HA Molecules Research Articles

Effect of photoinitiator on chain degradation of hyaluronic acid

ObjectivesPhotocrosslinking systems of polymers have been widely studied using UV or visible light irradiation. However, the photodegradation behavior derived from light irradiation was rarely reported, comparing with the photocrosslinking. In this study, the tyramine-modified hyaluronic acid (HA/Tyr) hydrogel was prepared using riboflavin (RF) as a photoinitiator, and the degradation behavior of HA by the reactive oxygen species (ROS) generated in photochemical process was investigated.Materials and methodsThe HA/Tyr conjugate was synthesized by EDC/NHS chemistry to introduce phenol group. Degree of substitution (DS, %) of phenol group to HA molecule was about 25%. The structural change of HA/Tyr was measured by proton nuclear magnetic resonance (1H-NMR) and attenuated total reflectance infrared spectroscopy (ATR-FTIR), and the rheological properties of photocrosslinked HA/Tyr hydrogel were investigated by rheometer.ResultsThe HA/Tyr solution with 25% substitution formed a stable hydrogel via visible light irradiation in the presence of RF photoinitiator. Rheological data of HA/Tyr solution showed that the storage modulus (G’) was increased with increasing HA concentration. Additionally, it was found that RF initiated by visible light irradiation induced the degradation of HA molecular chain, and consequently reduced the viscosity of HA/Tyr solutions.ConclusionThe results indicate that RF-based photoinitiator system caused the degradation of HA molecule by ROS generated in photochemical process as well as the crosslinking of HA/Tyr.

Hydrophilic modification on polyvinyl alcohol membrane by hyaluronic acid

PVA was dissolved in mixed solvent (DMSO and water) and followed by several freeze-thaw cycles in a mold to produce PVA membrane. Surface modification of PVA membranes by HA molecules was investigated to improve the hydrophilicity of the membrane surface thereby reducing adsorption of the proteins onto the membrane. The surface composition, water contact angle, optical and mechanical properties, surface morphology, cell compatibility and protein adhesion were systematically investigated. ATR-FTIR spectra, XPS, SEM and AFM indicated that PVA membranes were successfully modified by grafting of the HA. The modified membranes showed increased hydrophilicity and cytocompatibility, decreased surface roughness and mechanical properties, and suppressed cell and protein adhesion compared to the pristine membrane. In general, the achievement of the HA coating with anti-adhesive property can potentially be widely used on surface modification of artificial cornea and other biomedical implants.

Algorithm for Extracting Weak Bands Kinetics from the Transient Absorption Spectra of the Rhodobacter sphaeroides Reaction Center.

An algorithm to extract kinetics of the ion radical bands from the strong absorption background in the transient absorption spectra of the Rhodobacter sphaeroides reaction centers upon femtosecond excitation of the primary electron donor is suggested. The rising kinetics of the transient absorption band at 1020 nm and the bleaching kinetics of the 545-nm band constructed using the proposed method are adequately fitted by the kinetic equations for sequential electron transfer from the excited primary donor to the BA (monomeric bacteriochlorophyll) molecule, and then to the HA (bacteriopheophytin serving as an electron acceptor) molecule with the rate constants of 3.5 ± 0.2 and 0.8 ± 0.1 ps, respectively. The kinetics of the bacteriochlorophyll absorption band at 600 nm shows both the ultrafast bleaching of the P870 dimer and slower bleaching of the BA monomer due to its transition to the anion radical. The plotted kinetics of the ion radical bands is in agreement with the concentration profiles of the charge-separated states produced by the global target analysis of experimental data using the model of sequential electron transfer in the reaction centers.

Change of phenotypic properties of escape mutants and readaptants of influenza virus A (H1N1)pdm09 under the influence of selected mutations in the molecule of hemagglutinin.

