JPS62230620A - Alkali salt of heteropolyacid ion - Google Patents

Abstract

PURPOSE:The titled alkali salt of high molar ratio type of rare earth element, useful as a physiological activator and an optical catalyst, having improved stability and solubility of H3O<+>, obtained by dripping a specific strong acid solution to a heated alkali solution having dissolved WO3, etc., to form a salt, cooling the solution and precipitating the salt. CONSTITUTION:A heated alkali solution having dissolved WO3 or MoO3 is neutralized by dripping a strong acid solution having dissolved oxides of an element of group V of the periodic table and a rare earth element to the solution to form a salt, the solution is optionally incorporated with KHCO3, etc., adjusted to approximately to neutral pH (e.g. about 7.4) and cooled. Precipitate is filtered off and dried to give the titled alkali salt of high molar ratio type of rare earth element shown by the formula (L is one or more of rare earth elements of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er and Yb; X is one element of group V of the periodic table of Sb, As and P; M is W or Mo; x, m, n and p are positive integer and x>=2), white crystal with a single composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to an alkali salt of a heteropolyacid ion, which is a new chemical substance useful as a pharmaceutical, a photochemical catalyst, and the like.

[Prior art and problems]

Polyacid ions, which are cluster compounds, have traditionally attracted attention as chemical catalysts. Its characteristics are: ■ The ion size is 6-25 people and the molecular weight is 103-104.
In an aqueous solution, it is easily decomposed into mononuclear ions by OH-, for example, it is stable against H30+. Therefore, it has high solubility in water and polar solvents, (1) has a large number of hydrated molecules (Example 50H20), and (2) incorporates many types of heteroatoms. ■It is a strong oxidizing agent. Most of the redox reactions are reversible, and the main point is that 6 itself forms a mixed valence complex and acts as a multi-electron pooling agent. Among these characteristics, ■ and ■ are particularly important properties as redox catalysts. Also, ■ and ■ indicate that the catalyst is effective not only as a solid phase catalyst but also as a liquid phase catalyst. On the other hand, the property of ■ is K e
In the case of a molecular capsule called gging, it is very useful for transporting atoms taken into the center while completely shielding them from the surrounding field.

[Purpose of the invention]

The present invention has the characteristics of the polyacid ion described above.

Moreover, it is an object of the present invention to provide a novel alkali salt of a heteropolyacid ion that plays an important role as a physiologically active substance or a chemical catalyst.

[Summary of the invention]

The novel compound of the present invention has a general formula in which at least one element selected from Nd, Ss, Eu, Gd, Ho, Er, Yb, and X is one element selected from the group consisting of Sb, All, and P. 1M is tungsten or molybdenum, 0 is oxygen, x, m, n.

The rare earth element-containing heteropolyacid ion represented by p is a positive integer, and is an alkali salt of a rare earth high molar ratio heteropolyacid ion satisfying X≧2.

The rare earth heteropolyacid compound represented by the above general formula has already been discovered. For example, the report by Mr. Peacock and Mr. Weakley (R.

D, Peacock and T, J, R, We
akley; J, Chem.

Soc, (A), pp, 1836-1839 (
(1971) ), when x=p, LX2 compound [Ce(P Wt+ 0ss)z] ・24H20
YaKn [Nd(P Wll 03g)2] ・26H
20 etc. are installed at IJX door. However, these conventionally known LX compounds are so-called rare earth low molar ratio compounds in which X≦1 in the general formula (for example, x=1/2 in the LX2 compound of Mr. Peacock et al.), and the present invention 1. The rare earth high molar ratio heteropolyacid salt of the present invention, which has completely different properties from the compound of Because it contains a high concentration of rare earth elements in its anions, it is extremely promising as an ultraviolet-excited luminescent material or a physiologically active material, as will be described later.

