。铊盐的分子式是TINO3
。这里用铊盐的目的是作重原子干扰。

------------------------------

Several mineral salts such as KI, NaI, Pb(OAc),,
TlNO, were investigate as heavy atom perturbers
for introduction the SS-RTP signal of ANS. Except
for Pb(OAc),, three other salts could produce RTP
of ANS, but the RTP emission of ANS was not
stable enough especially for low ANS concentrations
when I- was used as a heavy atom perturber. Thus,
TlNO_3, was chosen in the following RTP investigations.
Fig, 2 shows the effect of TlNO_3, concentration on
the RTP emission of ANS. The RTP intensity of
ANS remains maximum when the concentrations are
higher than 0.1 M. Thus, 0.1 M TlNO_3, was used

crystal ice

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Aug 22, 2006, 11:48:02 AM8/22/06
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这是函子找的关于TINO3的资料,谢谢函子。
 

crystal ice

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Aug 22, 2006, 11:53:12 AM8/22/06
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thallium (I) nitrate 
分子式:TlNO3
半数致死量 
 LD50/ LC50 小 鼠 口 服 15mg/kg
化学性质: 无味的白色粉末状晶体,不会自燃, 但是加到火里能加速燃烧, 毒性较高,能被皮肤吸收而致中毒,易溶于水, 对鱼和其它水生生物有毒性

危险性分析
对健康的潜在危害 
thallium 是一种毒性很高的元素,它能对人体健康产生急性和慢性的危害, 它可以通过呼吸道吸入, 摄入甚至于皮肤的大量吸收而使人致死, thallium (I) nitrate能够刺激眼睛,皮肤,呼吸道,,在吸入时损害呼吸系统, 急性的和慢性的摄入可能引起胃肠 , 神经,心血管,血液, 视觉察,肝脏和肾脏系统中毒以及出现脱发现象.
 
译自 TECKCOMINCO
thallium nitrate, MATERIAL SAFETY DATA SHEET
 
作者: Araceli  2006-7-15 16:01

 

crystal_ice

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Aug 22, 2006, 11:55:17 AM8/22/06
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thallium(I) nitrate
根据美国职业安全健康管理委员会,美国政府工业保健协会,职业安全和健康国家研究中心,

提供的数据 , 皮肤与thallium(I) nitrate 暴 露 接 触
的安全极限数据为 0.1mgTL/m2( 皮肤
),高于这个数据就会被皮肤吸收,引起中毒.
知情人请核对童老师实验室的thallium(I) nitrate 溶 液 的

浓 度, 论 文 原 文 上 也 许 有, 如 果 他们使 用 的
铊 盐 溶 液 远 高 于 这 个 浓 度 ,那 么 即 使 加 到
奶 蜜 等液 体 化妆 品 中 也 很 难 被 稀
释,朱令如果每天都使用这种化妆品, 铊 盐渗
入脸部皮肤的毛细
血管,也会随血液被带到全身各组织器官,引起
急性或慢性中毒


作者: 81.203.146.* 2006-7-17 04:28

Enfamil

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Aug 22, 2006, 11:56:30 AM8/22/06
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关于 Thallium Nitrate:

http://www.state.nj.us/health/eoh/rtkweb/1841.pdf

第六页, physical data , water solubility : soluble in hot water

Enfamil

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Aug 22, 2006, 11:57:55 AM8/22/06
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http://www.state.nj.us/health/eoh/rtkweb/1841.pdf

关于thallium nitrate , 第六页中提到: water solubility: soluble
in hot water

crystal_ice

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Aug 22, 2006, 11:59:40 AM8/22/06
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毒理信息(译文)
普通信息: thallium
是一种很毒的物质,能引起急性和慢性中毒,
如果通过呼吸道,消化道及皮肤吸入足够的量,就会使人致死(达到致死量).

急性中毒症状:
皮肤和眼睛:
铊的化合物能够直接被皮肤吸收,所引起的症状与呼吸道和消化道吸入引起的症状相同.对眼睛和皮肤能产生刺激效果.

