Formation of Chiral Structures in Photoinitiated Formose Reaction

Article abstract of DOI:10.1134/S0018143918020145

The possibility to synthesize biologically important sugars and other chiral compounds without any initiators in the UV-initiated reaction of formaldehyde in aqueous solution has been shown for the first time. An optically active condensed phase due to an

Full text of DOI:10.1134/S0018143918020145

ISSN 0018-1439, High Energy Chemistry, 2018, Vol. 52, No. 2, pp. 108–116. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © S.V. Stovbun, A.A. Skoblin, A.M. Zanin, V.A. Tverdislov, O.P. Taran, V.N. Parmon, 2018, published in Khimiya Vysokikh Energii, 2018, Vol. 52, No. 2,
pp. 94–102.
PHOTOCHEMISTRY
Formation of Chiral Structures in Photoinitiated Formose Reaction
S. V. Stovbuna, *, A. A. Skoblina, A. M. Zanina, V. A. Tverdislovb, O. P. Taranc, d, and V. N. Parmonc, e, f
aSemenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
bFaculty of Physics, Moscow State University, Moscow, Russia
cBoreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
dNovosibirsk State Technical University, Novosibirsk, Russia
eNovosibirsk State University, Novosibirsk, Russia
fTomsk State University, Tomsk, Russia
*e-mail: s.stovbun@yandex.ru
Received September 7, 2017
Abstract⎯The possibility to synthesize biologically important sugars and other chiral compounds without
any initiators in the UV-initiated reaction of formaldehyde in aqueous solution has been shown for the first
time. An optically active condensed phase due to an sp3-hybridized carbon atom has been detected. It has
been shown that this phase is formed due to the spatial cleavage of antipodes in the racemate, similar to the
cleavage of enantiomers following the sign of chirality in the known experiments of Pasteur. The results
have been obtained under the conditions that correspond to modern ideas about the form and vector of pre-
biological evolution and, therefore, can be of fundamental importance for understanding the processes of
biopoiesis.
Keywords: biopoiesis, chirality, formose reaction, formaldehyde, photoionization
DOI: 10.1134/S0018143918020145
INTRODUCTION
tiate the conversion of formaldehyde into sugars
by physical action: radiolysis [9] or UV irradiation
[10–14]. The factor common for these works is the
mandatory use of the main catalysts (CaCO3,
Ca(OH)2, Na2CO3, NaHCO3, NaOH, Mg(OH)2
Compounds with optically active (chiral) carbon
atoms provide the basis for biopoiesis—the process of
transformation of the inanimate nature into the living
nature. This is one of the most significant cross-cut-
ting trends in chemical and biological evolution [1]. In (except for [14]), as well as the use of dilute aqueous
particular, the polypeptide chain of proteins consists
of residues of L-amino acids, whereas D-deoxyribose
forms polymer chains of the double helix of DNA.
Except for special cases, carbohydrates and lipids are
also homochiral. The basis for chirality of molecular
structures in living systems is carbon in sp3 hybridiza-
tion.
Asymmetric carbon could enter the organic world
at the stage of the primary atmosphere of the planetes-
imal, containing formaldehyde H2C=O (FA) [2], for
example, through the Butlerov autocatalytic reaction
solutions. From the point of view of physicochemical
modeling of the synthesis of macromolecules from
maximally simple precursors (de-novo), it is, of
course, preferable to carry out the formose reaction
under the action of UV in gas (vapor) or equally con-
centrated water phase containing only FA molecules.
It is well known that the absorption band of the car-
bonyl group of the FA molecule has a maximum at 260 nm
with an absorption coefficient ε < 100 L/(mol cm)
[14]. However, in aqueous solution, FA interacts with
water molecules to form methylene glycol (MG),
which absorbs radiation with a shorter wavelength,
whose concentration in dilute solutions is much higher
than the concentration of free FA molecules. There-
fore, absorption of a quantum of light with a wave-
length λ ≤ 260 nm by FA molecules leads to breaking
the O–H and C=O bonds in the MG and FA mole-
cules, respectively, to form reactive species. It is rea-
sonable to assume simultaneous occurrence of at least
two groups of parallel reactions:
(the formose reaction1 in foreign terminology) (see
reviews [3–6]), in which any monosaccharides or
other organic compounds capable of producing ene-
diol forms can act as an autocatalyst (“seed”) [7, 8]. In
these chemical reactions, a set of monosaccharides
was found, starting with the simplest C2 glycolic alde-
hyde, up to C8. On the other hand, it is possible to ini-
1
Formose is
a mixture of synthetic carbohydrates—sugars
obtained from FA in the Butlerov reaction.