The alkaline salt of the rare earth high molar ratio heteropolyacid of the present invention is subjected to a neutralization reaction by dropping a strong acid solution in which rare earth L ions and oxides of group Ⅰ elements of the periodic table are dissolved into a heated alkaline solution in which 1M03 is dissolved. The process of synthesizing a salt using a salt produces a condensate in a solution, which can be isolated from the solution as a precipitate by cooling under approximately neutral (slightly alkaline) conditions. On the other hand, the rare earth low molar ratio heteropolyacid alkali salts that have been reported so far are prepared by dissolving raw material polyacid crystals (for example, HsXP1204o) and rare earth L ions in a heated aqueous solution under neutral conditions, reacting them, and precipitating by cooling. I am getting .

The present invention will be described in detail below based on examples.

[Embodiments of the invention]

(1) 2.5H KOH is dissolved in 30 mA pure water, and 4.0 g of WOs is poured into this alkaline aqueous solution and dissolved by heating. On the other hand, Eu(NOx)a ・6 Hz
OO, 4~0.7g and 5b20.1.1g in concentrated hydrochloric acid 4m
1 and leave it for about 10 minutes. This HCm solution is dropped into the aqueous alkali solution of the Wo3 solution. 1 g of KHCO3 was added to this mixed solution to adjust the pH to about 7.4, and then cooled to about 5°C. After leaving it as it is for 2 hours, the precipitate formed at the bottom of the vessel is filtered off, and the resulting filtrate is left to dry at room temperature to obtain white single composition crystals. Elemental analysis of this crystal grain revealed that it was approximately 17% in weight percentage. Eu:
4.47. Sb: 0.90. W: 63.
5. H2O: The result was changed to 4.99. That is, in this case, the Eu/Sb molar ratio is 4. According to the elemental analysis results, the salt composition is Kzs[Eu4SbWa70ta+] ・38 H2O
or Kzs[EuaSbWasO+sa] ・37
Estimated to be H2O. Using exactly the same method, Eu(N
Ox)s ・6 Hz Instead of O, Pr(NOx)s @
For 5H20, use Nd(No3)3/6H20.

The analysis results show that a rare earth compound with a high molar ratio of 4 was obtained for both Pr/Sb and Nd/Sb molar ratios.

When these heteropolyacid salt crystals are irradiated with a 253.7 nm low-pressure excited mercury beam, strong photoluminescence (P
L) was observed. PL is based on the core transition of the rare earth ions contained, and in the Eu-containing heteropolyacid salt, the 614.2 nm line of Eu'+ ion → 7F3 and the 613 nm line of 5Do-)'F2 strongly emit red color. Based on the transition of 'F3/z-'I+a/z*'F'3/z→4th stage/2+'F3/2→'I9/2 of Nd3+ ion in Nd-containing heteropolyacid salt, <
1.33~1.38 μm + 1-06~1-08
μm e 0-89 to 0-92 pm line (all infrared) was observed. On the other hand, for the Pr-containing heteropolyacid salt, the 1710 afterglow time of PL light is 1.36 m at room temperature.
sec, 77 was 1.29 msec.

Even when the aqueous solution of the heteropolyacid potassium salt was photoexcited, the same emission spectrum as above was obtained.

For comparison, we used the report by Peacock et al. as a conventional heteropolyacid salt in the same system [E u (S bW + + 039) 2] ・25
H20 was selected and the ultraviolet excitation PL was measured. When excited with the same stimulation intensity of Hg 253.7, the PL intensity emitted from the conventional heteropolyacid salt is 1/8 to 1/8 that of the heteropolyacid salt of the present invention containing a high molar ratio of Eu.
It was 1/10. It was confirmed that the PI and strength of other rare earth ion-containing heteropolyacid salts were several times better than that of the polyacid salt of the present invention. This shows the high luminous efficiency of the rare earth high molar ratio heteropolyacid salt of the present invention.

