Hoff Plots Research Articles

Insights into the Main Protease of SARS-CoV-2: Thermodynamic Analysis, Structural Characterization, and the Impact of Inhibitors.

The main protease (Mpro) of SARS-CoV-2 is an essential enzyme for coronaviral maturation and is the target of Paxlovid, which is currently the standard-of-care treatment for COVID-19. There remains a need to identify new inhibitors of Mpro as viral resistance to Paxlovid emerges. Here, we report the use of native mass spectrometry coupled with 193 nm ultraviolet photodissociation (UVPD) and integrated with other biophysical tools to structurally characterize Mpro and its interactions with potential covalent inhibitors. The overall energy landscape was obtained using variable temperature nanoelectrospray ionization (vT-nESI), thus providing quantitative evaluation of inhibitor binding on the stability of Mpro. Thermodynamic parameters extracted from van't Hoff plots revealed that the dimeric complexes containing each inhibitor showed enhanced stability through increased melting temperatures as well as overall lower average charge states, giving insight into the basis for inhibition mechanisms.

Development of a superheated water chromatography method for the sustainable determination of preservatives in foods and cosmetics

The present research focused on the use of high temperatures to achieve fast separations in Liquid Chromatography (LC) and minimize the consumption of organic solvents. Particularly, superheated water was employed, by exploiting the decrease in dielectric constant of water when increasing the temperature. To realize this kind of application, the availability of LC columns resistant at high temperature is mandatory. Recently, porous graphitic carbon (PGC) columns have been proposed as stationary phases resistant up to 250 °C. Hardware modifications were also necessary to guarantee the efficient heating of the mobile phase prior of entering the column, as well as its rapid cooling before detection by photodiode array (PDA). Specifically, an LC system was interfaced to a GC oven, which hosted the LC column; to achieve a fast and efficient heating of the eluent coming from the autosampler prior to enter into the column, a pre-heating tube was interposed between the autosampler outlet and the column inlet. Instead, a cooling loop was connected between the column outlet and the PDA cell. A mixture of 1-nitroalkanes was used to evaluate the performance of the system in terms of dead volumes, band broadening and peak shape, as well as chromatographic efficiency and resolution. The use of higher temperatures allowed to perform analyses at higher flow rates in reduced analysis time and was also in terms of peak bandwidth resulting to increased efficiency for the most retained compound. Moreover, van't Hoff plots were obtained at different temperature, confirming that the most retained analyte greatly benefited of the temperature increase.The system was applied to the analysis of parabens in cosmetic and food products. The method combined eco-sustainable sample preparation with high-temperature LC separation on a PGC column and was fully validated in terms of linearity, precision, accuracy and detection and quantification limits. The developed method was critically evaluated by comparing the output of different metric tools implemented in the last decade for the quantitative assessment of the greenness.

UPLC-PDA factorial design assisted method for simultaneous determination of oseltamivir, dexamethasone, and remdesivir in human plasma

A green and simple UPLC method was developed and optimized, adopting a factorial design for simultaneous determination of oseltamivir phosphate and remdesivir with dexamethasone as a co-administered drug in human plasma and using daclatasvir dihydrochloride as an internal standard within 5 min. The separation was established on UPLC column BEH C18 1.7 μm (2.1 ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 100.0 mm) connected to UPLC pre-column BEH 1.7 μm (2.1 ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes $$\\end{document} 5.0 mm) at 50 °C with an injection volume of 10 μL. The photodiode array detector (PDA) was set at three wavelengths of 220, 315, and 245 nm for oseltamivir phosphate, the internal standard, and both dexamethasone and remdesivir, respectively. The mobile phase consisted of methanol and ammonium acetate solution (40 mM) adjusted to pH 4 in a ratio of 61.5:38.5 (v/v) with a flow rate of 0.25 mL min−1. The calibration curves were linear over 500.0–5000.0 ng mL−1 for oseltamivir phosphate, over 10.0–500.0 ng mL−1 and 500.0–5000.0 ng mL−1 for dexamethasone, and over 20.0–500 ng mL−1 and 500.0–5000.0 ng mL−1 for remdesivir. The Gibbs free energy and Van't Hoff plots were used to investigate the effect of column oven temperatures on retention times. Fluoride-EDTA anticoagulant showed inhibition activity on the esterase enzyme in plasma. The proposed method was validated according to the M10 ICH, FDA, and EMA’s bioanalytical guidelines. According to Eco-score, GAPI, and AGREE criteria, the proposed method was considered acceptable green.