呼吸道与消化道
:如果从呼吸道与消化道吸入,铊盐化合物的毒性更大.可以刺激呼吸道甚至于使呼吸系统受到损害,急性铊中毒可以引起胃肠道出血,胃肠炎,心动过速和头痛.其它胃肠道症状还包括异常疼痛,恶心,呕吐和腹泻.
铊中毒也会影响到神经系统导致运动性共济失调
,肢体下端感觉异常,引起外微弱的外周神经炎和肌肉萎缩.神经疾病的症状表现为颤抖,脑病,颅神经方面则包括思维混乱.
死亡通常是由心脏和呼吸衰竭引起的


作者: 81.203.146.* 2006-7-17 05:47  

Enfamil

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Aug 22, 2006, 12:02:49 PM8/22/06
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在查到的有关网页上提到了, 如果溶液spill
该如何紧急处理. 我想,做实验的, 尤其是孙同学,
专门拿溶液做实验, 难道老师不怕溶液打翻?
难道老师不给她说说一般的救护知识和感染症状?

crystal_ice

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Aug 22, 2006, 12:13:15 PM8/22/06
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论文里有一张图,描述了Effect of TlNO3, conoentration on the
RTP intensities of
ANS by the SS-RTP method.

图上,画了TINO3 的 concentration 从 0 --- 0.2M 的曲线。

所以, 肯定 从 0 -- 0.2M 的CONCENTRATION 都配制过。

但 在 0.1M 的 CONCENTRATION 下,达到了最大值,
所以最后可能主要配制
0.1M 的 concentration.

这里有学化学的末?呵呵。。。

crystal_ice

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Aug 22, 2006, 12:15:29 PM8/22/06
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铊盐的浓度:

是不是说明铊盐的浓度实验过从0-0.2M.
最后选用的是0.1M?

crystal_ice

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Aug 22, 2006, 12:22:42 PM8/22/06
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清华的论文里另一个实验里
说明用到了0.25M/ml TINO3

Effects of concentrations of SDS, TlNO, and
Na,SO, were studied by a three-factors three-levels
orthogonal design array method. The optimum conditions
found are: 3 ml of 0.20 M SDS, 1 ml of 0.25 M
TlNO3, and 1 ml of 0.15 M Na,S03 mixed with
ANS and H,SO,; the solution was finally diluted to
10 ml with water.

Message has been deleted

crystal_ice

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Aug 22, 2006, 12:33:25 PM8/22/06
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我觉得有必要查一下在不同时间里清华实验室配制的铊盐溶液浓度。

看来他们做了不同浓度的对比实验,并在不同的实验中选用了不同的浓度。

假设取信孙维没有亲自配制溶液,
那如果是她取走了溶液,只能取走现成的。
第二次中毒更严重,有没有可能是取得铊盐溶液浓度更高?


在1楼的文章里,浓度大概有:
(1) 一个实验过0--0.2M/ML 的浓度。选用了 0.1M/ML
(2) 另一个实验用的是0.25M/ML的浓度。


我可能还有漏掉的,回头在看看。

Enfamil

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Aug 22, 2006, 1:10:47 PM8/22/06
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水晶的分析有些道理

crystal ice

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Aug 22, 2006, 4:05:36 PM8/22/06
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谢谢。
 
来自孙维声明:
其实化学系在实验中使用铊有很长历史了,而且有不少人在国内外相关杂志上发表论文,在97年4月我开始被调查之后,我查阅了一些文献,看到学校化学系不同人发表的论文从91年(那时我还没入学)起有若干篇(收稿日期分别为1991年10月16日,1994年12月20日,1995年8月16日,1995年10月2日,1995年11月8日和1996年2月16日),直到97年公安开始调查,化学系才禁止使用铊。我想很可能还有我没有查到的文章,或还有使用过铊却还没有发表的论文。
查),直到97年公安开始调查,化学系才禁止使用铊。我想很可能还有我没有查到的文章,或还有使用过铊却还没有发表的论文。
 
---------
现在这篇是1995年8月16日收稿的,还需要查1994年12月,1995年10月,1995年11月,和1996年2月的论文,不知是否都是这个实验实的。


 
On 8/22/06, Enfamil <enfa...@gmail.com> wrote:
水晶的分析有些道理

Enfamil

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Aug 22, 2006, 4:19:14 PM8/22/06
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from www.helpzhuling.org