108

FORMATION OF CHIRAL STRUCTURES
109
(1) polymerization of MG (СН2(OH)2) to form ling reagent (1 mL) and water (1 mL) with 30 mg of
our product were poured into a test tube. The upper
part of the test tube was heated until the beginning of
boiling. The top layer turned first yellow (Cu(OH))
and then red-orange (Cu2O).
paraformaldehyde (PF) n(НО–СH2–ОН)
(H2CO)n + nH2O;
(2) oligomerization of FA to form mono-, di-, and
polysaccharides:
→
To determine the composition of the organic prod-
ucts of the reaction, gas-liquid chromatographic-
mass-spectrometric (GLC-MS) analysis was used
with preliminary derivatization by the silylation
method [15]. The initial sample (analyte-1) was sepa-
rated by dissolving in water under room conditions
into the water-soluble fraction (with subsequent evap-
oration) (analyte-2) and the water-insoluble fraction
(precipitated for 24 h; then the amount of the precipi-
tated substance remained unchanged) (analyte-3).
The samples of analyte-2 and analyte-3 for GLC–
MS analysis were prepared by two methods.
The first method: 20 mg of each sample was dis-
solved in 2 mL of distilled water.
The second method: hydrolysis of the samples
obtained upon irradiation (oligomeric compounds)
was carried out in order to obtain monomeric mole-
cules. For this purpose, 20 mg of each sample was
placed in 150 mL of a 1 mol/L HCl solution and
heated in a boiling water bath for 2 h with constant agi-
tation with a magnetic stirrer. To prevent evaporation
of water and other components of the reaction mix-
ture, reflux condensers were used.
The analysis of samples of analyte-2 and analyte-3
and their hydrolysates for the content of monosaccha-
rides and other organic compounds was carried out by
the of GLC-MS method with preliminary derivatiza-
tion by the silylation method [8].
Chromatographic–mass spectrometric analysis of
the derivatized samples was carried out on an Agilent
7000B instrument (USA) equipped with an Hp-5ms
capillary column measuring 30 m × 0.25 mm ×
0.25 μm. The chromatographic conditions were as fol-
lows: gradient heating of the column from 80 to 280°C
at a speed of 8°C/min.
The phase transition temperatures were deter-
mined using a differential chromel–alumel thermo-
couple, an F116/2 microampere meter, and a U800X
digital microscope.
Н–СН=О + Н–СН=О → СH2ОН–СН=О +
H2С=О → СH2ОН–СНОН–СН=О + … etc.
The above background served as the basis for per-
forming this work, whose aims were as follows:
⎯to study the possibility of the formation of chiral
products (sugars and others) upon UV photolysis with
a wavelength of λ = 254 nm of an aqueous FA solution
in the absence of any catalysts;
⎯to study the possibility of formation of macro-
scopic chiral phases in the products of this reaction.
This work models the processes which, in the
framework of modern concepts, could actually take
place at the stage of the primary atmosphere of the
planetesimal. It is quite obvious that carrying out such
physicochemical modeling is of interest for under-
standing the processes of biopoiesis.
EXPERIMENTAL
We used in the experiments a highly concentrated
(95%) solution of FA in water, obtained by decompo-
sition of paraformaldehyde at 160–170°C for 1.5 h.
The mass of the initial solution was 600 g. UV irradia-
tion was carried out with a DRSh-100 lamp (without a
filter) onto the exposed surface of the solution placed
in a glass 2-L beaker, with continuous stirring. The
distance between the lamp and the surface of the solu-
tion was 10 cm. To eliminate the spontaneous low-
temperature conversion of FA to PF, a thermostating
temperature of 70°C was chosen. The experiment was
terminated in 8.5 h after complete solidification of the
initial solution.