Effects of Heterogeneous Mixing of Imidazolium-Based Ionic Liquids with Alcohols on Complex Formation of Ni(II) Ion.

Understanding the complex formation of metal ions in room-temperature ionic liquids (ILs) is essential for the application of ILs in solvent extraction. Nevertheless, the research on metal complex formation in ILs lags behind other applications. The complex formation equilibria may be influenced by specific interactions among the metal ion, ligand molecule, and IL cation and anion. In the present investigation, the complex formation of Ni2+ with ethanol (EtOH) and methanol (MeOH) molecules in ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([CNmim][TFSA], where N represents the alkyl chain lengths of 2 and 8) was discussed in terms of the microscopic interactions among alcohol molecules, [CNmim]+ and [TFSA]-, and the mesoscopic mixing states of alcohols in [CNmim][TFSA], with N = 2-12. The microscopic interaction of alcohol molecules with the imidazolium ring H atoms in the ILs was evaluated by using ATR-IR and 1H and 13C NMR spectroscopies. The self-hydrogen bonding of alcohol molecules was clarified from the O-H stretching vibration of alcohol molecules. MeOH molecules can be more strongly hydrogen-bonded with themselves than EtOH molecules due to the less steric hindrance and the weaker dispersion force of MeOH with the IL cation's alkyl chain. In fact, small-angle neutron scattering (SANS) experiments revealed the more heterogeneous mixing of MeOH with the ILs by the self-hydrogen bonding among MeOH molecules than EtOH. The longer the IL cation's alkyl chain, the more the MeOH clusters significantly form. In contrast, the formation of EtOH clusters becomes weaker with elongating the alkyl chain. Ultraviolet (UV)-visible spectroscopic measurements on Ni2+-[CNmim][TFSA]-alcohol solutions with N = 2 and 8 revealed that di-, tetra-, and hexa-alcohol-Ni2+ complexes are formed in both the ILs. With N = 2, the stabilities of Ni2+-EtOH and Ni2+-MeOH complexes are comparable in the IL. However, with N = 8, the complexes are more stable in the EtOH solutions than in the MeOH solutions. This is because the less heterogeneous mixing of EtOH molecules with the IL results in the larger enthalpic contribution in the complex formation, as shown by the thermodynamic parameters estimated by the van't Hoff plots on the stability constants at several temperatures.

The Development of One New Normal Phase Liquid Chromatography Method and Thermodynamic Investigation of Olodaterol Hydrochloride Enantiomer.

In order to improve and replace the enantiomer method outlined in the olodaterol hydrochloride draft monograph (From the European Pharmacopoeia forum), one new, simple, and fast enantioselective normal phase high-performance liquid chromatography chiral method was developed on polysaccharide-based Chiral MX (2) (4.6 × 250 mm, 5 μm) column. n-Hexane, ethanol, and diethylamine in the ratio of 40:60:0.1 (V/V/V) were selected as mobile phase at a flow rate of 0.8 mL/min, and the detection was performed on a photodiode array detector at 225 nm with 5 μL injection volume. The column temperature was set at 40°C for better peak shape and sensitivity. The analysis time can be shortened to 15 min, whereas the resolution between enantiomer and olodaterol was found to be even more than 10.0, which was far better than that obtained with the reported method in this draft monograph. The developed chiral method was validated in accordance with ICH Q2 (R1), including specificity, LOD&LOQ, precision, linearity, accuracy, and robustness. Thereby, the proposed method was demonstrated to be suitable for the determination of enantiomer inolodaterol hydrochloride bulk drug and drug product. Besides, the thermodynamic parameters were evaluated on the basis of Van't Hoff plots that was used to explain correlative chiral recognition mechanisms with the chiral stationary phase.

