UA124315C2 - METHOD OF LABELING LIQUID CARBOHYDRATES WITH FLUORESCENT MARKER - Google Patents

Abstract

A method of labeling liquid hydrocarbons with a fluorescent marker, comprising adding a fluorescent marker - a solution of a long-wave phosphor in an organic solvent, and as a long-wave phosphor using a square acid derivative.

Description

The invention relates to the area of problems of the fuel and energy complex and the development of chemical technologies, methods of "hidden" labeling of liquid hydrocarbons, such as, for example, fuels of various types (gasoline, diesel fuel, marine fuel, boiler fuel) and different manufacturers, lubricants (motor, transmission and special oils, mineral lubricants, plastic lubricants), petroleum-based liquids, using phosphors that emit light in the long-wave range of the spectrum. The invention can be used to create a system for protecting fuel of various types and purposes against falsification, counterfeiting or theft.

Currently, Ukraine does not have its own means of protecting liquid fuel or fuel-lubricating materials against any types of counterfeiting (forgery and dilution) and smuggling (unauthorized import, export, transportation and unauthorized deliveries to gas stations).

Existing methods of laboratory control of fuels make it possible to detect only their compliance with accepted standards in terms of composition and content of impurities, but do not allow to establish the origin of these materials, that is, whether they were imported into Ukraine or produced in Ukraine on legal grounds, or whether they are contraband or counterfeit goods. They try to solve this problem by introducing special additives (labels or markers) into the fuel, the presence and concentration of which can be established only with the help of laboratory analyzes in specialized laboratories or with the help of special devices. Markers solve two problems at the same time: identification of the type of fuel and detection of the fact of its dilution. So, for example, in Great Britain, the color of the dye ZoiImepi Kay 24 in combination with quinizarin, which acts as an antioxidant, was chosen to indicate the type of fuel to which a low tax is applied. On the territory of Europe, the so-called "EigotagkKeg" is necessarily introduced into the fuel, which is sold at a reduced tax. This marker has a yellowish color (also called

Boimepi Meiom/ 124), which is not immediately visible to the naked eye when adding the necessary diluted concentration to the fuel, but which can be detected by adding an acid solution and short-term boiling if necessary. Blue dye is similarly applied to kerosene in the UK to distinguish jet fuel from diesel. Among other dyes used for the visual marking of liquid hydrocarbons, we can name: zoiImepi Kea 24, 5oiImepi Kea 19, 5oiImepi Vice 36, apa 5oimepi Sgeep 3. In some countries, along with the visual marking of fuel, hidden labels are also used, which detect

From the use of certain reagents or during extraction in an alkaline or acidic medium.

The visibility of the coloring has certain disadvantages, as it allows criminal groups to detect and remove the dye and sell subsidized fuel at a higher cost, resulting in reduced tax revenues. Therefore, the protective materials (labels) that are added must work in very low concentrations, that is, easily and reliably determined using special devices, but, at the same time, not be detected visually (by the color of the liquid) or using traditional means of recognizing protective signs (for example, with the help of ultraviolet currency detectors). In addition, they must not affect the operational properties of the fuel, be inert to the parts of machines and engines, be non-toxic after use or combustion in the engine and not pollute the environment.

Solving this task is also complicated by the fact that fuel components and metal surfaces of tanks and pipelines in which fuel is stored or transported can aggressively act on the label and destroy it, while the label must remain stable and not reduce its concentration in the fuel during entire storage period.

All of the above factors determine the urgency of creating new materials for inconspicuous, i.e., "hidden" marking of liquid fuels for various purposes.

The largest number of "hidden" markers is revealed by the formation of color when using certain reagents or during extraction in an alkaline or acidic environment and belongs to the class of azo or diazo dyes.

The known synthesis of fuel markers based on the reaction of p-alkylaniline with a diazo salt of aniline derivatives (5. Zimzhaprgazor "Reigoiyesht ptagkeg5 zupipezizei iot p-aiKuirepgepe apa apiipe degpmaiimev", Ipa. Epd. Snet. Vev., 2003, 42, pp. 5054- 5059). These markers are invisible in diesel fuel, and the color appears during extraction with a solution of 1,2-diaminoethane in propane-1,3-diol and methanol.

