Utilizing Laser Activation of Photothermal Plasmonic Nanoparticles to Induce On-Demand Drug Amorphization inside a Tablet.

Poor aqueous drug solubility represents a major challenge in oral drug delivery. A novel approach to overcome this challenge is drug amorphization inside a tablet, that is, on-demand drug amorphization. The amorphous form is a thermodynamically instable, disordered solid-state with increased dissolution rate and solubility compared to its crystalline counterpart. During on-demand drug amorphization, the drug molecularly disperses into a polymer to form an amorphous solid at elevated temperatures inside a tablet. This study investigates, for the first time, the utilization of photothermal plasmonic nanoparticles for on-demand drug amorphization as a new pharmaceutical application. For this, near-IR photothermal plasmonic nanoparticles were tableted together with a crystalline drug (celecoxib) and a polymer (polyvinylpyrrolidone). The tablets were subjected to a near-IR laser at different intensities and durations to study the rate of drug amorphization under each condition. During laser irradiation, the plasmonic nanoparticles homogeneously heated the tablet. The temperature was directly related to the rate and degree of amorphization. Exposure times as low as 180 s at 1.12 W cm-2 laser intensity with only 0.25 wt % plasmonic nanoparticles and up to 50 wt % drug load resulted in complete drug amorphization. Therefore, near-IR photothermal plasmonic nanoparticles are promising excipients for on-demand drug amorphization with laser irradiation.

Preparation of Acifluorfen-Based Ionic Liquids with Fluorescent Properties for Enhancing Biological Activities and Reducing the Risk to the Aquatic Environment.

In this work, 12 novel herbicidal ionic liquids (HILs) based on acifluorfen were prepared by pairing with the fluorescent hydrazides or different alkyl chains for increasing activities and reducing negative impacts on the aquatic environment. The results showed that the fluorescence of coumarin hydrazide in the HILs was applied as the internal and supplementary light source to meet the requirement of light wavelength range of acifluorfen, which improved the phytotoxicity of acifluorfen to weeds by enhancing singlet oxygen generation with increased sunlight utilization. The herbicidal activities of HILs were related positively with the length of chain of cation under high light intensity and depended mainly on the fluorescence characteristic of the cation under low light intensity, and the double salt IL forms of acifluorfen containing coumarin hydrazide and n-hexadecyltrimethylammonium had enhanced efficacies against broadleaf weeds in the field. Compared with acifluorfen sodium, HILs had lower water solubility, better surface activity, weaker mobility in soils, and higher decomposition temperature. These results demonstrated that HILs containing different cations provided a wider scope for fine-tuning of the physicochemical and biological properties of herbicides and established a promising way for the development of environmentally friendly herbicidal formulations.

Dissolution of a fibrous peptide by terahertz free electron laser.

Fibrous peptides such as amyloid fibrils have various roles in biological system, e.g., as causal factor of serious amyloidosis in human and as functional regulator of cell formation in bacteria and eukaryotes. In addition, the fiber-type format is promising as biocompatible scaffold. Therefore, the dissolution method of peptide fibril is potentially useful at many scenes in medical and material fields: as reductive way of pathogenic amyloid, as modification technique of cell structure, and as fabrication tool of biomaterials. However, the fibril structure is generally difficult to be dissociated due to its rigid stacked conformation. Here, we propose a physical engineering technology using terahertz free electron laser (FEL) at far-infrared wavelengths from 70 to 80 µm. Infrared microscopy analysis of the irradiated fibril of calcitonin peptide as a model showed that ß-sheet was decreased, and α-helix, turn, and others were increased, compared to those of the fibril before the FEL irradiation. Interestingly, the dissociative effect by the far-infrared laser was remarkable than that by the mid-infrared laser tuned to 6.1 µm that corresponds to amide I. In addition, simple heating at 363 K deformed the fibril state but increased the amount of ß-sheet, which was contrast with the action by the FEL, and scanning-electron microscopy and Congo-red staining revealed that the fibril was collapsed power-dependently within a range from 25 to 900 mJ energies supplied with the FEL at 74 µm. It can be considered that irradiation of intense terahertz wave can dissociate fibrous conformation of peptide with little influence of thermal effect.

Immunomodulatory effect of γ-irradiated Astragalus polysaccharides on immunosuppressed broilers.