Uncalcined Zn/Al Carbonate LDH and Its Calcined Counterpart for Treating the Wastewater Containing Anionic Congo Red Dye

In this investigation, Zn/Al carbonate layered double hydroxide (ZAC-LDH) and its derived material on calcination were synthesized for removing the anionic azo dye Congo red (CR) from wastewater. Numerous factors were methodically investigated, including temperature, adsorbent dosage, pH, starting Dye Concentration (DC), and contact time. The CR elimination percentage dropped as the initial DC increased from 25 mg/L to 100 mg/L at 30 °C for uncalcined LDH, and from 97.96% to 89.25% for calcined LDH. The pH analysis indicates that the highest level of dye removal was recorded within the acidic pH range through the electrostatic attraction mechanism. The sorption kinetics analysis results demonstrated that the pseudo-second-order kinetic model exhibited a stronger fit to both uncalcined LDH and CZA-LDH, with the maximum correlation coefficient value. The Van’t Hoff plots indicate the spontaneous nature of the physisorption process with a negative ΔG° (<−20 kJ/mol), while the endothermic adsorption process exhibited a positive ΔH°. The X-ray diffraction of calcined LDH reveals a significant intercalation of CR dye molecules, both prior to and following adsorption, showcasing a distinctive memory effect. The Brunauer–Emmett–Teller (BET) gas sorption measurements were performed to support the mesoporous nature of ZAC-LDH and CZA-LDH. The FTIR spectrum confirms the interaction of dye molecules on the surface of uncalcined and calcined LDH. These findings emphasize the efficacy of both the synthesized LDHs in removing CR dye, with CZA-LDH demonstrating superior efficiency compared to uncalcined LDH in the context of CR removal from wastewater.

A green reaction-based turn-off fluorescence sensor for determination of copper ions: DFT calculations, quenching mechanism, green chemistry metrics, and application in environmental samples.

When Cu(II) reacts with ascorbic acid (AA) to form Cu(I), Cu(I) can combine with eosin Y (EY) to form ionic associations, resulting in significant fluorescence quenching of the EY. Based on the turn-off of fluorescence in the chemosensor EY, a green reaction is proposed herein for the detection of Cu(II). The novel detection method for Cu(II) demonstrates simplicity, high sensitivity, and excellent selectivity, rendering it suitable for analyzing environmental samples. A static fluorescence quenching mechanism is validated through the Stern-Volmer relationship, and the thermodynamic parameters of the reaction are explored using a van 't Hoff plot. The reaction mechanism is investigated via fluorescence spectra, absorption spectra, and density-functional theory (DFT) calculations. The probe's green nature is confirmed by applying four green analytical chemistry metrics.

Spectroscopic and in silico characterization of the interaction between synthetic 2-substituted-naphtho-1,4-quinones and human serum albumin

The intermolecular interaction between 2-(N-phenyl-N-methyl)aminonaphtho-1,4-quinone (1) and 2-(4-N-methylaminophenyl)naphtho-1,4-quinone (2) and human serum albumin (HSA) was investigated using spectroscopic techniques combined with in silico calculations via molecular docking. Steady-state titration of HSA fluorescence by 1 and 2 (λexc 295 nm) in PBS at 305, 310, and 315 K, as well as studies employing time-resolved fluorescence emission, demonstrated that the HSA:1 and HSA:2 interaction occurs through a static quenching mechanism. The Stern-Volmer constant (Ksv) values, (1.56 ± 0.08) and (3.05 ± 0.10) × 104 L/mol at 310 K for HSA:1 and HSA:2, respectively, indicate a moderate binding affinity. Van't Hoff plots showed that HSA:1 and HSA:2 interactions are spontaneous (negative ΔGo) with a hydrophobic character (ΔSo value of 0.00707 ± 0.00106 and 0.0392 ± 0.0062 kJ/mol K for HSA:1 and HSA:2, respectively) and specific electrostatic interactions (ΔHo value of –22.7 ± 3.3 and −14.4 ± 1.9 kJ/mol for HSA:1 and HSA:2, respectively). Synchronous fluorescence results showed significant perturbation in the microenvironment of the tryptophan residue (Trp-214). Circular dichroism indicated that after interaction with naphthoquinones 1 and 2, the HSA structure remains predominantly in the α-helix form. Finally, molecular docking revealed the formation of hydrophobic, electrostatic, and hydrogen bond interactions with the surrounding amino acid residues in subdomain IIA of HSA, which contains the Trp-214 residue, validated with the experimental drug-displacement assays. Overall, spectroscopic and in silico characterization of HSA:1 and HSA:2 might reflect in a low half-life in the human bloodstream, indicating the necessity of methods to improve the bioavailability, e.g., studies on the type of administration (oral versus intravenous).

