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
------------------------------
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
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
http://www.state.nj.us/health/eoh/rtkweb/1841.pdf
第六页, physical data , water solubility : soluble in hot water
关于thallium nitrate , 第六页中提到: water solubility: soluble
in hot water
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
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。。。
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?
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.
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。
水晶的分析有些道理
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.
where to find these?
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
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。
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。
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???????????
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