After the emergence and spread of pandemic H1N1 viruses in 2009, antigenic epitopes recognized by neutralizing antibodies against the hemagglutinin of influenza A/Moscow/01/09(H1N1)pdm09 viruses were studied. The purpose of the study was to obtain readapted variants of the virus from a low-virulent escapemutant that has an increased affinity of the avian and the human types cellular receptors compared to the wild type and the comparative study of their antigenic and receptor specificity. Viruses were accumulated in 10-day-old chicken embryos. The MAB panel against HA of influenza virus strain A/IIV-Moscow/01/09(H1N1)sw1 was used in the form of ascites fluids from mice. Immunization of mice, HI testing, elution of viruses from chicken erythrocytes, PCR and sequencing of readapted variants were performed by standard methods. The amino acid substitution A198E acquired in the process of readaptation leads to changes in the antigenic specificity. A correlation was found between a decrease in virulence of a low-virulent escape mutant associated with the substitution D190N in the hemagglutinin molecule and an increase in the hemagglutinating titer to inhibitors in normal mouse serum. Viruses with low affinity of cellular receptor analogs and carrying amino acid substitutions have an increased ability to elute from chicken erythrocytes. The results discuss the effect of mutations in the HA molecule of the influenza A(H1N1) pdm09 virus to the change in antigen specificity; virulence for mice, adsorption-elution at cellular receptors. A comparative study of the antigenic specificity and receptor-binding activity of the escape mutants was conducted for the hemagglutinin of the influenza virus A/Moscow/01/2009 (H1N1)swl, and the readapted variants obtained for one of the escape mutants with reduced virulence for mouse. Monitoring the pleiotropic effect of mutations in the hemagglutinin H1 molecule is necessary to predict variants of the virus with pandemic potential.

The Molecular Basis for Antigenic Drift of Human A/H2N2 Influenza Viruses.

Influenza A/H2N2 viruses caused a pandemic in 1957 and continued to circulate in humans until 1968. The antigenic evolution of A/H2N2 viruses over time and the amino acid substitutions responsible for this antigenic evolution are not known. Here, the antigenic diversity of a representative set of human A/H2N2 viruses isolated between 1957 and 1968 was characterized. The antigenic change of influenza A/H2N2 viruses during the 12 years that this virus circulated was modest. Two amino acid substitutions, T128D and N139K, located in the head domain of the H2 hemagglutinin (HA) molecule, were identified as important determinants of antigenic change during A/H2N2 virus evolution. The rate of A/H2N2 virus antigenic evolution during the 12-year period after introduction in humans was half that of A/H3N2 viruses, despite similar rates of genetic change.IMPORTANCE While influenza A viruses of subtype H2N2 were at the origin of the Asian influenza pandemic, little is known about the antigenic changes that occurred during the twelve years of circulation in humans, the role of preexisting immunity, and the evolutionary rates of the virus. In this study, the antigenic map derived from hemagglutination inhibition (HI) titers of cell-cultured virus isolates and ferret postinfection sera displayed a directional evolution of viruses away from earlier isolates. Furthermore, individual mutations in close proximity to the receptor-binding site of the HA molecule determined the antigenic reactivity, confirming that individual amino acid substitutions in A/H2N2 viruses can confer major antigenic changes. This study adds to our understanding of virus evolution with respect to antigenic variability, rates of virus evolution, and potential escape mutants of A/H2N2.

Hyaluronic Acid Nanoparticle Composite Films Confer Favorable Time-Dependent Biofunctions for Vascular Wound Healing.