Enthalpies and entropies of hydration from Monte Carlo simulations.

The changes in free energy, enthalpy, and entropy for transfer of a solute from the gas phase into solution are the fundamental thermodynamic quantities that characterize the solvation process. Owing to the development of methods based on free-energy perturbation theory, computation of free energies of solvation has become routine in conjunction with Monte Carlo (MC) statistical mechanics and molecular dynamics (MD) simulations. Computation of the enthalpy change and by inference the entropy change is more challenging. Two methods are considered in this work corresponding to direct averaging for the solvent and solution and to computing the temperature derivative of the free energy in the van't Hoff approach. The application is for neutral organic solutes in TIP4P water using long MC simulations to improve precision. Definitive results are also provided for pure TIP4P water. While the uncertainty in computed free energies of hydration is ca. 0.05 kcal mol-1, it is ca. 0.4 kcal mol-1 for the enthalpy changes from either van't Hoff plots or the direct method with sampling for 5 billion MC configurations. Partial molar volumes of hydration are also computed by the direct method; they agree well with experimental data with an average deviation of 3 cm3 mol-1. In addition, the results permit breakdown of the errors in the free energy changes from the OPLS-AA force field into their enthalpic and entropic components. The excess hydrophobicity of organic solutes is enthalpic in origin.

Quantification of crystallinity during indomethacin crystalline transformation from α- to γ-polymorphic forms and of the thermodynamic contribution to dissolution in aqueous buffer and solutions of solubilizer.

The thermodynamic properties and dissolution of indomethacin (INM) were analyzed as models for poorly water-soluble drugs. Physical mixtures of the most stable γ-form and metastable α-form of INM at various proportions were prepared, and their individual signal intensities proportional to their mole fractions were observed using X-ray powder diffraction and Fourier transform infrared spectrometry at standard temperature. The endothermic signals of the α-form, with a melting point of 426 K, and that of the γ-form, with a melting point of 433 K, were obtained by differential scanning calorimetry (DSC). Furthermore, an exothermic DSC peak of the α/γ-phase transition at approximately 428 K was obtained. As we computed the melting entropy of the α-form and that of its transformation, the frequency of the transition was quantitatively determined, which indicated the maximum of the α/γ-phase transition at an α-form proportion of 68%. Subsequently, the thermodynamic contributions of the α- and γ-forms were analyzed using a Van't Hoff plot for solubility in aqueous solutions at pH 6.8. The dissolution enthalpies for α- and γ-forms were 28.2 and 31.2 kJ mol-1, respectively, which are in agreement with the quantitative contribution predicted by the product of the temperature and melting entropy. The contribution of melting entropy was conserved in different dissolution processes with aqueous solvents containing lidocaine, diltiazem, l-carnosine, and aspartame as solubilizers; their γ-form Setschenow coefficients were -39.6, +82.9, -17.3, and +23.2, whereas those of the α-form were -39.7, +80.4, -16.7, and +22.7, respectively. We conclude that the dissolution ability of the solid state and solubilizers indicate their additivity independently.

Cyclic CO2 absorption/desorption property of Li3NaSiO4 under the partial pressure of CO2 for practical applications.

The temperature for realizing the cyclic CO2 absorption/desorption property of Li3NaSiO4 by repetition of switching a CO2/N2 gas mixture and N2 with a partial pressure of CO2, P(CO2), of 0.1 bar was optimized using the pseudo van't Hoff plot of LiNaCO3 + Li2SiO3 ↔ Li3NaSiO4 + CO2 prepared by thermogravimetry at various P(CO2) values.

