1070-4272/03/7607-1143$25.00C 2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 7, 2003, pp. 1143!1151. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 7,
2003, pp. 1176!1184.
Original Russian Text Copyright + 2003 by Sakvarelidze, Izmailova, Levachev, Rodin, Yampol’skaya, Kharlov, Nuss, Chezlov.
AND POLYMERIC MATERIALS
Interaction of Photographic Gelatins with Various Hardeners
in the Aqueous Phase
M. A. Sakvarelidze, V. N. Izmailova, S. M. Levachev, V. V. Rodin,
G. P. Yampol’skaya, A. E. Kharlov, P. V. Nuss, and I. G. Chezlov
Moscow Movie and Video Institute (Division of St. Petersburg State University of Motion Pictures and
Television), Moscow, Russia
Moscow State University, Moscow, Russia
Institute of Eye Diseases, Russian Academy of Medical Sciences, Moscow, Russia
St. Petersburg State University of Motion Pictures and Television, St. Petersburg, Russia
Received December 2, 2002; in final form, March 2003
Abstract-The properties of photographic gelatins in the aqueous phase were studied as influenced by
hardeners of various types. The effect of molecular-weight distribution of gelatins, reagent ratios, and tem-
perature on hardening was analyzed.
Gelatin plays various functions in production and
operation of light-sensitive materials; in particular, it
acts as an active medium in generation of photograph-
ic and physicochemical properties of emulsion layers.
In various stages of generation of a photographic
material, it is often necessary to change colloidal and
chemical properties of gelatin by its chemical modifi-
cation with hardeners . Therefore, it is urgent to
study the effect of various hardeners on the properties
of gelatin macromolecules in the bulk [2, 3] and at
the phase boundary [4, 5].
In this work we continued our studies of the mech-
anism of gelatin interaction with hardeners in aqueous
medium. We analyzed the relative reactivity of some
gelatin fractions with respect to hardeners of various
types using high-performance liquid chromatography
(HPLC), the molecular mechanism of interaction of
gelatin with hardener (high-resolution
H NMR spec-
troscopy), the size of gelatin macromolecules chemi-
cally modified with hardeners (photon-correlation
spectroscopy), and hydrodynamic parameters of
macromolecules (capillary viscometry).
Gelatin is a product of thermal, acidic, alkaline, or
enzymatic denaturation of collagens. Non-fractionated
gelatin is a mixture of a-, b, and g-chains; two last
components are the fragments linked with chemical
bonds, double and triple a-chains, or their fragments.
These fractions are different in their molecular weight,
colloidal, chemical, physicochemical, conformation,
and configuration parameters, and reactivity .
In , the molecular-weight distribution (MWD) of
a series of domestic and imported photographic gela-
tins was studied by gel electrophoresis in polyacryl-
amide gel and HPLC. Based on these results, a data-
base on the gelatin MWD as influenced by raw mate-
rials and treatment procedures was developed.
Using HPLC, we studied the selectivity of interac-
tion of various type of hardeners with separate gelatin
fractions as influenced by the contact time, tempera-
ture, and reagent concentration. We used a PL gel
nm Mixed-B column (Hewlett3Packard) with the
corresponding precolumn, a PUMP P-500 pump
(Pharmacia), and an HP (l = 630 nm) differential
flow refractometer as detector (Hewlett3Packard) .
The column was calibrated with respect to water-
soluble collagen. The molecular weight M of the
gelatin fractions was determined from the following
log M =33 0.057t, (1)
where t is the retention time.
In our work we studied polydisperse bone gelatin
prepared by alkaline denaturation (sample no. 1) and
low-molecular-weight gelatin obtained by acidic treat-
ment of pigskin (sample no. 2); the molecular-weight
distribution of the gelatins studied is illustrated in
Fig. 1 and Table 1.
In our study we used the hardeners of various
types: protected formaldehyde [tetra(hydroxymethyl)-
urea (LIKI-1) and N, N, N, N-tetra(hydroxymethyl)-