Known hidden markers based on azo or diazo dyes for marking fuel (US patent

Mo 6514917, C0O9B 29/08 and US patent Mo 8257975, (z01M 33/26). These markers are practically colorless in the fuel, but are obtained during extraction (acidic or alkaline) and/or with the use of a developing agent.

Phthalenes (US patent Mo 6002056, С10Й 1/00 and US patent Mo 6482651, СО70 307/88) and anthraquinone-based dyes (US patent Mo 5205840, СО9В 1/00) are known for marking petroleum products, the color of which appears after extraction in alkaline medium.

However, multi-step detection procedures for latent markers, including extraction or development with reagents, tend to complicate the detection process and are inconvenient for field use. In addition, visual identification or the use of absorption spectroscopy as an identification method have certain disadvantages, among which are the low sensitivity of these methods, as well as the need to introduce high concentrations of the dye (on average, 10-100 ppt). A large amount of tracer added can have a bad effect on engine parts or the environment, so it is advisable to reduce the tracer concentration to 1 ppm or less.

Fluorescent measurement methods are currently one of the most sensitive and, at the same time, cheap methods of analysis, which allows you to significantly reduce the concentration of the label added to fuel, increase the "hiddenness" and reliability of labeling, and reduce the cost of protection and detection. Fluorescent methods of analysis can be easily automated, and detection can be implemented both on standard spectral equipment in the presence of appropriate methods of analysis, and with the help of specialized (specially designed to solve this task) devices, including in a compact portable or field version.

Known phosphors for use in liquid hydrocarbons (US patent Mo 6991914, C120 1/44 and US patent Mo 9469717, B01M 21/76) that emit light in the region up to 550 nm.

It is known that due to the content of condensed aromatic hydrocarbons, liquid petroleum products have absorption and fluorescence that interfere with identification by means of short-wave markers, the "region of transparency" in this case starts from 550 nm. Therefore, the use of known phosphors for labeling liquid hydrocarbons is not convenient due to overlap with the fuel's own fluorescence.

For "hidden" marking, it is appropriate to use long-wave phosphors that glow in the red or near-infrared region of the spectrum.

There is a known method of marking liquid hydrocarbons with markers based on squaraine, crocon, phthalo- and naphthalocyanine new dyes (US patent Mo 5525516, C10I. 1/232), the maximum absorption wavelengths of which are greater than 600 m.

Known squaraine markers based on benzindolenine derivatives overlap quite a bit

Because of the narrow range of absorption wavelengths (650-690 nm), which limits their use as a source of fluorescence excitation in the narrow zone of 650-680 nm. In addition, the phthalocyanines and naphthalocyanines claimed in this patent contain metal or silicon atoms in their structure, which will lead to the formation of a solid residue during combustion in the engine and rapid wear of engine materials and parts.

We chose the last of the above analogues as a prototype based on the number of common features.

The task of this invention is the development of a simple method of labeling liquid hydrocarbons with fluorescent markers based on long-wavelength phosphors, which have high solubility and photostability in hydrocarbons, do not contain metal atoms in their structure and cover a wide spectral range of absorption, which allows their emission to be excited by a large set of various light sources .

The solution to the problem is achieved by the fact that in the method of labeling liquid hydrocarbons with a fluorescent marker, which consists in dissolving a fluorescent marker in a liquid hydrocarbon - a concentrated solution of a long-wave phosphor in an organic solvent, according to the invention, derivatives of the square acid of general formula I or general formula II are used as long-wave phosphors , or the general PP formula: in? 2 A 2 in in U Kk

N

Gu

Kk M

HM, o lot - in r k where A is -0, -5, -M-Va, -C(B2)(VU), moreover, K2, B? and B: - is -SOVE, -SM, -SOM(VU) (VU), -

SOOVNVI, moreover, KU, Ve, V! and VEK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -OH85, -SOVK, -SM, -"SOM(NU) (Ve), -SOOV! groups where KU is a branched or linear aliphatic group or an aromatic group; 0 - this-oh,-57;

U and E are O, 5, Ze, MAN" and C(K)(B)); where B" is -H, an aliphatic, alicyclic or aromatic group; IN! and VI - aliphatic groups, alicyclic groups, aromatic groups or B! and B) form

CYCLE;

And YIV is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH»8, -SOVK, -SM, -SOM(VU)(Vg), -SOOV! groups;

IN? and B2 are independently -H, -СМ, -СОМ(ВУ(Бе), -СООВИ, -МО», -ОН»e, an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be replaced by -СМ, -СОМ(ВУ)(Бе), -СООВИ, -МО», -ОВ9 or aliphatic groups; in? 2 A 2 in in U Kk

Fu sn -

Kk M 7

M.