Spectroscopic and thermodynamic characterization of the interaction between sugar-stabilised silver nanoparticles and wheat germ agglutinin (WGA), a chitin binding lectin

Nanomaterials have lately been investigated in agriculture as eco-friendly and effective antifungal agents. Many nanomaterials, notably metal nanoparticles, have strong antifungal properties. Among metal nanoparticles, Ag nanoparticles have received the most attention as antifungal agents. Many plant lectins have been identified as antifungal agents. Conjugating AgNPs with antifungal lectins is thus expected to improve Ag nanoparticle antifungal efficacy. Understanding the molecular interactions and physical features of lectin-sugar-stabilised nanoparticle conjugates is critical for future applications. WGA has traditionally been used as an anti-tumor and antifungal agent. To investigate the prospect of developing an effective biocompatible antifungal system with applications in medicine and agriculture, fluorescence spectroscopy was used to investigate the interaction between sugar-stabilised silver nanoparticles and WGA. During the association, protein intrinsic fluorescence emission is suppressed by about ∼15 % at saturation, with no significant shift in fluorescence emission maxima. Binding tests reveal a strong bond. Stern-Volmer analysis of the quenching data indicates that the interaction happens via a static quenching process that induces complex formation. The study of hemagglutination activity and interaction experiments in the presence of particular sugar shows that the lectin's sugar-binding site is separate from the nanoparticle-binding site, and cell recognition is conserved in the lectin-nanoparticle complex. The Van't Hoff plot thermodynamic parameters suggest that the contact is hydrophobic. The fact that ΔGo is negative shows that the binding is a spontaneous process. CD spectroscopy experiments reveal that the lectin's secondary structure is not affected while binding to the nanoparticle. Our findings suggest that a stable WGA-silver nanoparticle combination may emerge for a variety of applications.

Preparation of two zwitterionic polymer functionalized stationary phases and comparative evaluation under mixed-mode of reversed phase/ hydrophilic interaction/ion exchange chromatography

Zwitterions are a promising choice to prepare separation materials because of their hydrophilicity and biocompatibility. We described the preparation of two zwitterionic polymer functionalized stationary phases and evaluation under mixed-mode chromatography. A zwitterionic monomer, S-(4-vinylbenzyl) cysteine (SVC), was synthesized and bonded to silica via reversible addition fragmentation chain transfer (RAFT) polymerization to afford a zwitterionic stationary phase, Sil-SVC. A hydrophobic monomer, N-(4-phenylbutan-2-yl) acrylamide (NPA), was copolymerized with SVC onto the stationary phase (Sil-SVCNPA) for comparison. The stationary phases were characterized with FT-IR, TGA, EA, and zeta-potential measurements. Mobile phase composition (ACN content, pH and salt concentration) was varied to study the retention property. Linear solvation energy relationship and Van't Hoff plot were used to investigate the retention mechanism and how chromatographic conditions influenced it. Both stationary phases showed a mixed-mode of RPLC/HILIC/IEC and satisfactory performance in separating hydrophobic analytes (alkylbenzenes and polycyclic aromatic hydrocarbons), hydrophilic nucleotide and bases, and anions, high column efficiency of 60,000 plates·m−1 was achieved. In summary, zwitterionic polymers are attractive options to prepare stationary phases and the retention property can be easily regulated by copolymer.

Experimental and numerical study of hydrogen absorption in the MmNi5−xMx compound

In this paper, the hydrogen storage properties of the MmNi4.6Al0.4 and MmNi4.6Fe0.4 compounds are compared experimentally and theoretically. The experimental curves of the activation process, experimental isotherms of absorption and the Van't Hoff's plot were first investigated. Following that, a theoretical model is contrasted with the experimental data. The mathematical equations of this model contain parameters, such as the number of hydrogen atoms per site (n1, n2), the densities of the receiving sites (N1m, N2m), and the energy parameters (P1, P2). All these parameters are obtained by numerically adjusting the experimental data. Depending on the applied temperature, the relevant parameters of the suggested model were identified and described. Entropy, internal energy, and other thermodynamic variables that govern the absorption reaction were all calculated and displayed as a function of pressure and temperature.