Vascular stent implantation is the primary treatment for coronary artery disease. Surface modification of coronary stents is a topic of interest to prevent thrombosis and restenosis and to promote endothelization. However, bioactive coatings on implants have not yet been fully developed for the time-ordered biological requirements of vascular stents. The first month after vascular stent implantation, the pathological changes in the injured vascular tissue are complex and time-ordered. Therefore, vascular stents possess time-dependent biofunctions with early phase anticoagulant and anti-inflammatory properties. In the later stage, inhibitory effects on smooth muscle cell proliferation and the promotion of endothelial cell adhesion might meet the requirements of vascular repair. We fabricated three types of hyaluronic acid nanoparticles (HA-NPs) by subjecting HA and poly(ether imide) to ethyl(dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide coupling reaction. The HA-NPs prepared by HA with a molecular weight of 100 kDa showed the best stability in a hyaluronidase environment. HA-NP composite films (HA-NCFs) were then fabricated by coimmobilizing selected HA-NPs (100 kDa) and HA molecules (100 kDa) through amide reaction on PDA/HD coated 316 L stainless steel surfaces. The detachment behavior of HA-NPs (100 kDa) in PBS for 20 days indicated that the HA-NPs (100 kDa) gradually detached from the surface. In vitro tests (anticoagulant and anti-inflammatory tests, endothelial cells, and smooth muscle cells seeding, and bacterial adhesion test) indicated that the newly fabricated HA-NCFs have inhibitory effects on the adhesion of fibrinogen, platelets, macrophages, bacteria, SMCs, and ECs. As the HA-NPs detached from the surface, the HA-NCFs showed excellent gradual comprehensive biocompatibility, which promoted adhesion and proliferation of ECs while still exerting inhibitory effects on the platelets, macrophages, and SMCs. Finally, in vivo SS wire implantation test (aortic implantation in healthy Sprague-Dawley rats) showed that HA-NCFs possessed anti-inflammatory properties, inhibited the proliferation of smooth muscle cells, and promoted re-endothelialization. In particular, HA-NCFs with time-dependent biofunctions showed better antirestenosis effects than those of surfaces modified with molecular HA, which exhibited constant biocompatibility. This study provides an important basis for the construction of HA-NP composite films with favorable time-dependent biofunctions for the time-ordered biological requirements of vascular stent.

Topological Design of Star Glycopolymers for Controlling the Interaction with the Influenza Virus.

The precise design of synthetic polymer ligands using controlled polymerization techniques provides an advantage for the field of nanoscience. We report the topological design of glyco-ligands based on synthetic polymers for targeting hemagglutinin (HA, lectin on the influenza virus). To achieve precise arrangement of the glycounits toward the sugar-binding pockets of HA, triarm star glycopolymers were synthesized. The interaction of the star glycopolymers with HA was found to depend on the length of the polymer arms and was maximized when the hydrodynamic diameter of the star glycopolymer was comparable to the distance between the sugar-binding pockets of HA. Following the formula of multivalent interaction, the number of binding sites in the interaction of the glycopolymers with HA was estimated as 1.8-2.7. Considering one HA molecule has three sugar-binding pockets, these values were reasonable. The binding mode of synthetic glycopolymer-ligands toward lectins could be tuned using controlled radical polymerization techniques.

Influence of the Coagulation Mechanism on the Coagulation Performances Using New Composite Coagulants: Role of the Raw Water Characteristics

To improve the coagulation performances, new composite coagulants were used to treat different water samples. The results indicate that Ca2+ has no significant effects on the removal efficiency for turbidity in the kaolin system. The residual aluminum decreased from 0.15 mg·L-1 to 0.10 mg·L-1 (AlCl3 was used as coagulant and the coagulant dosage was 0.10 mmol·L-1). The presence of Ca2+ led to the decrease of the amount of negative charges in the HA system and the residual aluminum decreased due to the decrease of the complexation between the HA molecules and Al-based coagulants. When the raw water contained BSA molecules and the coagulant dosage was 0.16 mmol·L-1, the flocs formed by PACl with Ca2+ were larger (~50 μm) than the flocs generated by PACl and the settleability also improved. Under alkaline conditions (pH=8.5), the DOC concentration decreased after coagulation process by~0.2-0.6 mg·L-1 and the residual aluminum decreased by~0.4-0.7 mg·L-1 using composite coagulants. Under acidic conditions (pH=5.5), the concentrations of DOC and residual aluminum did not significantly differ.

Hyaluronic acid selective anchoring to the cytoskeleton: An atomic force microscopy study.