In this study, we irradiated Astragalus polysaccharides (APS) using 25 kGy 60 Co γ ray to obtain γ-irradiated Astragalus polysaccharides (IAPS) and then investigated the effects of IAPS on growth performance and immune function of cyclophosphamide (CPM)-treated broilers. The physicochemical properties of APS and IAPS (molecular weight, water solubility, viscosity, morphological and structural properties) were evaluated. Then, 384 one-day-old Arbor Acres broiler chicks with similar initial weight were randomly assigned into 6 groups: the non-treated group (control), and CPM-treated groups were fed either a basal diet or the diets containing 900 mg/kg APS, or 900, 600, 300 mg/kg IAPS, respectively. On days 16, 18, and 20, all broilers except for the control group were intramuscularly injected with 0.5 ml CPM (40 mg/kg·BW). Broilers in the control group were intramuscularly injected with 0.5 ml sterilized saline (0.75%, wt/vol). This trial lasted for 21 days. The physicochemical treatment showed that γ irradiation could decrease the molecular weight and viscosity, and increase the water solubility of APS (p < 0.05), whereas the structural properties of APS was not affected. In the animal trial, 900 mg/kg APS or 900, 600 mg/kg IAPS relieved the decreased growth performance, thymus index, T lymphocytes proliferation, serum IgG concentration, NOS activity and the increased blood heterophil:lymphocyte ratio in CPM-treated broilers (p < 0.05). CPM-induced decreases in B lymphocytes proliferation and serum IgM concentration were only increased by IAPS at 900 mg/kg (p < 0.05). Overall, both APS and IAPS alleviated CPM-induced immunosuppression. Especially, IAPS possessed better immunomodulatory effect than APS, indicating that γ irradiation could be used as an effective method to enhance the immunomodulatory activity of APS.

Effect of gamma irradiation on structure, physicochemical and immunomodulatory properties of Astragalus polysaccharides.

Astragalus polysaccharides (APS) were treated with different gamma irradiation doses (10, 25, 50, 100 and 150 kGy) to investigate the effects of gamma radiation processing on structure, physicochemical and immunomodulatory properties. The results revealed both the number-average and weight-average molecular weight of APS significantly decreased with increasing irradiation dose, whereas the solubility was increased after irradiation. A decrease in the apparent viscosity, as well as an increase in amount of small fragments of APS granules was also observed with increasing irradiation dose. FT-IR spectra indicated that gamma irradiation introduced no significant changes into the functional group status of APS. High irradiation dose (>50 kGy) caused a significant increase of yellowness and a slightly decrease of thermal stability of APS. Further, the immunomodulatory activity of irradiated APS was evaluated on Caco2 cells. APS irradiated at dose of 25 kGy exhibited the highest ability to induce nitric oxide production and up-regulate the mRNA expression of inflammatory cytokines, occludin, zonula occludens protein-1 (ZO-1) and toll-like receptor 4 (TLR4), as well as the protein expression of ZO-1 and TLR4. These findings indicate that gamma irradiation modification with a proper dose enhance immunomodulatory activity of APS by improving physicochemical properties without changing the functional groups.

Toward Developing a Predictive Approach To Assess Electron Beam Instability during Transmission Electron Microscopy of Drug Molecules.

During drug development control of polymorphism, particle properties and impurities are critical for ensuring a good quality, reproducible, and safe medicine. A wide variety of analytical techniques are employed in demonstrating the regulators control over the drug substance and product manufacturing, storage, and supply. Transmission electron microscopy (TEM) offers the opportunity to analyze in detail pharmaceutical systems at a length scale and limit of detection not readily achieved by many traditional techniques. However, the use of TEM as a characterization tool for drug development is uncommon due to possible damage caused by the electron beam. This work outlines the development of a model, using molecular descriptors, to predict the electron beam stability of active pharmaceutical ingredients (API). For a given set of conditions and a particular imaging or analytical mode, the total number of electrons per unit area, which causes observable damage to a sample in the TEM, can be defined as the critical fluence ( CF). Here the CF of 20 poorly water-soluble APIs were measured using selected area electron diffraction. Principal component analysis was used to select the most influential molecular descriptors on CF, which were shown to be descriptors involving the degree of conjugation, the number of hydrogen bond donors and acceptors, and the number of rotatable bonds. These were used to generate several multiple linear regression models. The model that provided the best fit to the measured CF data included the ratio of the number of conjugated carbons to nonconjugated carbons, the ratio of the number of hydrogen bond donors to acceptors, and the ratio of the number of hydrogen bond acceptors to donors. Using this model, the CF of the majority of the compounds was predicted within ±2 e-/Å2. Molecules with no hydrogen bond acceptors did not fit the model accurately possibly due to the limited sample size or the influence of other parameters not included in this model, such as intermolecular bond energies. The model presented can be used to support pharmaceutical development by quickly assessing the stability of other poorly soluble drugs in TEM. Provided that the model suggests that the API is relatively stable to electron irradiation, TEM offers the prospect of determining the presence of crystalline material at low levels at length scales and limits of detection unobtainable by other techniques. This is particularly so for amorphous solid dispersions.