M, / pe in? in Оу and х PI where A is 0, -5, -М-Ва, -С(В)(ВУ), moreover, K2, В? and B: - is -SOVE, -SM, -SOM(VU) (VU), -

SOOVNVI, moreover, KU, Ve, V! and VEK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -OH9, -SOVK, -SM, -"СОМ(ВУ(Ве), СООВИ groups, where Ez9 is a branched or linear an aliphatic group, or an aromatic group;

U and U are O, 5, Be, M-B" and C(B) (VI); where B" is -H, an aliphatic, alicyclic or aromatic group; IN! and VI - aliphatic groups, alicyclic groups, aromatic groups or B! and B) form

CYCLE;

ВІ AK is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -"СОМ(НУ) (Ве), -СООВИ groups;

Vii Kg is independently H, -CM, -"СОМ(НУ(Ве), -СООВИ, MO", -ОН», an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be substituted -СМ, -СОМ(ВУ)(Ве), -СООВИ, -MO», -ОВ9 or aliphatic groups;

EE M i o / v v r y YII where A is 0, -5, -M-ВНа, -С(В)(Нг), moreover, Me, A? and r is -"SOVK, -SM, -SOM(VU (VU), -

SOOVBVI, moreover, KU, Ve, V! and EC is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -ОНе, -СОВК, -СМ, -СОМ(НУ(Ве), СООВИ groups, where КУ is a branched or linear aliphatic group, or an aromatic group, p is -O,-5;

Zo A'YIK is -H, a branched or linear aliphatic group;

IN? and B are independently Н, -СМ, -СОМ(ВУ)(Бе), -СООВИ, МО», -ОН»8, - Ш(Б8У) (ВУ), an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be replaced by -СМ, -СОМ(ВУ(Бе), -СООВИ, МО», -ОНе or aliphatic groups.

The marker is a concentrated dye solution used for marking fuel and lubricant materials for the purpose of its subsequent detection and/or quantitative determination.

Long-wavelength phosphors claimed as liquid hydrocarbon markers have absorption and fluorescence maxima in the range 530 to 760 nm and, as a result, can be easily detected by appropriate instruments that measure the fluorescence of solutions. At the same time, there is a visually imperceptible change in the color of the marked sample, which allows for "hidden" marking.

In addition, long-wavelength phosphors claimed as markers of liquid hydrocarbons are characterized by high solubility in liquid hydrocarbons subject to labeling (this makes it easy to obtain such a concentration of the phosphor that is reliably detected by fluorescence methods), have chemical stability for long-term storage of the labeled product relative to sunlight , water, oxygen, temperature, etc. and chemical inertness to all components of the liquid to be labeled (dyes, additives, etc.).

It should be noted that the luminescence intensity of the marker should be sufficient for its reliable detection. The increase in the intensity of the analytical signal is facilitated by the high brightness of the phosphor, which is the product of the multiplication of the extinction coefficient by the quantum yield.

Table 1 shows the spectral characteristics of typical dyes of square acid derivatives of the general formula I, II, PI (absorption maxima (Atach(aye)) and fluorescence (X, tach(et)), as well as extinction coefficients and quantum yields of squaraine dyes, which allow to evaluate the efficiency of the phosphor as a fluorescent marker by its brightness indicator).

Table 2 shows the obtained data on changes in fluorescence intensity (Ifl) of solutions of compounds 24 and 26 (see Table 1) in diesel fuel during 1, 2, 3, b and 12 months of their storage (average data based on the result of fluorescence measurement of two of parallel prepared solutions for each point, three parallel measurements were performed for each solution).

In fig. 1 shows the fluorescence spectra of some markers (Table 1, compounds 26, 24 and 22).

In fig. 2 shows changes in the fluorescence spectra of some markers (Table 1, compounds 26, 24): (a) - in diesel fuel over time; (b) - their stability curves.

For the practical use of a fluorescent dye as a fuel marker, a high stability of the dye and its spectral characteristics with regard to long-term storage of the marked product in relation to sunlight, water, oxygen, temperature, components (additives) is necessary.