The hyaluronic acid component of the glycocalyx plays a role in cell mechanotransduction by selectively transmitting mechanical signals to the cell cytoskeleton or to the cell membrane. The aim of this study was to evaluate the mechanical link between the hyaluronic acid molecule and the cell cytoskeleton by means of atomic force microscopy single molecule force spectroscopy. Hyaluronic acid molecules on live cells were targeted with probes coated with hyaluronic acid binding protein. Two different types of events were observed when the detachment of the target molecule from the probe occurred, suggesting the presence of cytoskeleton- and membrane-anchored molecules. Membrane-anchored molecules facilitated the formation of tethers when pulled. About 15% of the tested hyaluronic acid molecules were shown to be anchored to the cytoskeleton. When multiple molecules bonded to the probe, specific detachment patterns were observed, suggesting that a cytoskeletal bond needed to be broken to improve the ability to pull tethers from the cell membrane. This likely resulted in the formation of tethering structures maintaining a cytoskeletal core similar to the ones observed for cells over-expressing HA synthases. The different observed rupture events were associated with separate mechanotransductive mechanisms in an analogous manner to that previously proposed for the endothelial glycocalyx. Single cytoskeleton anchored rupture events represent HA molecules linked to the cytoskeleton and therefore transmitting mechanical stimuli into the inner cell compartments. Single membrane tethers would conversely represent the glycocalyx molecules connected to areas of the membrane where an abundance of signalling molecules reside.

Selection of influenza virus resistant to the novel camphor-based antiviral camphecene results in loss of pathogenicity

Due to the ability of influenza virus to develop drug resistance, the search for novel antivirals is an important goal of medical science and health care systems. We assessed the ability of the influenza virus to develop resistance to the hemagglutinin inhibitor camphecene and characterized laboratory-selected resistant strains. We showed by electron microscopy that camphecene decreases the number of virions fusing their envelopes with endosomal membranes. A 160-fold decrease in virus susceptibility was observed after six passages in cells. This was associated with the emergence of a V458L mutation in the HA2 subunit of HA and with a decrease in viral pathogenicity. Molecular modeling predicts that this substitution results in a more stable HA molecule compared to wild-type HA; and an altered camphecene-binding site. Therefore, despite the relatively rapid development of resistance, camphecene remains promising as a potential antiviral due to the low pathogenicity of resistant viruses that may arise.

The effect of the molecular weight of hyaluronic acid on the physicochemical characterization of hyaluronic acid-curcumin conjugates and in vitro evaluation in glioma cells.

In this study, a redox-sensitive glioma-targeting micelle system was designed to deliver curcumin (CUR) by conjugating it to hyaluronic acid (HA-s-s-CUR, HSC) via disulfide linkage. The effect of the molecular weight of HA on the physicochemical characteristics of HSC conjugates and their in vitro effects in glioma cells were also explored. These conjugates formed nano-scale micelles (209-926 nm) independently in aqueous solution. The micelles greatly increased the solubility of CUR and improved its stability, which is crucial for harnessing the therapeutic potential of this active molecule. The redox sensitivities of different HSC micelles were measured by using a dynamic light scattering method and in vitro release assay, which showed that the low (50 kDa) and medium molecular weight (200 kDa and 500 kD) HA-based conjugates were sensitive to GSH, whereas higher molecular weights (1000 kDa and 2000 kDa) did not show redox-sensitivity. Increased cytotoxicity and uptake of low and medium molecular weight-modified HSC conjugates by the glioma cells further confirmed that the sensitive micelles are more effective for intracellular drug delivery compared to the high molecular weight-modified HSC conjugates or the plain CUR. In summary, the molecular weight of HA affects the physicochemical attributes of HSC conjugates. Only HSC micelles made with HA molecules less than 500 kDa exhibit redox sensitivity.

Joint nociceptor nerve activity and pain in an animal model of acute gout and its modulation by intra-articular hyaluronan.