Extracting thermodynamic properties from van ’t Hoff plots with emphasis on temperature-sensing ion channels

ABSTRACT Transient receptor potential (TRP) ion channels are among the most well-studied classes of temperature-sensing molecules. Yet, the molecular mechanism and thermodynamic basis for the temperature sensitivity of TRP channels remains to this day poorly understood. One hypothesis is that the temperature-sensing mechanism can simply be described by a difference in heat capacity between the closed and open channel states. While such a two-state model may be simplistic it nonetheless has descriptive value, in the sense that it can be used to compare overall temperature sensitivity between different channels and mutants. Here, we introduce a mathematical framework based on the two-state model to reliably extract temperature-dependent thermodynamic potentials and heat capacities from measurements of equilibrium constants at different temperatures. Our framework is implemented in an open-source data analysis package that provides a straightforward way to fit both linear and nonlinear van ’t Hoff plots, thus avoiding some of the previous, potentially erroneous, assumptions when extracting thermodynamic variables from TRP channel electrophysiology data.

Preparation of nanosized liquid-like clusters of irinotecan hydrochloride trihydrate for injection concentrate to reduce carbon footprint

The surprisingly stable irinotecan hydrochloride trihydrate injection concentrate having a supersaturated concentration of 20 mg/mL at 25 °C was due to the frustration of 150 nm sized liquid-like nanosized clusters formed by the aggregation of dimers of 1.5 nm in an aqueous phase, evidenced by the non-linearity of van’t Hoff plot and dynamic light scattering measurement. The adoption of this stable supersaturated solution at 20 mg/mL by manufacturers as the commercial concentration was beneficial due to the less volume being involved throughout the manufacturing, handling, storage and transportation of the commercial product, while also enabling a versatile on-site concentration adjustment by dilution prior to intravenous administration. Regarding the physical characteristic of the solid state of irinotecan hydrochloride trihydrate, it was found to exist as a channel hydrate as evidenced by single-crystal, and high-temperature X-ray diffraction experiments. Dehydration takes place at approximately 35 °C as demonstrated by thermogravimetric analysis. Because of its non-stoichiometric nature under various RH values revealed by dynamic vapor sorption, the irinotecan hydrate salt raw material must be kept at 25 °C or below, and under the relative humidity of 40 % to 60 % to maintain the original stoichiometric ratio of the raw material.

Synthesis, characterization and multi-spectroscopic DNA/HSA interaction studies of synthetic human Follicle-Stimulating Hormone Beta 33–53 peptide conjugated PEGylated graphene oxide nanoparticles

The objective of the current study was to synthesize, characterize and explore the interaction of PEGylated graphene oxide (pGO) and synthetic human Follicular stimulating hormone β 33–53 peptide conjugated PEGylated graphene oxide nanoparticles (pGO-FSH) with human serum albumin (HSA) and calf thymus DNA (CT-DNA). The pGO/ pGO-FSH nanoparticles were synthesized using a modified Hummer’s method, and the FSH peptide was conjugated through a maleimide crosslinking reaction. Synthesized nanoparticles were then characterized using techniques like FT-IR, UV–Visible absorbance, CD and Raman spectroscopy, and XRD and TGA. Morphological and particle size analysis was studied using SEM, TEM, DLS, and zeta potential measurements. The presence of FSH β 33–53 peptide was confirmed qualitatively and quantitatively using CD spectroscopy and Bradford’s assay. Binding studies of pGO/pGO-FSH nanoparticles with HSA and DNA were carried out using biophysical techniques. The complex formation between pGO/pGO-FSH nanoparticles and HSA was revealed by UV absorbance spectroscopy, and the observed fluorescence quenching was confirmed by steady-state fluorescence spectroscopy. Time-resolved fluorescence quenching studies have shown that dynamic quenching plays an important role in binding HSA with pGO/pGO-FSH nanoparticles. However, structurally no significant changes were observed in the native structure of HSA upon binding with pGO/pGO-FSH nanoparticles suggesting that the latter did not induce any structural distortions together, confirmed by DSC, FT-IR, and CD spectroscopy experimental findings. Binding constants and thermodynamic parameters calculated using double logarithmic and Van’t Hoff plots suggested weak and moderate binding affinity along with the involvement of hydrophobic and hydrogen bonding interactions between HSA and pGO/pGO-FSH nanoparticles, respectively. UV absorbance and fluorescence spectroscopy have revealed that pGO/pGO-FSH nanoparticles interact with DNA by binding at the minor groove region. These findings were further confirmed by DNA melting and viscosity studies. CD and FT-IR spectroscopy studies have shown no changes in the helical structure of B-form of DNA, thereby emphasizing the groove-binding nature of pGO/pGO-FSH nanoparticles. The obtained results are useful in further considering the potentiality of pGO-FSH nanoparticles as drug-delivery systems for in vivo applications, especially to target ovarian cancer.