Thallium (TI), a rare form of metallic element, naturally exists in the
form of compound and can be found in few minerals. There are over ten
Thallium compounds, which normally include: thallium sulfate, thallium
nitrate, thallium formate, thallium acetate, thallium carbonate,
thallium oxide, thallium phosphate, thallium chloride, thallium
bromide, thallium iodide and thallium acetate etc. All are highly
poisonous chemicals. Thallium can be used for manufacturing optical
glass and paint. Thallium sulfate was once a component of rodents and
ants killer. But since 1975, the USA has prohibited the use of thallium
in rodents or insecticide. Thallium compounds are also used as catalyst
in organic synthesis and agents for phosphorescence in analytical
chemistry.

Tsinghua University has published at least the following 3 essays since
1995:

Tong AJ, Wu YG, and Li LD: Solid-substrate and micellar-stabilized room
temperature phosphorescence of two anilinonaphthalenesulfonates. Anal
Chim Acta 1996, 322: 91-97.
Li LD, Chen YL, Zhao Y, and Tong AJ: Room-temperature phosphorescence
of dansyl chloride solution in the absence of protective medium and its
medium effect. Anal Chim Acta 1997, 341: 241-249.
Li LD, Long WQ, and Tong AJ: Determination of photophysical rate
constants for the non- protected fluid room temperature phosphorescence
of several naphthalene derivatives. Spectroc Acta Pt A-Molec Biomolec
Spectr 2001, 57: 1261-1270.

Enfamil

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Aug 22, 2006, 4:20:37 PM8/22/06
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需要查1994年12月,1995年10月,1995年11月,和1996年2月的论文,

where to find these?

crystal ice

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Aug 22, 2006, 5:15:38 PM8/22/06
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先存下几篇李隆弟1994-1997年的文章。1997年的那篇文章用了TI, 1 和 2 的文章名和 那篇文章类似,不知是否也用了,但查不到原文。
 
1. Longdi Li, Shi zhong Yang, Room Temperature Phosphorescence Properties of 27 coumarins Derivative on the Filter paper, Anal. Chim. Acta, 1994, 296(1), 99-105

2. Longdi Li, Weiguo Huang, Room Temperature Phosphorescence properties of Dansyl Chloride and Its Derivatives, Anal. Chim. Acta, 1995, 312, 345-350

3. 陈永丽,李隆弟*,童爱军, 香豆素衍生物TICT态与荧光介质效应, 分析科学学报,1996,12(4),175-180

4. Longdi Li, Yongli Chen, Yu Zhao, Aijun Tong, Room Temperature phosphorescence of Dansyl Chloride Solution in the Absence of protected Medium and its Medium Effect, Anal. Chim. Acta, 1997, 341, 241-249


 
On 8/22/06, Enfamil <enfa...@gmail.com> wrote:

crystal_ice

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Aug 22, 2006, 5:31:22 PM8/22/06
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这是收稿于1996年7月的论文。这篇文章是关于荧光效应的。用
Thallium Nitrate 作重原子微扰。
所以几乎可以推断上面的 1, 2, 3 篇
文章(都是关于荧光效应), 也用了Thallium Nitrate
作重原子微扰。

看来孙维找到的有关铊盐文章大致就是她工作过的实验室出来的。不知为何她觉得这些文章能帮助她排除嫌疑?

Room-temperature phosphorescence of dansyl chloride solution in the
absence of protective medium and its medium effect

Longdi Li, Yongli Chen, Yu Zhao and Aijun Tong

Department of Chemistry, Tsinghua University, Beijing 100084, China

Received 9 July 1996; revised 27 November 1996; accepted 16 December
1996. ; Available online 25 March 1998.