The main (by mass) product formed was parafor-
maldehyde. This reaction, side for us, occurs accord-
ing to scheme (1) (see above). Due to the expected
small yield of the sugars formed according to scheme
(2) and in order to minimize the losses upon separa-
tion of the desired carbohydrates from PF, sublima-
tion of PF obtained upon irradiation, enhanced by
evacuation, was chosen. The residual vapor pressure of
PF permitted us to do this under rather mild condi-
tions (70–80°C), but for a long time (265 h). The total
yield of nonvolatile products was no less than 0.7 wt %.
This product will be further referred to as analyte-1. A
qualitative analysis of analyte-1 for sugars was carried
out using the classical Fehling reagent as follows:
potassium tartrate (150 g) was dissolved in a 1-L flask
in 600–700 mL of sodium hydroxide solution with a
density of 1.12. To the resulting potassium–sodium
tartrate, a solution of copper sulfate (34.636 g CuSO4
Thin layer chromatography was also used for the
studies.
The optical activity of aqueous solutions (disper-
sions) of analyte-1, analyte-2, and analyte-3 was stud-
ied using a polarimeter with a cell 20 cm long.
Optical microscopy in transmitted light (using a
MIKMED-6 microscope) of xerogel (or dispersed
precipitate) of analyte-1 obtained by slow drying of its
aqueous solutions (dispersions) on a slide was carried
out. A polarizer was placed between the light source
per 160 mL water) was gradually added. The resulting and the slide, and an analyzer (that is, the second
clear solution was diluted with water to 1 L. The Feh- polarizer) between the slide and the microscope
HIGH ENERGY CHEMISTRY Vol. 52 No. 2 2018

110
STOVBUN et al.
×106
+ EI TIC Scan #15_14.03.d
1
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
1
4
3
8
9
10
11
13
7
15
6
5
*
2
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Counts vs. Acquisition Time, min
4
Fig. 1. Chromatogram of the analyte-2 sample derivatized by silylation.
objective. The polarizer and analyzer axes were ber of C atoms of 6 (0.944), glucose-C6 (0.947), arab-
directed at an angle of 90° (dark field regime).
inose-C5 (0.976), xylose-C6 (0.977), and sucrose-C12
(0.923)), it can be seen that the sugars tested, con-
tained in analyte-1, can belong to the group of sugars
with the number of carbon atoms within 12, which
does not contradict the data obtained in the Fehling
reaction.
The qualitative composition of products obtained
upon photolysis was more precisely determined by the
GLC-MS method. The results of analysis of the ana-
lyte-2 and analyte-3 samples prepared by the first
method, that is, dissolved in distilled water and deri-
vatized, are shown in Figs. 1, 2 and Tables 1, 2, respec-
tively. The tables show decoding of chromatographic
peaks, including the retention times and peak areas, as
well as the percentage of individual peaks with respect
to the total area of all peaks.
Analyte-2 sample (Fig. 1, Table 1). According to
the results of the GLC-MS analysis, 3 peaks of 16 were
identified, which comprised 32% of the total area of all
peaks. Note that here and below, the notation D(L) is
introduced to emphasize that GLC-MS does not dis-
tinguish antipodes. It was shown that about 13.8% was
glycerol, followed by D(L)-xylopyranose (9.1%) and
β-D(L)-(+)-xylopyranose (9.1%).
Analyte-3 sample (Fig. 2, Table 2). 8 peaks of 22
were identified, which comprised 63% of the total area
of all peaks. Polyol glycerol and polyol of undeter-
mined structure (peak 3) comprised 12.6%, glycolic
acid 11.8%, and glycolic aldehyde 4.5%. The relative
content of monosaccharides was close to 34%: two of
them were not identified (peaks 7 and 12), fructose
comprised 13.9%, and galactose ~2%.