Light Control of Protein Solubility Through Isoelectric Point Modulation.

We previously described the photoactivated depot or PAD approach that allows for the light control of therapeutic protein release. This approach relies on the ability to use light to change a protein's solubility. Traditionally this was accomplished by linking the protein to an insoluble but injectable polymer via a light cleaved linker. This allows the injected material to remain at the site of injection, until transcutaneous irradiation breaks the link between polymer and protein, permitting the protein to be absorbed. However, there are multiple problems associated with polymer based approaches: The polymer makes up a majority of the material, making it inefficient. In addition, after protein release, the polymer has to be cleared from the body, a significant design challenge. In this work, we create materials that form photoactivated depots of insulin without the need for polymers, by linking photolysis to an isoelectric point shift, which itself is linked to a solubility shift. Specifically, we linked basic groups to insulin via a light cleaved linker. These shift the normal pI of insulin from 5.4 to approximately 7. The result of this incorporation are materials that are completely soluble in mildly acidic solutions but precipitate upon injection into a pH 7 environment, i.e., the skin. We successfully synthesized four such modified insulins, demonstrating that their pI values were shifted in the expected manner. We then analyzed one of them, P2-insulin, in detail, demonstrating that it behaves as designed: It is soluble in a formulation pH of 4, but precipitates at pH 7.2, its approximate pI value. Upon irradiation, the photocleavable link to insulin is broken, and completely native and soluble insulin is released from the depot in a well behaved, first order fashion. These materials are 90% therapeutic, form completely soluble and injectable formulations in mildly acidic conditions, form insoluble depots at neutral pH, efficiently release soluble protein from these depots when irradiated, and leave behind only small easily absorbed molecules after irradiation. As such they approach ideality for photoactivated depot materials.

Does laser diode irradiation improve the degree of conversion of simplified dentin bonding systems?

OBJECTIVE: This study aimed to investigate the effect of laser diode irradiation on the degree of conversion (DC), water sorption (WS), and water solubility (WSB) of these bonding systems in an attempt to improve their physico-mechanical resistance. MATERIAL AND METHODS: Two bonding agents were tested: a two-step total-etch system [Adper™ Single Bond 2, 3M ESPE (SB)] and a universal system [Adper™ Single Bond Universal, 3M ESPE (SU)]. Square-shaped specimens were prepared and assigned into 4 groups (n=5): SB and SU (control groups - no laser irradiation) and SB-L and SU-L [SB and SU laser (L) - irradiated groups]. DC was assessed using Fourier transform infrared spectroscopy with attenuated total reflectance. Additional uncured resin samples (≈3.0 µL, n=5) of each adhesive were also scanned for final DC calculation. For WS/WSB tests, similar specimens (n=10) were prepared and measured by monitoring the mass changes after dehydration/water storage cycles. For both tests, adhesive fluids were dropped into standardized Teflon molds (6.0×6.0×1.0 mm), irradiated with a 970-nm laser diode, and then polymerized with an LED-curing unit (1 W/cm2). RESULTS: Laser irradiation immediately before photopolymerization increased the DC (%) of the tested adhesives: SB-L>SB>SU-L>SU. For WS/WSB (µg/mm3), only the dentin bonding system (DBS) was a significant factor (p<0.05): SB>SU. CONCLUSION: Irradiation with a laser diode improved the degree of conversion of all tested simplified dentin bonding systems, with no impact on water sorption and solubility.

Does laser diode irradiation improve the degree of conversion of simplified dentin bonding systems?

