Fluorescence response of hypocrellin B to the environmental changes in a mimic biological membrane—liposome

Liposome is well known as not only a drug-delivery system but also a simple model for biological membranes. It was reported that fluorescence properties of hypocrellins were changeable over some extreme pH values. In the current work, the effects of the microenvironments on the fluorescence properties of HB in liposome, including approximately physiological range of pH values pH = 6.0-8.0, concentration of cholesterols and ionic strength of the solution, were studied. It was found that the fluorescence intensity of HB was sensitive to and also regulated by the microenvironments. When concentration of cholesterols and ionic strength keep invariable in PBS solution, there exists the maximum for the fluorescence of HB-liposome at pH 7.4 while the minimum for that of HB at pH 7.0. In addition, when pH value keeps constant (7.2), there exists the maximum at the ionic strength of 0.12 mol/kg while that at the concentration of 6×10^?4 mol/L for cholesterols. On the other hand, in PBS solution, the lower the ionic strength is, the higher the fluorescence intensity is. The environment-sensitive fluorescence may be potentially applicable to probe some specific environmental features in cells or tissues.

     

Thermodynamics of partitioning of benzocaine in some organic solvent/buffer and liposome systems

The thermodynamics of partitioning of benzocaine (BZC) were studied in octanol/buffer (ROH/W), isopropyl myristate/buffer (IPM/W), cyclohexane/buffer (CH/W), and dimyristoyl phosphatidylcholine (DMPC) and dipalmitoyl phosphatidylcholine (DPPC) liposome systems. In all cases the partition coefficients were greater than unity; therefore the free energies of transfer were negative, that is, the processes of transfer of BZC from aqueous media to organic systems were spontaneous. The partition coefficients were approximately three-fold higher in DMPC liposomes compared with the ROH/W system in the 30 degrees -40 degrees C temperature range. The enthalpies of transfer from aqueous media to ROH and IPM were negative, but positive for CH, while this property was negative for DMPC liposomes and positive for DPPC liposomes. The entropies of transfer were positive in almost all cases, except for DMPC. The results presented here confirm the lipophilic nature of BZC.     

Self-aggregation of synthetic zinc 31-hydroxy-131-oxo-17,18-cis-chlorin in a non-polar organic solvent

Zinc methyl 3¹-demethyl-17,18-cis-bacteriopheophorbide-d was prepared as a model of naturally occurring bacteriochlorophyll-d. From the absorption spectral analysis, the synthetic cis-chlorin self-aggregated in a non-polar organic solvent to give an oligomer possessing red-shifted and broadened peaks, compared to the non-aggregated form. The red-shifted values by self-aggregation were smaller than those observed in the corresponding trans-isomer, indicating that self-aggregates of the cis-isomer took on more disordered supramolecular structures than those of the trans-isomer.     

Synthesis and Properties of An Aminated hypocrellin B

Photodynamic therapy (PDT), using red light and photosensitizers (Sens ), is a promising new treatment for tumor. The naturally occurred hypocrellins,including hypocrellin A (HA) and hypocrellin B (HB,1), have been proposed as the potential photosensitizers for PDT. It has been the subject of many investigations to improve the red absorption and water-solubility of natural hypocrellins by the structural modifications1~3. In this paper, a new derivative 2 was synthesized from 1 and charact…     

Spectroscopic studies and photodynamic actions of hypocrellin B in liposomes

Hypocrellin B (HB), a lipid-soluble natural pigment of perylenequinone derivative, is considered as potential photosensitizer for photodynamic therapy. Liposomes loaded with HB can constitute a simple model system, appropriate for better understanding the photodynamic action of HB in vivo. The steady-state absorption and emission spectra, quantum yield and lifetime of fluorescence of HB incorporated into egg L-a-phosphatidyl-choline (EPC) liposome were examined. The photochemical properties (Type I and/or Type II) of HB have also been studied in aqueous dispersions of small unilamellar liposomes of EPC using electron paramagnetic resonance and spectrophotometric methods, respectively. The quantum yield of 1O2 generated by HB is ca 0.76 in chloroform solution and it did not change upon the incorporation of HB into liposomes of EPC. The superoxide anion radical was generated by the electron transfer from the anion radical of HB (HB.-) to oxygen. The disproportionation of O2.- can generate H2O2 and ultimately the highly reactive .OH via the Fenton reaction. It could be that the disproportionation proceeded too fast, so we could not detect O2.- directly in aqueous dispersions of liposome EPC. Moreover, the self-sensitized photooxygenation of HB embedded in liposomes was studied, and almost fully (87%) inhibiting this reaction of HB by p-benzoquinone (as the quencher of O2.-) in aqueous dispersion of liposome EPC indicated that the radical mechanism (Type I) might be mainly involved in this oxygenation. All these findings suggested that the photodynamic action of HB proceeded via both Type-I and -II mechanisms, but Type-I mechanism might play a more important role in the aqueous dispersion.     