Determination of change in enthalpy and entropy for hydride formation and decomposition of palladium using in-situ electrical resistance measurement with various hydrogen pressures

Detection of hydride formation and decomposition of palladium is performed on pure palladium in the hydrogen gas atmosphere up to 0.5 MPa between room temperature and 673 K using an in-situ electrical resistance measurement system. Introduction of hydrogen gas increases the electrical resistance about 1.1 time higher than that in vacuum. Electrical ratio-temperature plot gives a peak during heating and cooling with the temperature changing ration of 0.067 K/s under hydrogen gas, which are associated with the hydride composition and decomposition. Change in enthalpy ΔH and entropy ΔS are determined using van't Hoff plot, and the values were comparable to the reported ones obtained by pressure-composition-temperature measurements. Those for hydride decomposition are 45.6±2.6 (kJ/mol) and 104.8±5.3 (J/mol), respectively, and those for hydride formation are -29.4±2.1 (kJ/mol) and 73.8±4.6 (J/mol), respectively. Furthermore, the measurement method is relatively simple and easy compared with pressure-composition-temperature measurements.

Correctness of the van 't Hoff analysis for homogeneous or heterogeneous retention

It is already known that the physical meaning of the numerical values of the calculated enthalpy (ΔH) and entropy (ΔS) change in chromatography via the van 't Hoff plot analysis is rather questionable. In the former work of these authors, it has been demonstrated that by serially coupling two reversed-phase columns of the same inner diameter but of different retention mechanism, the obtained thermodynamic values are not related to the numerical results obtained on the individual columns respectively. Since surface heterogeneity of the stationary phase is intrinsically present in chiral chromatography (enantioselective and non-selective sites), the calculation of ΔH and ΔS should be revisited in that field.In this study, more details of the pressure dependence were investigated. Using special POPLC columns, the effect of the column length on the calculated thermodynamic values was investigated. The calculated values differ by 30–400% when the column length is increased from 4 cm to 12 cm. The dependence of the calculated results on the applied flow rate was already highlighted earlier, and here the emphasis was put on the instrument on which the separation was performed. It turns out that there is a difference when using a Shimadzu HPLC system compared to using a Waters Acquity UPLC system.Because the Eyring method serves as an alternative route to calculate the thermodynamic values from chromatographic data, the differences obtained by the two methods were also investigated.

Advantages of polar organic solvent chromatography for enantioseparation of chiral liquid crystals

Three sets of fluorinated chiral liquid crystals were used to explore the polar organic solvent chromatography mode for their enantioseparation. The materials include a set of newly synthesized compounds with chiral center derived from 2-hexanol and two sets of compounds with chiral center derived from 2-/3-octanol. Baseline enantioseparation of all materials was achieved using binary mobile phases without additives. For some of the compounds exceedingly high values of enantioresolution (> 20) and enantioselectivity (> 4) were found. The chromatographic behavior of the sample set was studied on three different polysaccharide-based chiral columns – Chiralpak IA-U, IG-U and IB-U. Comparison of results from Chiralpak IA-U and IB-U shows the effect of amylose vs. cellulose polysaccharide backbone while comparison of Chiralpak IA-U and IG-U reveals the effect of 3,5-dimethylphenylcarbamate vs. 3‑chloro-5-methylphenylcarbamate substituent. The mobile phases tested included whole range of acetonitrile/methanol mixtures to demonstrate that acetonitrile-rich and alcohol-rich mobile phases offer different enantiorecognition mechanisms and can provide complementarity to some extent. The effect of temperature on enantioseparation was investigated on Chiralpak IA-U by constructing van't Hoff plots for selected liquid crystals in pure acetonitrile and pure methanol as mobile phases.