Isothermal titration calorimetric studies of surfactant interactions with negatively charged, ‘hairy’ latex nanoparticles

Isothermal titration calorimetry (ITC) measurements of the mixture of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) with negatively charged, hairy copolymer latices (poly-(2,3-epoxypropylmethacrylate-co-methacrylic acid) in different ratio) at high water excess indicate a monomer adsorption mechanism of CTAB by the polymer particles. The number of adsorbed CTAB molecules at saturation corresponds approximately to the number of negative elementary charges bound at the surface of the latices. The mixing enthalpy is the sum of demicellization and sorption enthalpies. At 25 °C for CTAB the demicellization enthalpy amounts to 10 kJ/mol, whereas the adsorption enthalpy varies from –7 kJ/mol (surface charge density of the latices =–0.37 C/m²) to +3 kJ/mol (=–0.085 C/m²). The hydrodynamic radius R_H of the latex particles upon titration of cationic detergent and salt (NaBr) decreases by about 2 nm until the onset of aggregation near the isoelectric point. Titration of nonionic or anionic detergents has much less influence on the hydrodynamic radius and produces no measurable adsorption heat. The results are consistent within a model of latex particles with extended negatively charged polymer chains interacting predominantly via Coulombic forces with detergents.     

Calorimeters for biotechnology

The isothermal and temperature scanning calorimeters manufactured by Calorimetry Sciences Corporation are briefly described. Applications of calorimetry to determine thermodynamics and kinetics of reactions of interest in biotechnology are described with illustrative examples.     

Hydration and Lyotropic Melting of Amphiphilic Molecules: A Thermodynamic Study Using Humidity Titration Calorimetry

The hydration of the lipid 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) and of the cationic detergent dodecyltrimethylammonium bromide (DTAB) has been studied by means of isothermal titration calorimetry (ITC), gravimetry, and infrared (IR) spectroscopy. During the experiments films of the amphiphiles are perfused by an inert gas of variable relative humidity. The measurement of adsorption heats using ITC represents a new adaptation of adsorption calorimetry which has been called the humidity titration technique. This method yields the partial molar enthalpy of water upon adsorption. It is found to be endothermic with respect to the molar enthalpy of water on condensation for the water molecules which interact directly with the headgroups of POPC and DTAB. Consequently, the spontaneous hydration of the amphiphiles is entropy driven in an aqueous environment. IR spectroscopy shows that hydration is accompanied by the increase in the conformational and/or motional freedom of the amphiphilic molecules upon water binding. In particular, a lyotropic chain melting transition is induced at a certain characteristic relative humidity. This event is paralleled by the adsorption of water. The corresponding exothermic adsorption heat is consumed completely (POPC) or partially (DTAB) by the hydrocarbon chains upon melting. Differential scanning calorimetry was used as an independent method to determine transition enthalpies of the amphiphiles at a definite hydration degree. Water binding onto the headgroups is discussed in terms of hydrogen bonding and polar interactions. The adsorption isotherms yield a number of 2.6 tightly bound water molecules per POPC and DTAB molecule.     

Experimental evidence of chiral crown ether complexation with aromatic amino acids

The complexation of L ‐ and D ‐enantiomers of phenylglycine, phenylalanine, and tryptophan with D ‐mannonaphto‐crown‐6‐ether in methanol solution was studied by NMR and isothermal titration calorimetry (ITC) at 298.15 K. The total heat effects attributed to the binding phenomena were measured in the range of 1.8 to 7.7 mJ, and the complexation was found stereo‐specific. The binding topologies were estimated basing on ¹H 2D‐ROESY experiments. The analysis of Job plots obtained from ¹H NMR‐monitored titrations proved the coexistence of 1:1 and 1:2 (crown ether:amino acids) complexes, which thermodynamic parameters, K_s, ΔG, ΔH°, and TΔS were determined with the aid of ITC. The 1:1 complexes were found enthalpically stabilized, generally by electrostatic interactions between the charged NH group of amino acid and crown ether macrocyclic moiety, while the binding of the second amino acid molecule was driven entropically due to solvatophobic effect. Strong enthalpy–entropy compensation points towards the uniform binding mode of all complexes studied. The mode of complex formation was found solvent dependent. For phenylalanine guest studied in various solvent systems, in contrast to the aqueous media, the noticeable chiral recognition is observed in methanol solution, and the complex stoichiometry (1:2 ether:Phe) differs from the 2:1 one, determined previously for the same host‐guest system in water (J. Thermal. Anal. Cal. 2006; 83: 575–578). Copyright © 2007 John Wiley & Sons, Ltd.     