RESULTS AND DISCUSSION
The product (analyte-1) obtained by irradiation of
the initial FA solution with UV light has a brownish
color. The product is practically insoluble in hexane,
ethyl acetate, acetone, glycerol, ammonia, hydrogen
peroxide, and slightly soluble in water. It is readily sol-
uble in benzene, cyclohexane, chloroform, carbon tet-
rachloride. Solutions or dispersions of analyte-1 are
optically inactive. The water-soluble portion of the
product is also optically inactive (analyte-2). It is a
white compound, viscous at room temperature; its
boiling point is 118°C at 760 mm Hg. The water-insol-
uble fraction (analyte-3) is a beige-colored crystalline
compound; its melting point is 137.5°C; its aqueous
dispersion is also optically inactive. The absence of
optical activity of the solutions or dispersions is quite
an expected result, since there is no significant chiral
asymmetric factor in the reaction under study, and the
reaction products are racemic.
Qualitative analysis of analyte-1 for monosaccha-
rides was carried out using the freshly prepared Feh-
ling reagent. The analysis is based on the reducing
ability of sugars [16]. It showed the presence of reduc-
ing carbohydrates in this product. It is well known that
all monosaccharides and only a part of disaccharides
(lactose, maltose, and cellobiose) belong to such car-
bohydrates. Therefore, it is reasonable to assume
the presence of some of these biologically important
sugars containing an asymmetric carbon atom in ana-
lyte-1.
The results of the GLC-MS analysis of the derivat-
ized hydrolyzate of the analyte-2 sample are shown in
Fig. 3, and the decoding of the most probable com-
pounds corresponding to the chromatographic peaks
is shown in Table 3. It should be noted that 16 of
17 peaks are identified. According to the data
An evaluation of the type of sugars in analyte-1 was
also carried out by thin layer chromatography using a
SiO2 sorbent and an eluent consisting of a mixture of
cyclohexane–benzene–methanol taken in a volume
ratio of 2 : 3 : 1. Comparing the retention factors Rf
obtained for chromatograms of analyte-1 (0.935) and obtained, the predominant products are polyols: diols
for a number of trial sugars (rhamnose with the num- (peaks 1, 3, 5–8), glycerol (peak 4), ribitol (peak 12),
HIGH ENERGY CHEMISTRY
Vol. 52
No. 2
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FORMATION OF CHIRAL STRUCTURES
111
×105 + EI TIC Scan #16_14.03.d
3.25
4
7
1
1
3.00
2.75
2
1
2.50
2.25
2.00
1.75
1.50
1.25
1.00
0.75
0.50
0.25
0
20
22
19
17
6
12
16
10
14
8
3
5
6
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Counts vs. Acquisition Time, min
4
Fig. 2. Chromatogram of the analyte-3 sample derivatized by silylation.
unidentified polyol (peak 13), and erythritol (peak 14). 1,4-diol (0.57%), erythritol (1.12%), and ribitol
The total content of polyols was 76.1%, of which the (0.5%). The total percentage of branched deoxysac-
highest content (37.2%) corresponds to glycerol, then charides (D(L)-erythro-pentitol-2-deoxy, D(L)-pen-
2-butene-1,4-diol (13.1%), 3-methylene-1,4-diol- tofuranose-2-deoxy, and D(L)-arabinohexitol-2-
butane (10.3%), and others. The following sugars were deoxy) was 3.3%. The contents of lactic acid (peak 2)
detected: fructose (12.4%), xylose (0.9%), and disac- and lactaldehyde (peak 16) were close to 1.3 and 1.1%,
charide sucrose (1.1%).
respectively. Disaccharides trehalose and maltose
(1.5% in total), monosaccharides lyscopyranose
(1.7%), talopyranose (0.17%), glycopyranose (0.9%),
fructose (0.64%), and a sugar of undetermined struc-
ture (peak 23, 0.72%) were identified.
The results of the GLC-MS analysis of the derivat-
ized hydrolyzate of the analyte-3 sample are shown in
Fig. 4, and the decoding of the most probable com-
pounds corresponding to the chromatographic peaks
is shown in Table 4. The structure of 18 peaks out of 31
was established, which comprised 49% of the total area tained significant amounts of polyols of different
of the peaks. Five different polyols were found, with structures, monosaccharides, and disaccharides; and
the content of glycerol (33.8%) being the highest, and deoxy sugars are found in the analyte-2 sample.