The solubility modelling of non-polar gases in polar and non-polar solvent based on scaled particle theory by artificial neural network

In this work, the effective parameters of the scaled particle theory (SPT) are used as the input to the artificial neural network (ANN) to calculate as the output, the solubility (mole fraction of gas in liquid phase) of non-polar gases in polar and non-polar solvents at 298.15?K and 101.325?kPa. It has been found that ANN used in this work should has five neurons in the hidden layer to achieve the least error. The results of ANN have been compared with the experimental values. The results of this comparison are quite satisfactory. The average relative deviations of the simulations in training and testing stages have been calculated 0.92% and 0.89%, respectively. Finally, the results of ANN were compared with the results of SPT. According to this comparison, it is clear that SPT as a thermodynamic model predicts the solubility of the studied gases in the solvents with the same accuracy of ANN which is a purely mathematical model.     

Small-angle neutron scattering of colloidal silica dispersions in a non-polar solvent

Small-angle neutron scattering studies were performed on dilute dispersions of colloidal silica spheres in mixtures of h₁₂- and d₁₂-cyclohexane. The particles consisted of a SiO₂-core and a layer of stearyl alcohol molecules terminally attached with a chemical bond (Si-O) to the particle surface. The contrast variation method was applied to reveal the internal structure of the particles. The matchpoints determined with this method were in accordance with those calculated from the mass density of the particles and the atomic composition, as determined with elemental analysis.For a detailed interpretation of the scattering curves, we assumed that the particles were spherosymmetrical and consisted of two concentric layers. With the relation we derived between the radius of gyration and the reciprocal contrast for such a model, it was possible to determine all the parameters characterizing the particle in terms of this model. The model calculations performed using these parameters fitted very well to the experimental intensities for high contrasts. For lower contrasts, the fit was somewhat less good. This is probably due to random fluctuations in the scattering length density within the particle core.The different radii as found by neutron scattering, agreed very well with those determined using other techniques, such as light scattering (static and dynamic) and electron microscopy.     

Adsorption of diazinon and fenitrothion on nanocrystalline alumina from non-polar solvent

Nanocrystalline ??-alumina was prepared by the sol-gel method from aluminum sec-butoxide and, after characterization by X-ray diffraction and transmission electron microscopy, was used as an adsorbent for two common organophosphorus pesticides, diethoxy-[(2-isopropyl-6-methyl-4-pyrimidinyl)oxy]-thioxophosphorane (diazinon) and dimethoxy-(3-methyl-4-nitrophenoxy)-thioxophosphorane (fenitrothion). Absorption of these pesticides from hexane was monitored by UV-vis and ³¹P NMR spectroscopies. Adsorption of the aforementioned pesticides by nanocrystalline alumina prepared by the sol-gel method and calcined at 500°C and 800°C was compared with their adsorption by micron-size commercial alumina. Sol-gel derived nanocrystalline alumina showed significantly higher activity than commercial alumina in the destructive adsorption of diazinon and fenitrothion. The bonding mode of pesticides over nanocrystalline and commercial ??-aluminas was investigated by infrared spectroscopy.     

Photobleaching of hypocrellin B and its butylamino-substituted derivative in solutions

Peptides derived from the heavy chain of the HLA Class-I molecules have been shown to modulate immune responses both in vivo and in vitro. Using a computer-aided rational drug design approach, novel immunomodulatory peptides were designed based on peptide 2702.75-85, derived from HLA-B2702. Several peptides were identified which had increased immunomodulatory activity, including peptides RDP1258 and its D-isomer the peptide Allotrap 1258. The present study using Skh/hr hairless mouse skin model evaluated the in vivo effects of Allotrap 1258 on acute UVB-induced skin inflammation. Here we demonstrate that intraperitoneal administration of Allotrap 1258 1 h prior to UV exposure resulted in significantly diminished levels of UV-induced tumor necrosis factor (TNF)-alpha protein production in the epidermis but had no effect on other parameters of the acute UV-induced inflammatory response. By virtue of its ability to suppress TNF-alpha protein production, Allotrap 1258 could prove to be an effective modulator of inflammatory responses.     