The method of marking liquid hydrocarbons with a fluorescent marker consists in adding to the liquid hydrocarbon being marked a fluorescent marker - a long-wavelength phosphor of formula I or formula II or formula PI in an amount from 1 mg/t to 1000 mg/t.

Due to the fact that the markers dissolve well in the fuel and lubricant material, their distribution is uniform. Markers are injected into the fuel in small concentrations, detected using a light source with a wavelength in the region of 500-750 nm by their luminescence, and their presence is identified by determining the maximum and intensity of luminescence in

From the region of 550-850 nm of a sample of labeled fuel, which is investigated by the method of fluorescence spectroscopy. It is also possible to excite fluorescence in labeled liquids with a semiconductor laser or a semiconductor diode. A particular advantage is the use of a semiconductor laser or a semiconductor diode with a wavelength of maximum emission in the spectral range from Atach - 100 nm to Atach «x 20 nm (where Atach is the wavelength of the maximum absorption of the marking substance). The maximum emission wavelength is 550-850 nm. The fluorescent light obtained in this way can be registered visually for rapid identification of the marker in the fuel, for example, in the field.

Marking does not lead to visually noticeable changes in the fuel, namely, changes in color, transparency, etc. In addition, the fuel marked with labels keeps all the necessary indicators within the limits of regulated regulatory documents and does not pose a threat to the environment or engine parts.

In order to minimize the cost of marking, to minimize the possible interactions of fuel markers with any of its ingredients, to ensure invisibility in marked fuel, the number of markers is set as small as possible. The total (mass) concentration of phosphor in the liquid to be labeled is chosen in the range from 1 mg/t to 1000 mg/t. Another reason for reducing the number of markers as much as possible can be to overcome their damaging effect (if any), for example, on the parts of combustion engines or the exhaust pipe, and to reduce the amount of dye emissions into the environment.

The above compounds of formula I or formula II or formula I can label such organic liquids as aliphatic or aromatic hydrocarbons (pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, test gasoline ), mineral oils, gasoline, kerosene, diesel and boiler fuel, natural or synthetic motor, hydraulic or transmission oils (for example, oils for automobile engines or sewing machines).

Examples of implementation and use of the proposed technical solution are given below.

Example 1. Preparation of a comparison solution of a fluorescent marker (see Table 1, compound 24) in gasoline.

To a sample of 4.0 mg of compound 24 in a glass cone, add 10 ml of methyl tert-butyl ether, and with a 10 ml glass pipette, sucking the liquid with the help of a rubber bulb, close the cone with a glass stopper and mix by shaking until a true solution is obtained.

The resulting solution has an intense blue color and a red fluorescence that can be observed visually. This concentrated solution is added to the fuel for marking. For this, 10 ml of a fluorescent label with a concentration of 400 mg/dm? the marker compound 24 is added to 100 liters of fuel. After thorough mixing, a comparison solution with a concentration of 40 mg/m3 of compound 24 in fuel is obtained. 10 ml of the comparison solution is hermetically sealed in a glass container made of transparent glass and stored in a dark place at a temperature not higher than 2576.

A reference solution is used to determine the presence of a fluorescent marker in the fuel samples under investigation.

Example 2

Preparation of a comparison solution of compound 24 in diesel fuel

To a portion of 4.0 mg of compound 24 in a glass cone, add 10 ml of 1-octanol with a 10 ml glass pipette, sucking the liquid with the help of a rubber bulb, close the cone with a glass stopper and mix by shaking until a true solution is obtained. The resulting solution has an intense blue color and a red fluorescence that can be observed visually.

This concentrated solution is added to the fuel for marking. For this, 10 ml of fluorescent label with a concentration of 400 mg/dm3 of compound 24 is added to 100 l of fuel. After thorough mixing, a comparison solution with a concentration of 40 mg/m3 of compound 24 in fuel is obtained. 10 ml of the comparison solution is hermetically sealed in a glass container made of transparent glass and stored in a dark place at a temperature not higher than 25 "С. The comparison solution is used to determine the presence of a fluorescent marker in the fuel samples under investigation.

Example C

Detection of compound 24 in gasoline (field conditions)

The fuel under investigation is placed in a glass tube, irradiated by a diode laser with light with a wavelength of 635-650 nm, and the color of the beam in the liquid is compared with that obtained for a comparison solution based on gasoline (see Example 1). In unmarked diesel fuel, the beam has practically no color, and in marked - there is a red color of the beam.