lower contents of ethylene glycol (0.73%), 2-butene- Hydrolysis of both samples permitted us to specify the
Hence, the analyte-2 and analyte-3 samples con-
Table 1. Components of the analyte-2 sample, specifying the numbering of peaks, retention times, peak areas, and their
percentage with respect to the total area of peaks
Peak number
Retention time
Area
Area, %
Compound
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
11.292
15
455251
81010
13.82
2.46
9.1
Glycerol
16.559
17.192
17.512
19.357
23.478
24.402
24.728
25.636
26.574
26.681
27.746
27.933
29.421
36.269
299785
300088
238 904
246149
206333
166998
140863
146532
166790
157450
216093
162195
132042
177290
(L,D)-Xylopyranose
β-(L,D)-(+)-Xylopyranose
9.11
7.25
7.47
6.26
5.07
4.28
4.45
5.06
4.78
6.56
4.92
4.01
5.38
HIGH ENERGY CHEMISTRY Vol. 52 No. 2 2018

112
STOVBUN et al.
Table 2. Components of the analyte-3 sample, specifying the numbering of peaks, retention times, peak areas, and their
percentage with respect to the total area of peaks
Peak number
Retention time
Area
Area, %
Compound
Glycolic acid
Glycerol
Polyola
(L,D)-Fructose
1
2
3
4
5
6
7
7.643
11.202
12.232
14.084
14.319
14.457
16.61
16.796
18.151
18.475
18.929
19.058
440590
401763
69146
517897
83669
11.8
10.76
1.85
13.87
2.24
4.48
14.14
1.98
2.58
2.66
3.57
3.88
167139
527763
Glycolic aldehyde
Sugar?a
8
9
10
11
12
74051
96235
99 470
133416
144972
Sugar?a
Galactose?a
13
72876
19.373
19.765
19.855
23.456
23.91
24.396
24.721
25.63
1.95
2.37
2.8
1.81
2.44
2.54
2.08
4.44
2.84
2.89
14
15
16
17
18
19
20
21
22
88557
104707
67562
91200
94838
77624
165912
106083
108029
26.672
27.131
a
The most probable of the compounds proposed by the database.
list of monomeric compounds involving in the poly- and water-soluble (analyte-2) and water-insoluble
mer structures. The optical isomers (enantiomers) of (analyte-3) products obtained by slow drying of their
practically all chiral products found in the formose aqueous solutions (dispersions) on a slide were used.
reaction are of considerable functional significance in
Figure 5 shows the results of optical microscopy of
natural systems (see Table 5) [10].
xerogel (dispersed precipitate) of analyte-1 in polar-
To study the optical activity of products of FA pho- ized light. It can be clearly seen that a significant por-
tolysis, xerogels (dispersed precipitates) of analyte-1, tion of the xerogel (or dispersed precipitate) structures
+ EI TIC Scan #16_hcl-2h.d
6
4
8
9
×105
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
13
15
* 2
1
16
5
17
3
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23
Counts vs. Acquisition Time, min
Fig. 3. Chromatogram of the analyte-2 sample derivatized by silylation after acid hydrolysis with 1 M HCl for 2 h.
HIGH ENERGY CHEMISTRY Vol. 52 No. 2
2018

FORMATION OF CHIRAL STRUCTURES
113
Table 3. Components of hydrolysate of the analyte-2 sample, specifying the numbering of peaks, retention times, peak
areas, and their percentage with respect to the total area of peaks
Peak number
Retention time
Area
Area, %
Compound
Ethylene glycol
Ethyl lactate
diola
Glycerol
diola
2-Butene-1,4-diol
2-Propanone-1.3-diol
3-Methylene-1,4-diol-butane
Fructose
1
2
3
4
5
6
7
8
9
10
11
12
13
6.073
6.431
9.971
103749
131994
74874
1.17
1.49
0.84
37.22
1.89
13.13
3.36
10.29
12.4
1.21
0.74
0.74
6.44
0.87
6.25
0.9
11.272
12.039
12.273
13.318
13.361
14.092
14.152
14.331
14.412
14.459
14.511
16.6
3299798
167528
1163630
297939
912410
1099177
107002
66029
Sugara
Ribitol
Polyol?a
Erythritol
4-Ketoglucose??a
65543
570575
14
15
76797
553715
16
17
17.049
18.488
79435
94526
Xylose
Sucrose
1.07
a
The most probable of the compounds proposed by the database.