The mechanisms whereby deposition of monosodium urate (MSU) crystals in gout activates nociceptors to induce joint pain are incompletely understood. We tried to reproduce the signs of painful gouty arthritis, injecting into the knee joint of rats suspensions containing amorphous or triclinic, needle MSU crystals. The magnitude of MSU-induced inflammation and pain behavior signs were correlated with the changes in firing frequency of spontaneous and movement-evoked nerve impulse activity recorded in single knee joint nociceptor saphenous nerve fibers. Joint swelling, mechanical and cold allodynia, and hyperalgesia appeared 3 hours after joint injection of MSU crystals. In parallel, spontaneous and movement-evoked joint nociceptor impulse activity raised significantly. Solutions containing amorphous or needle-shaped MSU crystals had similar inflammatory and electrophysiological effects. Intra-articular injection of hyaluronan (HA, Synvisc), a high-MW glycosaminoglycan present in the synovial fluid with analgesic effects in osteoarthritis, significantly reduced MSU-induced behavioral signs of pain and decreased the enhanced joint nociceptor activity. Our results support the interpretation that pain and nociceptor activation are not triggered by direct mechanical stimulation of nociceptors by MSU crystals, but are primarily caused by the release of excitatory mediators by inflammatory cells activated by MSU crystals. Intra-articular HA decreased behavioral and electrophysiological signs of pain, possibly through its viscoelastic filtering effect on the mechanical forces acting over sensitized joint sensory endings and probably also by a direct interaction of HA molecules with the transducing channels expressed in joint nociceptor terminals.

The Length of N-Glycans of Recombinant H5N1 Hemagglutinin Influences the Oligomerization and Immunogenicity of Vaccine Antigen.

Hemagglutinin glycoprotein (HA) is a principle influenza vaccine antigen. Recombinant HA-based vaccines become a potential alternative for traditional approach. Complexity and variation of HA N-glycosylation are considered as the important factors for the vaccine design. The number and location of glycan moieties in the HA molecule are also crucial. Therefore, we decided to study the effect of N-glycosylation pattern on the H5 antigen structure and its ability to induce immunological response. We also decided to change neither the number nor the position of the HA glycosylation sites but only the glycan length. Two variants of the H5 antigen with high mannose glycosylation (H5hm) and with low-mannose glycosylation (H5Man5) were prepared utilizing different Pichia strains. Our structural studies demonstrated that only the highly glycosylated H5 antigen formed high molecular weight oligomers similar to viral particles. Further, the H5hm was much more immunogenic for mice than H5Man5. In summary, our results suggest that high mannose glycosylation of vaccine antigen is superior to the low glycosylation pattern. Our findings have strong implications for the recombinant HA-based influenza vaccine design.

Pathogenicity and transmission of triple reassortant H3N2 swine influenza A viruses is attenuated following Turkey embryo propagation

Genetic lineages of swine influenza A viruses (SIVs) have recently been established in Turkeys in the United States. To identify molecular determinants that are involved in virulence and transmission of SIVs to Turkeys, we sequentially passaged two triple reassortant H3N2 SIV isolates from Minnesota in ten day old specific-pathogen free (SPF) Turkey embryos and tested them in seven-day old Turkey poults. We found that SIV replication in Turkey embryos led to minimal mutations in and around the receptor binding and antigenic sites of the HA molecule, while other gene segments were unchanged. The predominant changes associated with Turkey embryo passage were A223V, V226A and T248I mutations in the receptor-binding and glycosylation sites of the HA molecule. Furthermore, Turkey embryo propagation altered receptor specificity in SIV strain 07-1145. Embryo passaged 07-1145 virus showed a decrease in α2, 6 sialic acid receptor binding compared to the wild type virus. Intranasal infection of wild type SIVs in one-week-old Turkey poults resulted in persistent diarrhea and all the infected birds seroconverted at ten days post infection. The 07-1145 wild type virus also transmitted to age matched in-contact birds introduced one-day post infection. Turkeys infected with embryo passaged viruses displayed no clinical signs and were not transmitted to in-contact poults. Our results suggest that Turkey embryo propagation attenuates recent TR SIVs for infectivity and transmission in one week old Turkeys. Our findings will have important implications in identifying molecular determinants that control the transmission and virulence of TR SIVs in Turkeys and other species.

