รูป12 is a view (top) of SEM image showing a re-crystallized ซับสเตรต which is the quantum crystal ซับสเตรต alkali treated in the presence of a halogen ion
(Sodium hypochlorite treatment) (top view) and a graph (below) showing a result (elemental analysis) of the EDS spectra of the re-crystallized ซับสเตรต.
รูป13 is a graph showing a result of XPS measurement of the alkali-treated .recrystallization ซับสเตรต.
รูป14 is a graph showing a result of XPS measurements after etching the surface of the recrystallization ซับสเตรต.
Description of Embodiments
[0026] Hereinafter, the การประดิษฐ์นี้ will be demonstrated by way of examples that are to be understood as provided only for illustration and not intended to limit the scope of the การประดิษฐ์นี้.
(Example 1)
As shown in Figure 4, an สารละลายเอเควียส containing 1000ppm of ซิลเวอร์
ไธโอซัลเฟต was prepare and the 1 drop was added dropwise onto a phosphor bronze plate. After the phosphor bronze plate with the สารละลายเอเควียส drop thereon has been left standing for about 3 minutes, the solution on the plate was blown off . On the plate, a quantum crystals was obtained as shown in the SEM image at the right side of รูป4..
รูป 5 is a photograph showing various SEM images of the nano-particle
aggregate prepared in Example 1 (quantum crystal), and รูป 6 shows an
enlarged SEM image of nano-particles where there were thin hexagonal
columnar crystals of 100 nm more or less and having an unevenness surface of several nm order. We could not find out any specific facets of metal
nano-crystals in the quantum crystals.
Figure 7 is a microphotograph showing the relationship between quantum crystal shapes and the standing time after dropping onto the phosphor bronze ซับสเตรต, where it is recognized that firstly, a hexagonal quantum crystal is produced and then growing while maintaining the crystal shape.
รูป 8 is a graph showing results of EDS spectra (elemental analysis).of the
quantum crystals where not only ซิลเวอร์ but also elements derived from complex ligands can be detected in case of the quantum crystal on the phosphor bronze ซับสเตรต, while only ซิลเวอร์ can be detected in the case of the quantum crystals formed on a copper plate by using 1000ppm of ซิลเวอร์ ไธโอซัลเฟต in เอเควียส
solution and keeping it for the standing time of 3 minutes after dropping onto the copper ซับสเตรตs.
[0027] (Discussion on formation of the quantum crystal)
In case of 1000ppm of ซิลเวอร์ ไธโอซัลเฟต complex in an สารละลายเอเควียส,
hexagonal column crystals of 100nm more or less, are formed for the standing time of 3 minutes after dropping it onto a phosphor bronze plate, where it is
confirmed that irregularities of several nm order are found on the hexagonal
column quantum crystals from the SEM images (รูป 4, 5 and 6).and any specific facets derived from a metal nano-crystals are not found , while the EDS
elemental analysis shows ซิลเวอร์ and elements derived from the complexing
ligand. Accordingly, it can be estimated from the above analysis, that the whole particles show nano-crystals of ซิลเวอร์ complex and also the unevenness
appearance on the surface may be caused by the formation of spread quantum dots made of ซิลเวอร์ clusters in the complexes. From the aspect of phenomenon that the ซิลเวอร์ complex quantum crystals of the การประดิษฐ์นี้ can be formed on a phosphor bronze plate, while ซิลเวอร์ nano-particles alone can be deposited on the copper ซับสเตรต, it is estimated that, as the equilibrium potential of the ซิลเวอร์ ไธโอซัลเฟต complexes is 0.33 which is equivalent to the copper electrode potential with 0.34, there is deposited only ซิลเวอร์s with 0.80 on the copper
ซับสเตรต. On the other hand, in case of a phosphor bronze plate with the
electrode potential of 0.22, which is slightly less noble than that of the copper so that ซิลเวอร์ complex crystals seem able to be precipitated. The concentration of the ซิลเวอร์ complex in the สารละลายเอเควียส should be in a dilute region of 500 2000ppm, 2) the electrode potential of the metal ซับสเตรต with respect to the equilibrium potential of the metal complex solution is slightly less noble, 3 ) the metal complex should be deposited by the electrode potential difference
between the metal ซับสเตรต and the metal complex. Further, in case of
1000ppm of thiourea ซิลเวอร์ complex in สารละลายเอเควียส, the same function was can be observed.