obtained, glow on slides when the analyzer is posi- in electromagnetic interactions. Therefore, the only
tioned perpendicular to the polarization plane of light reason for the formation of the optically active struc-
passing through the sample, that is, in the dark-field tures detected can be the spatial cleavage of the antip-
regime (Fig. 5). This means the presence of optical odes in the racemate, similar to the cleavage of enan-
activity in the condensed phase of the xerogel struc- tiomers following the sign of chirality in the known
tures of the analyte-1 sample. The portion of optically experiments of Pasteur [18].
inactive structures in analyte-1 xerogel, according to a
Since in this case, this is a fairly realistic model of
visual estimate (Fig. 5), is negligible.
processes in the primary atmosphere of the Earth, this
In the sample as a whole, the antipodes, that is, the experiment demonstrates that spontaneous formation
left and right isomers of chiral products of photolysis, of chiral compounds (sugars) and subsequent sponta-
are formed in the same amounts. This follows from the neous spatial separation of antipodes to form macro-
equal reaction rates of the synthesis of antipodes, scopic fragments of chiral (optically active) phases in
which, in turn, follows from the conservation of parity systems similar to prebiological systems, can occur
×106
+ EI TIC Scan hcl_16-1.d
6
10
5
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
8
15
21
25
*
27
30
*
*
17
2
1
23
18
3
22
*
9
7
* 4
6
7
8
9
10 11
12
13 14 15 16
17
18 19 20 21 22
Counts vs. Acquisition Time, min
Fig. 4. Chromatogram of the analyte-3 sample derivatized by silylation after acid hydrolysis with 1 M HCl for 2 h.
HIGH ENERGY CHEMISTRY Vol. 52 No. 2 2018

114
STOVBUN et al.
Table 4. Components of hydrolysate of the analyte-3 sample, specifying the numbering of peaks, retention times, peak
areas, and their percentage with respect to the total area of peaks
Peak number
Retention time
Area
Area, %
Compound
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
6.078
6.437
9.984
204113
348061
200382
87073
9395519
3455734
158491
3050557
97263
3974000
176658
152499
222474
251139
2295983
293513
311569
121680
113041
168934
478846
140672
200599
0.73
1.25
0.72
0.31
33.78
12.42
0.57
10.97
0.35
14.29
0.64
0.55
0.8
Ethylene glycol
Lactic acid
10.923
11.291
12.291
13.088
13.381
13.888
14.113
14.172
14.203
14.349
14.432
14.48
14.532
14.909
16.13
16.416
16.919
17.057
17.563
17.965
Glycerol
2-Butene-1,4-diol
(L, D)-Fructose
0.9
8.25
1.06
1.12
0.44
0.41
0.61
1.72
0.51
0.72
Lactic aldehyde
Erythritol
Lyxopyranose
Ribitol
Sugar?a
(L, D)-Erithro-pentitol-2-deoxy?a
(L, D)-Erithro-pentofuranose-2-deoxy?a
(L, D)-Arabino-hexitol-2-deoxy?a
Beta-(L, D)-Methylfructofuranoside?a
Trehalose
24
25
26
27
126112
450204
335549
274633
18.361
18.384
18.478
0.45
1.62
1.21
18.847
18.878
18.936
19.692
0.99
0.58
0.17
0.97
28
29
30
162409
48612
270387
β-(L, D)-(+)-Talopyranose
Maltose?a
Glucopyranose?a
31
247706
20.066
0.89
a
The most probable of the compounds proposed by the database.
even in solutions of compounds with molecular
masses of no more than μ ~ 102 Da, that is, much ear-
lier than the chiral macromolecules were formed.
(1) The possibility of synthesizing biologically sig-
nificant sugars and other chiral compounds without
any initiators in the UV-initiated reaction of formal-
dehyde in an aqueous solution has been shown for the
first time.
CONCLUSIONS
(2) An optically active condensed phase due to sp3-
hybridized carbon atom has been detected.
In summary, in the physicochemical modeling of
de-novo, by photolysis of a concentrated solution of
formaldehyde and subsequent condensation of the
product of the formose reaction, the following experi-
mental results have been obtained:
(3) It has been shown that the optically active con-
densed phase is formed due to the spatial cleavage of
the antipodes in the racemate, similar to the cleavage
of enantiomers following the sign of chirality in the
known experiments of Pasteur.