Pressureless sintering and mechanical properties of hydroxyapatite/functionalized multi-walled carbon nanotube composite

This work aims to study the optimum sintering conditions of hydroxyapatite/functionalized multi-walled carbon nanotube (HA/f-MWCNT) composite with improved mechanical properties for bone implant applications using a pressureless sintering technique. The carboxyl functional group (COOH) introduced by the acid treatment on the MWCNT surface by which HA molecules are grafted onto the surface of functionalized MWCNT with strong interfacial bonding. The composite exhibits a lower hemolytic rate of 1.27%. The flexible nature of f-MWCNT makes them bend and attached to the HA grains, indicates that f-MWCNT bear significant stress by sharing a portion of the load and it leads to improve their mechanical properties. The maximum Vickers hardness of 3.6GPa is obtained for the HA/f-MWCNT composite sintered at 1100°C, whereas the highest compressive strength of 481.7MPa and fracture toughness of 2.38MPa.m1/2 achieved after sintering at 1150°C. This study demonstrated that HA/f-MWCNT composite create suitable structures by vacuum pressureless sintering technique to satisfy the mechanical requirements for bone tissues.

Concept model of the formation process of humic acid–kaolin complexes deduced by trichloroethylene sorption experiments and various characterizations

To explore the interactions between soil organic matter and minerals, humic acid (HA, as organic matter), kaolin (as a mineral component) and Ca2+ (as metal ions) were used to prepare HA-kaolin and Ca-HA-kaolin complexes. These complexes were used in trichloroethylene (TCE) sorption experiments and various characterizations. Interactions between HA and kaolin during the formation of their complexes were confirmed by the obvious differences between the Qe (experimental sorbed TCE) and Qe_p (predicted sorbed TCE) values of all detected samples. The partition coefficient kd obtained for the different samples indicated that both the organic content (fom) and Ca2+ could significantly impact the interactions. Based on experimental results and various characterizations, a concept model was developed. In the absence of Ca2+, HA molecules first patched onto charged sites of kaolin surfaces, filling the pores. Subsequently, as the HA content increased and the first HA layer reached saturation, an outer layer of HA began to form, compressing the inner HA layer. As HA loading continued, the second layer reached saturation, such that an outer-third layer began to form, compressing the inner layers. In the presence of Ca2+, which not only can promote kaolin self-aggregation but can also boost HA attachment to kaolin, HA molecules were first surrounded by kaolin. Subsequently, first and second layers formed (with inner layer compression) via the same process as described above in the absence of Ca2+, except that the second layer continued to load rather than reach saturation, within the investigated conditions, because of enhanced HA aggregation caused by Ca2+.

Multifunctional Lymph-Targeted ZnO:Gd@Hyaluronic Acid Nanospheres: Preparation and Application in Tumor Diagnose

A novel multi-modal lymph-targeted contrast agent, ZnO:Gd@hyaluronic acid (HA) nanospheres, is prepared by Gd dopped ZnO quantum dot, modified by silica shell and grafted by HA molecule. The physicochemical prop- erties are characterized and the lymphatic targeting is evaluated in vitro. Moreover, the contrast agent is used for in vivo lymphoma magnetic resonance imaging (MRI). The results show that the ZnO:Gd@HA nanospheres with 19% of quantum yield and 5.8 mM -1 •s -1 of relaxivity could be used for in vivo lymphatic targeting studies. Furthermore, they are highly targeted to lymph system in vitro and in vivo, and highlight their MRI in lymph tumor. Thus, the novel MRI contrast agent can be taken up selectively by lymphatic system and used as a potential multi-modal con- trast agent in lymphatic system.