Example 4

Detection of compound 24 in diesel fuel (field conditions)

The fuel under investigation is placed in a glass tube, irradiated by a diode laser with light with a wavelength of 635-650 nm, and the color of the beam in the liquid is compared with that obtained for a comparison solution based on diesel fuel (see Example 2). In unmarked diesel fuel, the beam has practically no color, and in marked - there is a red color of the beam.

Example 5

Detection of a fluorescent marker (see Table 1, compound 24) in industrial lubricant I-20 (laboratory conditions)

Fluorescence spectra of the lubricant sample under investigation are measured at room temperature using a Magap Sagu Esiirsee spectrofluorimeter in standard 1-cm quartz cuvettes with the following device settings: excitation wavelength - 600 nm, spectrum measurement range - 605-750 nm, optical wavelength slits excitation and emission - 5 nm each, the voltage on the photomultiplier - 800 V. The emission maxima are determined with an accuracy of 0.5 nm based on the result of three parallel measurements. The value of the fluorescence intensity is determined with an accuracy of 25 u.o. fluorescence. Three parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three fluorescence intensity values at the wavelength of the maximum fluorescence (647 nm for compound 24).

Example 6

Detection of a fluorescent marker (see Table 1, compound 26) in diesel fuel (laboratory conditions)

Fluorescence spectra of diesel fuel under investigation are measured at room temperature using a Magap Sagu Esiirsee spectrofluorimeter in standard 1-cm quartz cuvettes with the following device settings: excitation wavelength - 550 nm, spectrum measurement range - 550-750 nm, optical wavelength slits excitation and emission are 5 nm each, the photomultiplier voltage is 700 V. The emission maxima are determined with an accuracy of -0.5 nm based on the result of three parallel measurements. The value of the fluorescence intensity is determined with an accuracy of sch-5 u.o. fluorescence. Three 60 parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three fluorescence intensity values at the wavelength of the fluorescence maximum (575 nm for compound 26).

Example 7

Determination of the stability of compounds 24 and 26

To study the stability of marker solutions in fuel over time, an experiment was conducted comparing the fluorescence of freshly prepared solutions of compounds 24 and 26 and solutions with the same concentration that were stored for different periods of time.

The concentration of the markers was chosen to be that used in the labeling fuel, namely 40 mg/m3 for compound 24 and 80 mg/m3 for compound 26.

The stability of the spectral characteristics of compounds 24 and 26 in fuel is sufficiently high. Namely, during three months of storage in diesel fuel, the fluorescent signal of compounds 24 and 26 decreases by no more than 6 95, and in 12 months it loses no more than 10 95, which is sufficient for their practical use.

As can be seen from the description of the application materials, the claimed fluorescent markers fluoresce under simple test conditions and at very low concentrations (less than 2 ppm), dissolve well and do not react with components of fuel or fuel-lubricating materials, and also remain fairly stable over time with long-term storage.

Fuel of various types (gasoline, diesel fuel) and manufacturers, lubricants (motor, transmission and special oils, mineral lubricants, plastic lubricants), petroleum-based liquids can be used as labeling objects.

Table 1

Compound Structure Solvent Mtah(vv), NM Mtah(et), NM (E, M" cm" (Fe, bo

EZ nu ak SHHI 637 659 1 kn shana Chloroform

YIM, Derek Zh ( 15100 0) (4) me oh Samy gV g de, ZE 641 666 2 de rus su Chloroform

These t I: t R f R (103000) (4)

Han t WHAT is not sm i SUM

WITH

She

IN

. KR: 6 73 b 9 7

With CHO be, Chloroform (128000) (6)

S is shi M. that 461 (42)

Sk Z; Cuba

KE eV; -k zhim 602 701 4 schi on tires OR Chloroform (196000) (44)

ONE ro pe an 687 708 5 more in WHAT Chloroform no rophor (134000) (3)

What is Chloroform?