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FORMATION OF CHIRAL STRUCTURES
115
Table 5. Biological significance of the compounds obtained in the reaction
No.
1
Compound
Glycerol
Functional significance
The basic molecule from which triglycerides are formed, which are important compo-
nents in the process of metabolism in living organisms
2
3
Xylose
Participates in the processes of mutual transformations of carbohydrates, contained
in plant embryos as an ergastic compound
Contained in honey and some fruits, used to produce energy in the liver during glycolysis;
as a monosaccharide unit, included in sucrose and lactulose
Fructose
4
5
6
Sucrose
Glycolic acid
Glycolic aldehyde
Natural carbohydrate used for food, the main constituent of cane sugar and sugar beet
Included in the group of fruit alpha-hydroxy acids
Precursor of many biologically active compounds, for example, amino acid glycine;
as intermediate, involved in some biochemical processes, for example, in catabolism
of purines
7
Galactose
Incorporated in oligosaccharides (melibiose, raffinose, stachyose), some glycosides, plant
and bacterial polysaccharides (gums, mucus, galactans, pectins, hemicelluloses);
in the body of animals and humans, in lactose, group-specific polysaccharides, cerebro-
sides, keratosulfate, and others. In animal and plant tissues can be involved in glycolysis,
turning into glucose-1-phosphate, which is assimilated
8
9
Polyhydric alcohols Contained in mushrooms, fruits, and vegetables, as well as in humans and animals (eryth-
ritol); ribitol is incorporated in riboflavin and flavinadenine dinucleotides and is present
in the cell walls of gram-positive bacteria
Deoxysugars
Components of glycoside, oligo- and polysaccharides; their important representative
2-deoxy-D-ribose is in the composition of deoxyribonucleic acids (DNAs)
Produced by the degradation of glucose, forms in muscles
10
11
Lactic acid
Trehalose
Possesses therapeutic properties at the cell level, controlling the unfolding of proteins,
in the larvae of the chironomid Polypedilum vanderplanki, capable of withstanding dry-
ing, the accumulation in the cells of a large concentration of trehalose is one of the mech-
anism of resistance to drying
12
Maltose
In animal and plant organisms, maltose is formed during the enzymatic cleavage of starch
and glycogen
13
14
Lyscopyranose
Glucopyranose
In nature it is extremely rare, for example, as a component of some bacterial glycolipids
The monomer from which the two most important polysaccharides starch and cellulose
are formed
Fig. 5. Microphotograph (magnification ×40) of xerogel (dispersed precipitate) of analyte-1 in a polarizer and analyzer crossed
at 90° (dark field regime). The ratio of white–black contrast indicates a much larger proportion of optically active condensed
phases in the xerogel, in comparison with optically inactive phases.
HIGH ENERGY CHEMISTRY Vol. 52 No. 2 2018

116
STOVBUN et al.
10. Baly, E.C.C., Ind. Eng. Chem., 1924, vol. 16, p. 1016.
These experimental results have been obtained
under conditions corresponding to modern concepts
of the form and vector of prebiological evolution, and
therefore may be of fundamental importance for
understanding the processes of biopoiesis.
11. Shigemasa, Y., Matsuda, Y., Sakazawa, C., and Mat-
sura, T., Bull. Chem. Soc. Jpn., 1977, vol. 50, no. 1,
p. 222.
12. Pestunova, O., Simonov, A., Snytnikov, V., Stoy-
anovsky, V., and Parmon, V., Space Life Sciences: Astro-
biology: Steps toward Origin of Life and Titan before Cas-
sini, Bernstein M., Navarro-González, R., and
Raulin, F., Eds., Oxford: Elsevier, 2005, p. 214.
13. Delidovich, I.V., Taran, O.P., Simonov, A.N., Matvi-
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vol. 48, no. 3, p. 441.
14. Snytnikova, O.A., Simonov, A.N., Pestunova, O.P.,
Parmon, V.N., and Tsentalovich, Y.P., Mendeleev Com-
mun., 2006, vol. 15, no. 1, p. 9.
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