Synergistic Removal of Humic Acid in Water by Coupling Adsorption and Photocatalytic Degradation Using TiO2/Coconut Shell Powder Composite

The feasibility of applying nanoscale TiO2/coconut shell powder (TCNSP) composite to remove HA in aqueous solution was evaluated, and the optimization of the photocatalytic systems using newly developed TCNSP composite was performed. The developed TCNSP composite has high specific surface area (i.e., 454 m2/g) and great porosity (i.e., 66.9%) with pore size of less than 5 μm. High removal efficiencies (≥95%) of HA were observed due to the significant synergistic effects by coupling adsorption and photocatalytic reaction of TCNSP composite. As the initial concentration of HA increased, the degradation rate (Kapp) decreased due to HA sorption saturation to the surface of TCNSP composite and the photon interception by HA molecules in aqueous solution. Since the increased loading amount of TCNSP composite enhanced the number of active sites,Kappvalues increased until the optimum loading amount of TCNSP composite. As pH values increased, HA removal efficiency decreased due to increasing electrostatic repulsion between HA and TCNSP composite. Based on the response surface methodology, higher HA removal efficiencies were obtained with acidic condition, longer reaction time, and appropriated loading amount of TCNSP. Further pilot-scale study is in progress using TCNSP composite combined with UVC to remove HA from large amounts of surface water (i.e., 200 m3/d).

МАСС-СПЕКТРОМЕТРИЯ СУПРАМОЛЕКУЛЯРНЫХ КОМПЛЕКСОВ ГЛИЦИРРИЗИНОВОЙ КИСЛОТЫ И СТРЕПТОМИЦИНА

Глицирризиновая кислота (ГК), выделенная из корней солодки голой Glycyrrhiza glabra L. и Gl. uralensis F., обладает уникальными комплексообразующими свойствами, которые широко используются в синтезе новых лекарственных форм на основе молекулярных комплексов с фармаконами. В таких гетерогенных комплексах молекулы ГК выступают в роли полидентантных лигандов, образующих с фармаконами супрамолекулярные комплексы различной стехиометрии. Целью данной работы является изучение комплексообразования растительных гликозидов с антимикробным препаратом стрептомицином для создания новых низкодозных фармсубстанций на основе глицирризиновой кислоты. В представленной работе впервые синтезированы и изучены методом УФ-спектроскопии и масс-спектрометрии с ионизацией электрораспылением гетерогенные супрамолекулярные комплексы ГК с антибиотиком стрептомицином (СТ), полученные при различных концентрациях «хозяина» и «гостя» в соотношении 1 : 1 и 4 : 1. Зарегистрированные изменения в спектре поглощения СТ в присутствии ГК с помощью УФ-спектроскопии доказывают формирование гетерогенных комплексов ГК-СТ в жидкой фазе. С использованием масс-спектрометрии зарегистрировано эффективное взаимодействие ГК и СТ с образованием различных гетерогенных супрамолекулярных структур с соотношением «хозяин: гость» 1 : 1, 2 : 1, 3 : 1, 3 : 2. При увеличении концентрации ГК наблюдали как увеличение степени самоассоциации ГК (до 4), так и образование комплекса с соотношением 4 : 1. Результаты исследований демонстрируют высокий потенциал использования глицирризиновой кислоты для синтеза новых форм антибактериального препарата стрептомицина в виде нековалентных молекулярных комплексов.

Binding and setting of kaolin based materials with natural organic acids

In the present study, the correlation between adsorption experiments and the setting process of “geomimetic” materials prepared with humic-like solutions (HS) and a kaolin were investigated. Two HS were compared: a humic acid solution (HA, pH=13) and a fulvic acid solution (FA, pH=3). The adsorption experiments revealed a higher capacity of adsorption of the kaolin towards FA than HA, which could be attributed to the charge effects on the clay surface and to the organic molecule conformation depending on the pH. Materials elaborated, with high content of HA was consolidated after 4days of curing whereas no setting was observed for materials prepared in the same conditions with FA. The hypothesis of inter/intra-molecular H-bonding between carboxylate groups of HA molecules, taken in evidence by FTIR analyses, and carboxylic or hydroxyl groups, was proposed to explain the material setting. Indeed, the characterization of HA revealed a highly aromatic structure favorable to mesomeric effects which led to the apparition of negative and/or positive charges and thus increased the reactivity of HA molecules. The structure of FA rather aliphatic was not favorable to mesomeric effect. Moreover, goethite was “mechanically” added in the kaolin powder because this iron phase was identified to be favorable to material setting. In this study, the addition of iron hydroxides, as powder, did not improve the material setting.