Abstract Simplified dentin-bonding systems are clinically employed for most adhesive procedures, and they are prone to hydrolytic degradation. Objective This study aimed to investigate the effect of laser diode irradiation on the degree of conversion (DC), water sorption (WS), and water solubility (WSB) of these bonding systems in an attempt to improve their physico-mechanical resistance. Material and Methods Two bonding agents were tested: a two-step total-etch system [Adper™ Single Bond 2, 3M ESPE (SB)] and a universal system [Adper™ Single Bond Universal, 3M ESPE (SU)]. Square-shaped specimens were prepared and assigned into 4 groups (n=5): SB and SU (control groups - no laser irradiation) and SB-L and SU-L [SB and SU laser (L) - irradiated groups]. DC was assessed using Fourier transform infrared spectroscopy with attenuated total reflectance. Additional uncured resin samples (≈3.0 µL, n=5) of each adhesive were also scanned for final DC calculation. For WS/WSB tests, similar specimens (n=10) were prepared and measured by monitoring the mass changes after dehydration/water storage cycles. For both tests, adhesive fluids were dropped into standardized Teflon molds (6.0×6.0×1.0 mm), irradiated with a 970-nm laser diode, and then polymerized with an LED-curing unit (1 W/cm2). Results Laser irradiation immediately before photopolymerization increased the DC (%) of the tested adhesives: SB-L>SB>SU-L>SU. For WS/WSB (μg/mm3), only the dentin bonding system (DBS) was a significant factor (p<0.05): SB>SU. Conclusion Irradiation with a laser diode improved the degree of conversion of all tested simplified dentin bonding systems, with no impact on water sorption and solubility.

Antioxidant Vitamin E/Cyclodextrin Inclusion Complex Electrospun Nanofibers: Enhanced Water Solubility, Prolonged Shelf Life, and Photostability of Vitamin E.

Here, we demonstrated the electrospinning of polymer-free nanofibrous webs from inclusion complex (IC) between hydroxypropyl-ß-cyclodextrin (HPßCD) and Vitamin E (Vitamin E/HPßCD-IC NF). The inclusion complexation between HPßCD and Vitamin E was prepared by using two different molar ratios (Vitamin E/HPßCD; 1:2 and 1:1), which correspond to theoretical value of ∼13% (w/w) and 26% (w/w) loading of Vitamin E in the nanofiber (NF) matrix. After electrospinning and storage, a very high loading of Vitamin E (up to ∼11% w/w, with respect to fiber matrix) was preserved in Vitamin E/HPßCD-IC NF. Because of the cyclodextrin inclusion complexation, only a minimal weight loss (only ∼2% w/w) was observed. While pure Vitamin E is insoluble in water, Vitamin E/HPßCD-IC NF web has displayed fast-dissolving behavior. Because of the greatly enhanced water-solubility of Vitamin E, Vitamin E/HPßCD-IC NF web has shown effective antioxidant activity. Additionally, Vitamin E/HPßCD-IC NF web has provided enhanced photostability for the sensitive Vitamin E by the inclusion complexation in which Vitamin E/HPßCD-IC NF still kept its antioxidant activity even after exposure to UV-light. Moreover, a 3 year-old Vitamin E/HPßCD-IC NF sample has shown very similar antioxidant efficiency when compared with freshly prepared Vitamin E/HPßCD-IC NF indicating that long-term stability was achieved for Vitamin E in the CD-IC fiber matrix. In brief, our results suggested that polymer-free electrospun Vitamin E/HPßCD-IC nanofibrous webs could have potential applications in food, pharmaceuticals, and healthcare thanks to its efficient antioxidant activity along with enhanced water-solubility, prolonged shelf life, and high photostability of Vitamin E.

An experimental comparison of human and bovine rhodopsin provides insight into the molecular basis of retinal disease.

Rhodopsin is the visual pigment that mediates dim-light vision in vertebrates and is a model system for the study of retinal disease. The majority of rhodopsin experiments are performed using bovine rhodopsin; however, recent evidence suggests that significant functional differences exist among mammalian rhodopsins. In this study, we identify differences in both thermal decay and light-activated retinal release rates between bovine and human rhodopsin and perform mutagenesis studies to highlight two clusters of substitutions that contribute to these differences. We also demonstrate that the retinitis pigmentosa-associated mutation G51A behaves differently in human rhodopsin compared to bovine rhodopsin and determine that the thermal decay rate of an ancestrally reconstructed mammalian rhodopsin displays an intermediate phenotype compared to the two extant pigments.