改进21FS彩管会聚品位

本文运用6Sigma工具定量分析了由于21FS彩管QPF电子枪的受聚焦电压影响SP光点位置相对移动,从而导致产品在用户处静会聚一致性差的重要原因。并通过设计优化电子枪偏孔设计特点,从理论和试验实践上解决了聚焦电压对21”静会聚的影响。     

Isothermal titration calorimetry of Ni(II) binding to histidine and to N-2-aminoethylglycine

Isothermal titration calorimetry (ITC) is used to study the complexation thermodynamics of Ni(II) with histidine (His) and with N-2-aminoethylglycine (EDMA). The titrations were performed in HEPES and Tris buffers at various ionic strengths and pH values around 8. The results show the influence of the experimental conditions on the shape and fitting parameters of the calorimetric curves. For the studied systems, the main reaction is concomitant with a number of side reactions which contribute to the global energy measured. From the calorimetric data measured, the formation constants for the species NiHEPES⁺, Tris⁺His⁻, TrisNiHis⁺ and [Ni(EDMA)₂OH]⁻ have been evaluated for the first time and the values obtained properly validated.     

Biochemical and computational insights of adenosine deaminase inhibition by Epigallocatechin gallate

Epigallocatechin gallate, a flavonoid from Camellia sinensis possess various pharmacological activities such as anticancer, antimicrobial and antioxidant etc. Adenosine deaminase, (ADA), is a key enzyme involved in the purine metabolism, the inhibitors of which is being considered as highly promising candidate for the development of anti-proliferative and anti-inflammatory drugs. In this work we studied adenosine deaminase inhibitory activity of epigallocatechin gallate by using biophysical and computational methods. The enzyme inhibition study result indicated that epigallocatechin gallate possess strong inhibitory activity on ADA. ITC study revealed the energetics of binding. Also the binding is confirmed by using fluorescence spectroscopy. The structural details of binding are obtained from molecular docking and MD simulation studies.     

Sequence‐Defined Introduction of Hydrophobic Motifs and Effects in Lectin Binding of Precision Glycomacromolecules

This study investigates the influence of an increasingly hydrophobic backbone of multivalent glycomimetics based on sequence‐defined oligo(amidoamines) on their resulting affinity toward bacterial lectins. Glycomacromolecules are obtained by stepwise assembly of tailor‐made building blocks on solid support, using both hydrophobic aliphatic and aromatic building blocks to enable a gradual change in hydrophobicity of the backbone. Their binding behavior toward model lectin Concanavalin A (ConA) is evaluated using isothermal titration calorimetry (ITC) and surface plasmon resonance (SPR) showing higher affinities for glycomacromolecules with higher content of hydrophobic and aromatic moieties in the backbone. Finally, glycomacromolecules are tested in a bacterial adhesion inhibition study against Escherichia coli where more hydrophobic backbones yield higher inhibitory potentials most likely due to additional secondary interactions with hydrophobic regions of the protein receptor as well as a change in conformation exposing carbohydrate ligands for increased binding. Overall, the results highlight the influence and thereby importance of the polymer backbone itself on the resulting properties of polymeric biomimetics.     

Isothermal titration calorimetric studies of the pH induced conformational changes of bovine serum albumin

Bovine serum albumin (BSA) is a soft globular protein that undergoes conformational changes through several identified transition steps in the pH range 2–13.5. The ability to change conformation makes BSA capable of complexing different ligands from fatty acids to cations or drugs and carries them in the bloodstream. Microcalorimetric titration of BSA with NaOH solution was performed to measure the enthalpy of conformational changes. Two exothermic enthalpy changes were found in the course of the titration between pH 3 and 9.5, which can be identified with the E–F, and the F–N transitions. The enthalpy change at pH 3.5 (transition from the E to the F form of BSA, folding of intra-domain helices in domain I) is independent of the protein concentration. The second transition (F–N, folding of domain III) was observed at pH 4.8 for the 0.1% BSA solution, but it shifted to higher pH values as the protein concentration increased to 0.2% and 0.3%. The tightening of the protein structure with increasing pH was verified measuring intrinsic fluorescence of tryptophan residues. At even higher pH value, pH 10.5, fluorescence measurements revealed protein expansion. The BSA conformational changes were also measured by dynamic light scattering. The hydrodynamic diameter was smaller at the i.e.p. of BSA (5–7 nm at pH ~5) and larger at the two ends of the pH range (17.5 nm at pH 2 and 8.3 nm at pH 10).     

利用FB-MAPES算法估计Tomography SAR高度维信号源数

层析成像合成孔径雷达(Tomography SAR)结合空间谱估计技术解决层叠效应时,首先要估计出高度维信号源数目,信号源数估计得正确与否直接关系到后续处理的估计性能。用传统的信息论方法估计时,由于数据受乘性噪声影响,估计性能下降。该文提出一种新的信号源数估计方法：双向平滑多视幅相估计(FB-MAPES)滤波器算法。通过Monte Carlo仿真对信息论方法中的GMDL算法和FB-MAPES方法的估计性能进行了比较,试验结果表明该文提出的方法能够更好地适应乘性噪声的影响,因而在估计Tomography SAR高度维信号源数时性能优于传统的信息论方法。