(2) 1.8 g of NaOH was added to 25 ml of pure water and stirred, and 4.0 g of WO3 was mixed therein and further heated and dissolved. Apart from this, Ce(N 03)4
・Dissolve 5 to 0.8 g of 8 HzOO and 1.1 g of 5b203 in concentrated hydrochloric acid from 4 companies and leave it for about 10 minutes. This C
a. Drop the Sb-dissolved HCQ solution into the WO3-dissolved caustic soda solution. Add about 1 g of Na HCO3 to the solution and p
After adjusting H to about 7.3 to 7.5, the mixture is cooled to about 5°C. Leave it at this temperature for 2 hours and filter out the precipitate that formed at the bottom of the container.
When the obtained filtrate is dried at room temperature, white monocompositional crystal grains are obtained. As a result of elemental analysis, this is a rare earth compound of the same type as the heteropolyacid potassium salt of the previous example, and C
The e/Sb molar ratio was found to be 5. Using exactly the same method as above, use Eu(N 03) 3.6 H20 instead of Ce(N O3) 4.8H20, and Eu/
Crystals of Eu,Sb heteropolytungstate sodium salt having an Sb molar ratio of 4 were obtained. In order to investigate the physiological activity of these heteropolyacid salts of the present invention, the following living body administration experiment was conducted.

friend 1eukae + aia virus, a type of leukemia virus
) was suspended in physiological saline, and 0.2 mA of the suspension was injected into the lungs of 40 male mice (DBA-2 type) to infect them.

Each mouse weighs 20-23 g. Virus-infected mice were divided into four groups of 10 mice each, and a comparative experiment of heteropolyacid ion administration was conducted. The first group was not administered with heteropolyacid ions, the second group was administered with HPA-39 ions (s b9w2. Ce/Sb heteropolytungstate ion and Eu/Sb heteropolytungstate ion of the present invention were administered to the four groups, respectively.Heteropolytungstate ion was administered to the second group (HPA-39) one week after infection. The third and fourth groups were tested 2 weeks after infection. At the time of administration, heteropolyacid alkali salt crystals were quickly dissolved in physiological saline, and 3 mg (3 mg) was administered to each mouse.
The experiment was performed by directly injecting 150 mg/kg of mouse body weight into the lungs. Examining the survival rate of each group 100 days after virus infection, the first group, which did not receive any heteropolyacid ions, had a survival rate of 10%, and the second group, which had received HPA-39 ions relatively early, had a survival rate of 4.
0%, 70% for the third group to which the heteropolyacid ion of the present invention was administered, and 60% for the fourth group, demonstrating the excellent antiviral properties of the compound of the present invention. Separately, a toxicity test of the heteropolyacid ion of the present invention was conducted using mice that were not infected with the virus. When heteropolyacid salts were dissolved in physiological saline as described above and changes were examined for 40 days after injection into the abdomen and vagina of mice, changes were observed in mice up to 400+g per 1kg of mouse body weight when weighed with heteropolyacid salts. I couldn't. However, 600mg/k
Some mice died within 40 days when administered in doses of more than 1.5 g.

On the other hand, when HPA→39 was administered at doses of 250 w+g/kg or more, all mice died within 40 days. This is HPA-
Compared to No. 39, which is a tungstate containing only sb, the heteropolytungstate No. 1 of the present invention has a high molar ratio of rare earth element content to sb, and is considered to have a low proportion.

Similar excellent antiviral properties were also demonstrated with the potassium salt containing a high molar ratio of rare earths prepared in the previous example.

(3) Different types of heteropolyacid salts were synthesized by the same wet method as in the previous example. Rare earth ions mainly select Pr.
Also, in addition to sb, there are As and P.

A heteropolyacid anion was constructed using W as M.

Furthermore, K", Na", and Ca" are cations (alkali ions) that form salts with these anions.

S r” ” t B a ” +t N H4” g
CHs Na+ was used. The rare earth was dissolved in a strong acid solution in the form of a nitrate, a group V element of the periodic table, or an oxide to form a raw material aqueous solution.

The L/X molar ratio X determined by elemental analysis of the synthesized salts is shown in Table 1.

Table 1 (margin below) Synthesized heteropolyacid alkali salts containing a high molar ratio of rare earth elements In order to investigate the anticancer properties of these heteropolyacid ions of the present invention, experiments using mice were conducted.