Impact of thermo-chemo-sonic pretreatment in solubilizing waste activated sludge for biogas production: Energetic analysis and economic assessment.

The objective of this study was to determine the impact of solubilization during thermo-chemo-sonic pretreatment of waste activated sludge (WAS) on anaerobic biodegradability and cost for biogas production. The results revealed that it was possible to achieve 40-50% of solubilization of WAS when ultrasonic energy input was doubled (11,520-27,000kJ/kgTS). The cost to achieve 30-35% of solubilization of WAS was calculated to be 0.22-0.24USD/L, which was relatively lower than the cost of 0.53-0.8USD/L when 40-50% of solubilisation of WAS was achieved. There was no significant difference in biodegradability (0.60-0.64gCOD/gCOD) for samples with solubilization efficiency of 35-50%. Comparing energetic balance and economic assessment of samples with different solubilization percentages, the results showed that samples with 30-35% of solubilization had lower net cost (7.98-2.33USD/Ton of sludge) and negative energy balance compared to samples with other percentages of solubilization.

Avaliação da citotoxicidade do composto de inclusão de erlotinibe em hidroxipropil-beta-ciclodextrina e da hipertermia associada à cisplatina / Evaluation of cytotoxicity of erlotinib/hydroxypropyl-beta-cyclodextrin inclusion compound and of hyperthermia associated to cisplatin

Estratégias amplamente utilizadas para potencializar os efeitos citotóxicos de moléculas antitumorais com o objetivo de reduzir a dose aplicada e os efeitos colaterais são a inclusão molecular e a associação da quimioterapia com a hipertermia. No presente trabalho foram estudadas estas duas estratégias, sendo a primeira a inclusão molecular que é muito utilizada para aumentar a solubilidade, a absorção e a disponibilidade de moléculas; e a segunda, a hipertermia que é uma proposta de tratamento do câncer no qual as células do tumor são afetadas pela elevação da temperatura local, podendo ser associada com a quimioterapia para potencializar os efeitos dessa técnica. Para a inclusão molecular usou-se a hidroxipropil-¿-ciclodextrina (HP-¿-CD) a fim de aumentar a solubilidade, a absorção e a disponibilidade do erlotinibe (ERL), caracterizou-se fisico-quimicamente, e avaliou-se a citotoxicidade e a apoptosein vitro, e a angiogênese inflamatória in vivo em camundongos Swiss. Para avaliar o efeito citotóxico da hipertermia (aquecimento a 42°C ou 43°C por 1h) associada à cisplatina utilizou-se linhagens de câncer de mama triplo-negativos (MDA-MB-231, MDA-MB-436, MDA-MB-468 e HCC-1937), linhagens de câncer de colo do útero (ME-180 e SiHa) e linhagens de câncer de pulmão (A549 e H460). A caracterização físico-química mostrou a formação do complexo de inclusão em estado sólido e aquoso, e com uma razão molar entre o ERL e HP-¿-CD preferencialmente de 1:1. O estudo de solubilidade de fases mostrou um diagrama do tipo AL e a calorimetria de titulação isotérmica e a espectrometria de ressonância magnética nuclear, efeito Overhauser nuclear suportam essa formação...

Strategies widely used to potentiate the cytotoxic effects of antitumor molecules with the aim of reduce the applied dose and side effects are molecular inclusion and the combination of chemotherapy with hyperthermia. In this thesis, these two strategies were studied, the first molecular inclusion that is widely used to enhance solubility, absorption and availability molecules; and the second, hyperthermia which is a proposal for treatment of cancer where the tumor cells are affected by local temperature elevation and can be associated with chemotherapy to enhance the effects of this technique. For molecular inclusion used to hydroxypropyl--cyclodextrin (HP--CD) to enhance solubility, absorption and availability of erlotinib (ERL), was characterized physico chemically and evaluated the in vitro cytotoxicity and apoptosis, and in vivo inflammatory angiogenesis in Swiss mice. To evaluate the cytotoxic of hyperthermia (heating to 42°C or 43°C for 1h) associated with cisplatin was used triple-negative breast cancer cell lines (MDA-MB-231, MDA-MB-436, MDA-MB-468 and HCC-1937), cervical cancer cell lines (ME-180 and SiHa) and lung cancer cell lines (A549 and H460). The physico-chemical characterization showed the formation of the inclusion complex in solid and aqueous state and with a molar ratio between the ERL and HP--CD preferably 1:1. Phase-solubility ...