OM EN o, ee Y Shi 728 757 7 oo Dy on Chloroform nn sha rophor (166000) (46) bi» Z 0 Camus

KI mo em wai

Well I 647 668 zhi K- Hensy Chloroform shen rofor (104000) (43) eh V and still be bo SUM,

i sha 5AB 5OD fr Chloroform (55000) (22)

Same U i u M izkhn» cha SYA

VR 652 672 schi M Chloroform (177000) (65) "MV with GEN

VK SM

11 tires Chloroform 663 684 ots | th vy rofor (125000) (0)

EN is still in favor

Continuation of table 1

And here. chn vh i 683 701 12 kur i a Chloroform (208000) (47) was I oh

MSZHY pd

RVE nyu ne KZ 683 700 13 ssh me shah SCHA Chloroform pane Z sbe (183000) (15)

EV and

MEM M

Vaughn Zve. poison 683 699 14 and Chloroform beastyu bno (185000) (45)

And in

RK screen Chloofo M 688 708 seam refor (159000) (77)

SU CHU SYA shi schu shi no 653 664 16 ke sho in Chloroform (165000) (22)

SaNe bro ko z i Ov bo "7 efrnoiau Khporoform (112000) (35)

Ve yo; in 18 ee: shu Chloroform oche yo Xia (214000) (59) 1 9 I Horse th Chloroform 661 676 m I a 654 669 against (215000) (45) ? I Kk peche 633 642 21 Sho ne SCHI Chloroform

Te 00 yo (219000) (25) pivo M rani vu Shan 694 712 22 nn Chloroform (120000) (28) n more Kk

Mav nin o n ZSh hi Vo.

ЧИ мя Dena Ж her Doc ok, K: NO 648 663 more ptorophores (100000) i)

I Continuation of table 1 ee sha 6vo 696 sh Dec, poshi more Chloroform p. not ke sv; (120000) (6) it Chloroform nn NI eh z em I - - chi eh 65 1 667 і і poof Mav 7 І і Sk: MNE. se shi she BA 671 2 kn YACH with 7 х, 5 и ях

No. 635 647

S: OLYA, phone number 633 642

Chloroform and g Ay (225000) (25) 0525 7:

KYM se ECH ki VIMA no o CHI V NYA 663 31 MORE: ny she: Chloroform 678 a SHI 665 683 32 V she Chloroform (270000) (9)

She herself STILL "sv se A an I I."

That Zhoden bek KOT 652 nen NI she 647 that new roti, | foam (200000)

I t sh

Table 2

Sample Ill. Ifl. Ifl. Ifl., Ifl., Ifl., fresh 1 month 2 months From the month 6 months 12 months 24 vavkya | (zni CT on | 81657 8045 7855 76657 mg/m3 7 25 o, (una3.8 95) | (| on 5.2 95) | (| on 7.4 95) | (|) on 9.7 U) 26 BOVzhB (from the bottom | 49946 493410 48647 48248 80 mg/m3 7 7 o, (una1.895) | (in nazZ,095) | (| na4.3 95) | (| na 5.1 9)

Claims (1)

FORMULA OF THE INVENTION The method of labeling liquid hydrocarbons with a fluorescent marker, which includes the addition of a fluorescent marker - a solution of a long-wave phosphor in an organic solvent, which is distinguished by the fact that a square acid derivative of the general formula is used as a long-wave phosphor: zhu re HIT, Ye i same. y pe To SN still y raki y y cy i. also Code in B ke WRITE SHY what Z B . where A is 0, 5, "M-Va, -C(B) (B), and Ra, B? and in: - these are -SOVK, -SM, -"SOM(VU)(Ve), -SOONVI, and KU, Ve, V! and KK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -OH", -SOVK, -СМ, -СОМ(НУ) (Ве), -СООВИ-groups, where Kz is a branched or linear aliphatic group or an aromatic group; M and E are O, 5, B, M-B" and C(BE)(B)), where B" is -H, an aliphatic, alicyclic or aromatic group; IN! and VI - aliphatic groups, alicyclic groups, aromatic groups or EE! and B) form a cycle; AK is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -"СОМ(ВУ) (Ве), -СООВИ-groups; B2 and 2 are independently -H, -CM, -"СОМ(ВУ)(Бе), -СООВИ, -MO", -OH", an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in their alternately, they can be replaced by -СМ, -СОМ(ВУ)(Бе), -СООВИ, -МО», -ОВ9 or aliphatic groups. pana m chom zh: VK z ka Y dp vh M X Z I z i 5 i Ka ro sh yi y y ! in and Ah Kl: o ni EN M, press. I pi oh pn v In p Y ma nn nin kinnnnnnny 55Oo what em 0 yam OYUBo wavelength, nm Fig. 1