Phytochemical analysis of non-polar solvent extracts of the Wisteria sinensis leaves

A comparative study on the phytochemical composition of the n-hexane and chloroform extracts from Wisteria sinensis leaves collected in June and October is described. Continuous extraction in Soxhlet apparatus, as well as ultrasound-assisted technique, was used for the preparation of the extracts. All the extracts were analysed by GC/MS method. As a result, α-tocopherol was identified as the main component (56%) of the extracts from October leaves, whereas, β-sitosterol was identified as the main compound (47%) in the extracts from the June leaves. Additionally, pure α-tocopherol was isolated from n-hexane extract of the October leaves using column chromatography. A total of 6.25 mg of α-tocopherol was isolated from 1 g of dried leaves. The presence of the vitamin E in extracts from W. sinensis leaves is described here for the first time.     

Effect of organic solvent concentration on radioimmunoassay of aflatoxin B1

The effect of acetone and methanol contents in an aqueous casein-buffer solution pipetted with aflatoxin B1 into radioimmunoassay procedure, on some parameters of radioimmunochemical determination of aflatoxin B₁ has been studied. These organic solvents lower an antiserum titer and value of the zero specific binding, and at higher concentrations make worse the detection limit and the accuracy of radioimmunoassay. However, in radioimmunoassay of food extracts containing subresidual levels of aflatoxin, it could be advantageous to add the extract volume to the organic solvent concentration of 60%.     

Photochemical properties of hypocrellin A,B and their oxides

Hypocrellin A and B in methanol were autosensitized and photooxygenated to 1, 4, 6, 7 and 2, 5, 8, 9 respectively. 1 in methanol was photooxygenated to 6 and 7 under the sensitization by HB. 1 in methanol was photooxygenated to 7 under the sensitization by Rose bengal. 1 in benzene irradiated with medium-pressure-mercury lamp was photolyzed to 3 in the presence of iodine.     

Electronic spectra of hypocrellin A, B and their derivatives

In this paper, the electronic spectra of hypocrellin A and B (HA and HB) are studied in detail. It has been proved that their three visible absorption bands come respectively from the pi pi transition of their conjugated systems and intramolecular proton transfer. In dilute solutions, their fluorescence spectra consist of the fluorescence peak of the neutral monomolecule and that of the zwitter-ions that are formed through proton transfer of excited states. In concentrated solution, the longer wavelength emission band is composed of the overlapped fluorescence peaks of zwitter-ions and excimers. The fluorescence spectra of the crystalline hypocrellin A and B consist of the fluorescence peaks of zwitter-ions and excimers and the fluorescence of neutral monomolecules could could not be observed. Their relative intensities are closely related to the excitation wave-length.     

Univalent cation-exchange in organic solvent water and organic solvent-water-phenol mixtures

Selectivity coefficients, K(H)(M), for the exchange of alkali metal ions and ammonium ions with the hydrogen form of ZeoKarb 225 cation-exchange resin have been determined in various organic solvent-water and organic solvent-water-phenol mixtures. There is an increase in K(H)(M) in passing from purely aqueous conditions to media of increasing organic solvent content, frequently with the effect of producing magnified differences and selectivity reversals between one ion and another. The results are discussed in terms of the relationship between K(H)(M) and the reciprocal of the dielectric constant of the medium and also in the light of free energies of transfer of cations between methanol-water systems. The effect of phenol giving a lowering of K(H)(Cs) in methanol-water, of K(H)(K) and K(H)(Na) in ethanol-water and of K(H)(Na) and K(H)(L1) in acetone-water systems cannot be fully reconciled with the mechanism involving bonding proposed by earlier workers.     

Ultrafast solvent response upon a change of the solute size in non-polar supercritical fluids

Non-polar solvation dynamics has been investigated using steady-state absorption and emission spectroscopy of the NO A ²Σ⁺(3sσ) Rydberg state in fluid Ar over a wide range of densities spanning the supercritical regime. Equilibrium molecular dynamics simulations were implemented to derive a new isotropic NO A(3sσ)–Ar pair potential which was further used to investigate the role of local density enhancements on the solvation process by non-equilibrium molecular dynamics simulations. These density inhomogeneities were found to have no influence on the solvation dynamics. Furthermore, the latter was shown to take place in a strongly non-linear regime, especially at low temperatures. This process results from the dramatic change of solute–solvent short range interaction associated with the large solute size change upon excitation to the Rydberg state.     