Assessing the impact of synchrotron X-ray irradiation on proteinaceous specimens at macro and molecular levels.

Synchrotron radiation (SR) has become a preferred technique for the analysis of a wide range of archeological samples, artwork, and museum specimens. While SR is called a nondestructive technique, its effect on proteinaceous specimens has not been fully investigated at the molecular level. To investigate the molecular level effects of synchrotron X-ray on proteinaceous specimens, we propose a methodology where four variables are considered: (1) type of specimen: samples ranging from amino acids to proteinaceous objects such as silk, wool, parchment, and rabbit skin glue were irradiated; (2) synchrotron X-ray energy; (3) beam intensity; (4) irradiation time. Irradiated specimens were examined for both macroscopic and molecular effects. At macroscopic levels, color change, brittleness, and solubility enhancement were observed for several samples within 100 s of irradiation. At molecular levels, the method allowed one to quantify significant amino acid modifications. Aspartic acid (Asp), wool, parchment, and rabbit skin glue showed a significant increase in Asp racemization upon increasing irradiation time with rabbit skin glue showing the greatest increase in d-Asp formation. In contrast, Asp in silk, pure cystine (dimer of cysteine), and asparagine (Asn) did not show signs of racemization at the irradiation times studied; however, the latter two compounds showed significant signs of decomposition. Parchment and rabbit skin glue exhibited racemization of Asp, as well as racemization of isoleucine (Ile) and phenylalanine (Phe) after 100 s of irradiation with a focused beam. Under the experimental conditions and sample type and dimensions used here, more change was observed for focused and low energy (8 keV) beams than unfocused or higher energy (22 keV) beams. These results allow quantification of the change induced at the molecular level on proteinaceous specimens by synchrotron X-ray radiation and help to define accurate thresholds to minimize the probability of damage occurring to cultural heritage specimens. For most samples, damage was usually observed in the 1-10 s time scale, which is about an order of magnitude longer than SR studies of cultural heritage under X-ray fluorescence (XRF) mode; however, it is consistent with the duration of X-ray absorption spectroscopy (XAS) and microcomputed tomography (µCT) measurements.

Gamma irradiation induced modification of bean polysaccharides: impact on physicochemical, morphological and antioxidant properties.

In the present study starches from four bean varieties viz. red, yellow, black and white, were gamma irradiated in the dose range of 5-25 kGy to investigate the effect of radiation processing on physicochemical, morphological and antioxidant properties. Studies revealed positive correlation between gamma irradiation and solubility (r=0.91), irradiation and water absorption capacity (r=0.82) and negative correlations between irradiation and swelling power (r=-0.92), irradiation and pasting properties (r=-0.91) and irradiation and thermal properties (r=-0.89). Microscopic observation under scanning electron microscope indicated the development of surface cracking and fractures on the surface of starch granules with increase in dose. X-ray diffractometry revealed no significant change in diffraction patterns between control and irradiated starches, except a decrease in relative crystallinity. Irradiation increased the proportions of both rapidly digestible starch and enzyme resistant starch of bean starches and significantly prevented the retrogradation of bean starches during storage. Results of the DPPH radical scavenging activity and ferric reducing power indicated significant (p≤0.05) increase in antioxidant activity of all irradiated bean starches with increase in dose.

Dissolution and reconstitution of casein micelle containing dairy powders by high shear using ultrasonic and physical methods.

The effect of shear on the solubilization of a range of dairy powders was investigated. The rate of solubilization of low solubility milk protein concentrate and micellar casein powders was examined during ultrasonication, high pressure homogenization and high-shear rotor-stator mixing and compared to low-shear overhead stirring. The high shear techniques were able to greatly accelerate the solubilization of these powders by physically breaking apart the powder agglomerates and accelerating the release of individual casein micelles into solution. This was achieved without affecting the structure of the solubilized proteins. The effect of high shear on the re-establishment of the mineral balance between the casein micelles and the serum was examined by monitoring the pH of the reconstituted skim milk powder after prior exposure to ultrasonication. Only minor differences in the re-equilibration of the pH were observed after sonication for up to 3 min, suggesting that the localized high shear forces exerted by sonication did not significantly affect the mass transfer of minerals from within the casein micelles.