Ascites liver cancer cells were transplanted into 50 C3H mice (male), 10 of which were kept as they were, and the remaining 30
Divide the animals into 10 groups (4 animals in each group).

The heteropolytungstate ion containing a high molar ratio of rare earth elements (Na3 1 to 3-10) was administered to each group. Administration is once daily, 4B dissolved in 4 mA of physiological saline.
The experiment was carried out by intraperitoneally injecting an alkali salt of a heteropolyacid into each mouse. This administration started 7 days after the liver cancer cell transplantation and continued for 2 weeks. Within 30 to 40 days after cell transplantation, all the mice in the non-administered group died, but the survival rate in the group administered with the heteropolyacid ion of the present invention was good, and anticancer effects were observed. The number of surviving mice in each group 50 days after cell transplantation is as follows.

&3-1...4. &3-2...4. &3-3...
2゜Nα3-4...4. Isao 3-5...4. Nci3
-6...3. Nα3-7...3. Nα3-8...
4. &3-9...4. &3-10...4 50 days after transplantation, one surviving mouse was selected from each group and dissected to examine the state of liver enlargement. &3-1.3-
2.3-4.3-5.3-1o was almost normal (state before transplantation), but 3-3.3-6.3-7.3-8.
In No. 3-9, it was observed that the weight ratio was 1.5 to 3 times larger than the normal value. This result shows that there is a difference in effectiveness among the heteropolyacid ions of this patent.

(4) Heteropolyacid ammonium salts containing different types of rare earth ion L and metal M were synthesized in the same manner as in Examples (1) and (2). When M is MO, the oxide to be dissolved in 30 mQ of the aqueous alkali solution of the raw material is WO34
, Og to MOO32.9g. Its type and L
/X molar ratio X (estimated from analytical values) is shown in Table 2.

When you make a 1m 9% aqueous solution of each group shown and irradiate the aqueous solution with ultraviolet light (λ = 365 nm), the color of the solution becomes colorless →
It was found that the aqueous solution was colored blue, and once colored, it returned to colorless in the dark, indicating photochromism. Is the time required for coloring shorter for larger L/X molar ratios?
10 seconds or less when x=5, 30 seconds or less when x=4, x
In the case of =2, it was less than 1 minute. The time it takes to return to the original colorless state in the dark is slightly longer than the coloring time, but the larger X is, the shorter the time is, for example, less than 1 minute when x=5.

This is a conventionally known alkyl ammonium salt of polymolybdate, such as [NH3Pr lsτH2
MO8028] - The coloring time was much faster than the coloring time of 3 minutes and the fading time of 15 to 20 minutes for 3H20, indicating that the rare earth high molar ratio heteropolyacid acid salt of the present invention is also suitable as a photochromic material.

〔Effect of the invention〕

As described in detail in the Examples above, the rare earth high molar ratio heteropolyacid alkali salt (i.e., polyacid ion) of the present invention exhibits strong catalytic activity, and exhibits extremely excellent efficacy especially as a physiologically active substance and a photocatalytic agent. I understand. Since these compounds are polymers, it is not yet possible to determine their exact structures, but since they can be synthesized with good reproducibility using the wet method described in this example, if we further study the manufacturing method in the future, they can be used as industrial products. It is thought that it can be sufficiently mass-produced.

Claims (1)

[Claims] 1. The general formula is [L_xXMmOn]^p^-, where L
is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, H
At least one selected from o, Er, Yb, X
is one element selected from the group consisting of Sb, As, and P,
M is tungsten or molybdenum, O is oxygen, x
, m, n, p are positive integers, and is an alkali salt of a rare earth element-containing heteropolyacid ion satisfying x≧2. 2. Alkaline salts of heteropolyacid ions containing rare earth elements include potassium, sodium, ammonium, calcium,
The alkaline salt according to claim 1, which is a salt of an element selected from the group consisting of strontium and barium.