[0028] (Example 2)
A ซับสเตรต of ซิลเวอร์ ไธโอซัลเฟต quantum crystal made on the phosphor bronze plate in Example 1 was prepared and, on this ซับสเตรต an สารละลายเอเควียส of sodium hypochlorite having pH11 was dropped. After dropping of the สารละลายเอเควียส, the solution was allowed to stand on the ซับสเตรต for three minutes and is subsequently blown off to prepare a bio-chip for SERS. On the other hand, the serums obtained from 12 cases of gastric cancer patients, the serum obtained from 12 cases of the colorectal carcinoma patients and the serum
obtained from 12 cases of benign disease patients, all of them are diluted 10 times to prepare testing samples, which are subjected to a measurement of
Raman spectra with irradiated with 633nm laser light. There are observed
much correlation between the degree of progress and the peak rise values as well as the peak integral value in case of gastric cancer and colon cancer. In addition, in the case of gastric cancer, the peak became to develop in the
Raman spectrum developed after one minute of the laser irradiation, the peak became to develop in the Raman spectrum after 2-3 minutes after laser
irradiation in the case of colon cancer. Also, D is a graph showing a comparison of the Raman scattering peak rising values concerning gastric cancer, colon
cancer and benign disease. The peak of the gastric cancer samples and colon cancer samples are found to be significantly higher than that of .the benign
disease samples. While it is difficult to find the difference between the gastric cancer sample and the colon cancer samples concerning the peak rise value, it
is possible to identify both cancers considering the peak expression times and the peak integral value.
[0029] (Discussion on the ผลึกเมโส of ซิลเวอร์ออกไซด์ compound: Part 1)
The quantum crystal ซับสเตรต is subjected to a treatment of dropping 5%
sodium hypochlorite solution thereon and the dropped solution is removed off 2 minutes later to obtain crystals having structures shown in รูป 12, where
needle-shaped crystals and large clumps such as rugby ball-like mass are
observed and the respective compositions are subjected to analyzation at EDS spectra (elemental analysis),. After a result of the analysis, the needle-like crystals are both considered to consist of a composite crystal of ซิลเวอร์ออกไซด์ and ซิลเวอร์ chloride ,from the following reaction formulas and the result of Figure 12 does not show any chlorine and shows that the ซิลเวอร์ and oxygen is dominant.
Na 2 5 2 0 3 + 4NaCIO + H 2 0 --> Na 2 SO 4 + H 2 SO 4 ± 4NaCI (1)
Ag+ + NaCI —* Aga + Na + (2)
Ag + + 3Na0C1---* 2AgCI + NaCIO 3 + 2Na + (3) Ag + OH- —+ AgOH (4)
2Ag ++ 20H --4■g 2 0 + H 2 0 (5)
Thus, although it is considered that ซิลเวอร์ ions and ไธโอซัลเฟต ions are important in the formation of ผลึกเมโส according to the การประดิษฐ์นี้ by alkaline oxidation reaction in the presence of chloride ions and ,although the ซิลเวอร์ออกไซด์ is formed according to a conventional reaction, it is surprised that ซิลเวอร์ peroxide are predominantly formed from the following XPS measurement.
[0030] (Discussion of the ผลึกเมโส of ซิลเวอร์ออกไซด์ compound: Part 2) XPS measurement:
The เอเควียส sodium hypochlorite was added dropwise to the quantum crystal ซับสเตรต prepared as the above for 2 minutes, to make a re-crystal ซับสเตรต, which is subjected to a XPS analysis (using models: ULVAC-PHI (Ltd.) /
PHI5000 Versa Probe II (scanning X-ray photoelectron spectroscopy ) without etching for Ag and 0 by XPS measurement. In addition, for comparison, Ag in the powder of ซิลเวอร์ chloride and the powder of ซิลเวอร์ออกไซด์ were measured . On the other hand, the recrystallized ซับสเตรต was subjected to XPS measurement of Ag and 0 after etching for 5 minutes with an argon gas cluster ion gun. If the XPS measurement results of FIGS. 13 and 14 will be combined with the results of EDS according to รูป 12, the peak in the vicinity of 529eV is the peak derived from ซิลเวอร์ peroxide (AgO), while the peak in the vicinity of 530eV is the peak derived from ซิลเวอร์ออกไซด์ (Ag20). Further, If it is etched, the oxygen content decreases, while the 0 peak derived from the ซิลเวอร์ peroxide (AgO) in the vicinity of 529eV is still greater than the peak derived from the ซิลเวอร์ออกไซด์ in the vicinity of 530eV in case of etching , so that it is recognized that the ซิลเวอร์ peroxide was produced in the vicinity of the ซับสเตรต. It is assumed that the electrode
potential of the ซับสเตรต and the catalytic action are affected.to the meso
-crystal formation
The EDS measurement was carried on the above-mentioned re-crystal ซับสเตรต by using a JEOL Ltd. / JSM-7001F (field emission scanning electron microscope analysis).
In addition, even iif the สารล