Physicochemical properties of peanut protein isolate-glucomannan conjugates prepared by ultrasonic treatment.

Peanut protein isolate (PPI) was glycated with glucomannan through classical heating or ultrasound treatment in this work. The physicochemical properties of PPI-glucomannan conjugates prepared by ultrasound treatment were compared to those prepared by classical heating. Compared with classical heating, ultrasound treatment could accelerate the graft reaction between PPI and glucomannan and improve the concentration of available free amino groups of PPI. Solubility and emulsifying properties of the conjugates obtained by ultrasound treatment were both improved as compared to those obtained by classical heating and native PPI. Decreases of lysine and arginine contents during the graft reaction indicated that these two amino acid residues attended the covalent linkage between PPI and glucomannan. Structural feature analyses suggested that conjugates obtained by ultrasound treatment had less α-helix, more ß-structures and random coil, higher surface hydrophobicity and less compact tertiary structure as compared to those obtained by classical heating and native PPI.

Photosolvolysis of bulky (4-hydroxyphenyl)naphthalene derivatives.

Six new naphthylphenols , bearing bulky hydroxymethyl substituents on the naphthalene, were synthesized and their photoreactivity was investigated by preparative irradiation, fluorescence measurements, and laser flash photolysis. All derivatives (in S1) undergo deprotonation of the phenolic OH in the aqueous solution. Also, fluorescence quenching with HClO4 in the pH range 2-4 indicates that can be protonated in S1. Formation of QMs most probably takes place sequentially, triggered by the phenol deprotonation. However, with the present data, a mechanism that involves simultaneous deprotonation and the loss of OH(-) cannot be ruled out. Photodehydration takes place only for , , and , delivering the corresponding QMs which react with nucleophilic solvents giving the corresponding photosolvolysis products. The other less likely option for the formation of the observed solvolysis products from , , and may involve some radical species. Photodehydration of and was not observed which may be due to the anticipated high energy of the corresponding sterically-congested and . The most efficient photosolvolyses were observed for the 2,6-substituted naphthalenes.

Photodegradation of levofloxacin in aqueous and organic solvents: a kinetic study.

The kinetics of photodegradation of levofloxacin in solution on UV irradiation in the pH range 2.0-12.0 has been studied using a HPLC method. Levofloxacin undergoes first-order kinetics in the initial stages of the reaction and the apparent first-order rate constants are of the order of 0.167 to 1.807×10-3 min-1. The rate-pH profile is represented by a curve indicating the presence of cationic, dipolar and anionic species during the reaction. The singly ionized form of the molecule is non-fluorescent and is less susceptible to photodegradation. The increase in the degradation rate in the pH range 5.0-9.0 may be due to greater reactivity of the ionized species existing in that range. The rate appears to vary with a change in the degree of ionization of the species present in a particular pH range and their susceptibility to photodegradation. Above pH 9, the decrease in the rate of photodegradation may be a result of deprotonation of the piperazinyl group. The levofloxacin molecule is more stable in the pH range around 7, which is then suitable for formulation purposes. The photodegradation of levofloxacin was found to be affected by the dielectric constant and viscosity of the medium.

Influence of microwave pre-treatment on sludge solubilization and pilot scale semi-continuous anaerobic digestion.

Anaerobic digestion is widely applied for the recovery of energy from waste activated sludge. Pre-treatment methods are of high interest to increase the biodegradability of the sludge and to enhance the digestion efficiency. This paper studies the application of a microwave pre-treatment. An experimental set-up of two pilot scale semi-continuous digesters was used. During a long term experiment, one of the reactors was fed with untreated sludge, while microwave pre-treated sludge (336 kJ/kg sludge) was introduced in the second one. A solid retention time of 20 days was kept during the experiments. (Organic) dry solids, carbohydrates, proteins and volatile fatty acids were monitored during digestion. It was seen that the microwave pre-treatment resulted in an effective solubilization of the organic matter in the sludge. The changes to the sludge composition resulted in an increase in biogas production by 50%, while the methane concentration in both reactors remained stable.