Abstract
A unique fluid room-temperature phosphorescence (RTP) method, which is
different from the RTP methods developed previously and needs no
microscopically ordered medium, is developed. The RTP emission of
dansyl chloride (DNS-Cl) and its amino acid derivatives can be induced
directly in aqueous system by the addition of thallium nitrate as heavy
atom perturber and sodium sulfite as deoxygenator, λex/λem = 326/574
nm. A good linearity between the RTP intensity and the concentration of
DNS-Cl in the range 2.0 × 10−7−1.0 × 10−5 mol/l was obtained
with a detection limit of 1.9 × 10−8 mol/l. A comparative study of
RTP of DNS-Cl in the presence of cyclodextrins (CDs), surfactant
micelle, organic solvent and bovine serum albumin (BSA) has also been
carried out. This fluid RTP emission system of DNS-Cl is very
transparent and stable, and can be modulated by different organic
solvents. The quenching behavior of RTP by BSA presents a satisfactory
linearity between the concentration of BSA and IRTP, which can be used
in the quantitative analysis of BSA.

Author Keywords: Dansyl chloride; Fluid room-temperature
phosphorescence; Medium effect

crystal_ice

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Aug 24, 2006, 12:56:23 AM8/24/06
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更正一下:
是清华的论文里另一个实验里
说明用到了1ml 的 0.25M TINO3。 M 是 mol/L 的简写。

crystal_ice

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Aug 24, 2006, 12:57:51 AM8/24/06
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更正一下:

我觉得有必要查一下在不同时间里清华实验室配制的铊盐溶液浓度。


看来他们做了不同浓度的对比实验,并在不同的实验中选用了不同的浓度。

假设取信孙维没有亲自配制溶液,
那如果是她取走了溶液,只能取走现成的。
第二次中毒更严重,有没有可能是取得铊盐溶液浓度更高?

在1楼的文章里,浓度大概有:
(1) 一个实验过0--0.2M 的浓度。选用了 0.1M
(2) 另一个实验用的是0.25M的浓度。


我可能还有漏掉的,回头在看看。 这里M 是
mol/L的简写。

crystal ice

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Aug 24, 2006, 1:14:25 AM8/24/06
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查到了1997年这篇文章

"Room-temperature phosphorescence of dansyl chloride solution in the
absence of protective medium and its medium effect"

得到如下信息:
(1) Thallium nitrate
(TINO3, CP) and sodium sulfite (Na2S03) were purchased
from Beijing Chemical Plant (China) and used
as received.

铊盐是从北京化学厂买的并按买来的直接使用。

(2) 实验里用了0.25mol/l 的浓度。

"A 2.0 ml aliquot of
0.25 mol/l T1N03 and an aliquot of 0.1 mol/l
Na2S03 (and different organic solvents or CD,
BSA solution, for studying their effects) were then
added, and filled to the mark with water."

(3)还有一个实验当TINO3的浓度为 0.05 mol/l 时,效果最好。

"The results show that the appropriate concentration of
TlNO3 and Na$Os in the system is 0.05 mol/l and
0.01 mol/l, respectively. With these concentrations,
the pH of the solution just falls in the optimum pH
range described above."

鉴于1994-1996的文章也是关于荧光的,用作重原子微调的铊盐溶液浓度应大致相同。

crystal ice

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Aug 24, 2006, 1:54:10 AM8/24/06
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relative atomic/molecular mass of Thallium Nitrate (TINO3):
266.39

solubility:
95. 5 g/litre (20 度)

参阅:

http://www.inchem.org/documents/ehc/ehc/ehc182.htm#SectionNumber:1.8

所以
1 mol/l = 266.39 g/l
论文里见到用到的最大浓度: 0.25 mol/l = 66.5975 g/l = 0.0665975 g/ml;
假如致死量是 15mg/kg, 朱令的体重是50kg, 朱令需要 至少 intake 700mg,
那是不是用她们实验室的最大浓度铊溶液下毒,需要10 ml 溶液。 这可能吗???????????

Message has been deleted

Enfamil

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Aug 24, 2006, 3:51:57 PM8/24/06
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一般认为,铊对成人最小致死量约为12mg/kg,5~7.5mg/kg的剂量即可引起儿童死亡。...朱令成为中国首位利用“互联网”寻求拯救的病人。经过几个月的诊断...这种药物可以将铊元素从体内排除。“遗憾的是...经测定,河水中含铊量高达...

www.bswz.com/Article/Print.asp?ArticleID=5636 42K 2006-7-13 -
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