有机质子溶剂和有机-水溶液中质子浓度的精确测定

用水标准溶液标定的玻璃电极可用来测定有机质子溶剂和有机-水溶液中质子的水标准活度pHm质子的浓度可用-og[H2S^ ]=pHm-(-logγ-D)来精确测定。(-logγ-D)是一个常数，可以通过对有机质子溶剂和有机-水溶液中强酸-强碱滴定曲线的数学模拟后求得。因此避免了玻璃电极在有机溶剂中标定的困难。     

Ligand-stabilized metal nanoparticles in organic solvent

This critical review reports the fundamental behavior of metal nanoparticles in different organic solvents, i.e., metal organosol. An overview on metal organosol and then their smart synthetic approaches, characterization, and potential applications in the fields of catalysis and spectroscopy with special emphasis on SERS are embodied. Aspects of organosol fabrication, stabilization, morphology control, growth mechanisms, and physical properties as mono- and bimetallic nanoparticles are discussed. The article inspires the repetitive usage of metal nanoparticles as stable deliverable organic and molecular compounds.     

Relationship between photosensitizing activities and chemical structure of hypocrellin A and B.

Hypocrellins A (HA) and B (HB) are two main pigments isolated from the parasitic fungi Hypocrella bambusae (B. et Br) Sacc. and Shiraia bambusicola P. Heen found in China. These pigments have a long history as traditional medicinal agents. Although HA and HB have the same perylene quinonoid structure, there are different side rings. The different photosensitizing activities of HA and HB due to their different side rings were studied by electron paramagnetic resonance (EPR), spin trapping and spin counteraction techniques. It is demonstrated that the ability to generate active oxygen (1O2, O2.- and .OH) is stronger during HA photosensitization than during HB photosensitization. Under anaerobic conditions, the ability to generate HA.- during HA photosensitization is stronger than the ability to generate HB.- during HB photosensitization. There is a relationship between photosensitizing ability and chemical structure.     

Adsorption of diazinon and fenitothion on MCM-41 and MCM-48 mesoporous silicas from non-polar solvent

The adsorption of two common organophosphorus pesticides, diethoxy-[(2-isopropyl-6-methyl-4-pyrimidinyl)oxy]-thioxophosphorane (diazinon) and dimethoxy-(3-methyl-4-nitrophenoxy)-thioxophosphorane (fenitrothion), by MCM-41 and MCM-48 mesoporous silicas at room temperature was investigated. UVvis and IR spectroscopy, small-angle X-ray diffraction, and the specific surface area analysis (S _BET) were used to study the adsorption behavior of diazinon and fenitrothion. The results show that the MCM-41 and MCM-48 mesoporous silicas adsorb diazinon more efficiently than fenitrothion. The extraction of adsorbed materials from the adsorbents with polar solvents and subsequent analysis by ³¹P NMR showed that the adsorption of diazinon and fenitrothion on mesoporous silicas is destructive and non-destructive, respectively. Nitrogen adsorption measurements showed that the specific surface area of both silicas decreases after the adsorption of pesticides, and the larger effect is observed for diazinon. The article is published in the original.     

Synthesis of a novel comb-like copolymer used as dispersant in organic solvent and influence of free comb-like copolymer on CaCO3 suspension

A novel comb-like copolymer poly (1e)-graft-poly (ε-caprolactone) (SMA-g-PCL, SP), which can be used as an effective CaCO₃ dispersant in organic solvent, was prepared via the esterification reaction between SMA and PCL. The structures and compositions of the graft copolymer were determined by Fourier transform infrared spectrometry (FTIR), H-nuclear magnetic resonance (¹H NMR), and gel permeation chromatography (GPC), respectively. The influences of free comb-like copolymer on CaCO₃ suspension viscosity and rheological behavior were investigated. It was found that the particle-binding bridge generated among CaCO₃ particles through hydrogen bonding and/or electrostatic interactions increased the suspension viscosity as well as the depletion flocculation. On the other hand, it was noteworthy that the free comb-like copolymer could make the CaCO₃ suspension evolve from shear-thinning fluid or nearly Newtonian fluid into shear-thickening fluid. It was attributed to the formation of a transient network through intermolecular associations between the adsorbed SP and the free polymer chains under the action of shear. Finally, the fitting parameters from the Herschel–Bulkley model were in good agreement with the evolution of the rheological behavior of CaCO₃ suspension.