Porphyrin effect on the surface morphology of amphiphilic polymers as observed by atomic force microscopy

Complexes of porphyrin photosensitizers (PPS) with triblock copolymers of ethylene- and propylene oxide – Pluronics^® – exhibit markedly increased activity in the generation of singlet oxygen in aqueous media, as compared to pure porphyrins. Pluronics are amphiphilic polymers with surfactant properties suitable for a number of medical applications. PPS–Pluronic systems are considered as promising agents for photodynamic therapy which implies generation of singlet oxygen in the water-based human tissue.Importantly, Pluronics are capable of solubilization of not only water-soluble, but also hydrophobic PPS providing their transfer into the aqueous phase. It has been shown earlier that specific interactions of PPS with Pluronics must play a primary role for the photocatalytic properties of PPS–Pluronic systems. In the process of solubilization of a hydrophobic porphyrin by a Pluronic, both components are dissolved in an organic solvent, which is then removed, and the dry film is re-dissolved in water. Apparently, the initial binding between the porphyrin and the lipophilic part of the polymer takes place already at the stage of the film formation.We applied atomic force microscopy (AFM) to visualize structures formed by Pluronics upon their interactions with meso-tetraphenylporphyrin (TPP). We studied the surface structure of Pluronics^® F87, F108 and F127 crystallized alone or together with TPP on silicon substrates from chloroform solutions. We found Pluronics to form similar dendritic structures independently of their molecular weight and degree of hydrophobicity. In the presence of TPP, though, we observed formation of distinct convex structures on top of the Pluronic dendrites. These structures appeared to consist of multiple flat layers placed on top of each other. Their sizes varied among the three Pluronics. We believe that TPP aggregates interact with the hydrophobic units of Pluronics causing the polymer chains to pack themselves in a distinct manner around those TPP-containing “cores”. These interactions apparently direct formation of complexes between the porphyrin and the polymer upon their dissolution in water, thus resulting in the encapsulation of TPP aggregates inside a Pluronic micelle. A single mechanism for the TPP solubilization by Pluronics is consistent with the same catalytic activity of the three TPP–Pluronic systems observed in the photooxidation of tryptophan.     

Imidazole derivatives as absorption probes for pluronics core-shell aggregates micropolarity investigation

Using the absorption probes 1-H-imidazol-1-yloxy-4,5-dihydro-4,4,5,5-tetramethyl-2-ethyl-3-oxide, 1-H-imidazol-1-yloxy-4,5-dihydro-4,4,5,5-tetramethyl-2-nitrophenyl-3-oxide, and 1-H-imidazol-1-yloxy-4,5-dihydro-4,4,5,5-tetramethyl-2-undecyl-3-oxide, the micropolarity of micellar aggregates formed in aqueous solutions of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymers, Pluronics L62, L64, and F127, as well as in reverse micellar systems of F127/butanol/water, has been investigated These absorption probes have different hydrophilic/hydrophobic features and solvatochromic properties. Their specific absorption parameters, sensitive to changes in micropolarity, were calibrated using the reference curves carried out in homogeneous tetraethyleneglycol/water mixtures. The probes were able to detect changes in the micelle micropolarity induced by hydration. Thus, with the help of calibration solutions, the effective local hydration of the polymeric chain sensed by the molecular probe solubilized in the guest aggregate was quantified and hypothetical relative locations of the probes in micelles have been proposed. The probes evidence differences in the micropolarity function of the structure (nature) and concentration of the Pluronic block copolymers.     

Effects of Poly(Propylene Oxide)–Poly(Ethylene Oxide)–Poly(Propylene Oxide) Triblock Copolymer on the Gelation of Poly(Ethylene Oxide)–Poly(Propylene Oxide)–Poly(Ethylene Oxide) Aqueous Solutions

Poly(ethylene oxide)-poly(propylene oxide)–poly(ethylene oxide) ((EO)_n–(PO)_m–(EO)_n) block copolymers, commercially available as Pluronics (BASF Corp.) and Poloxamers (ICI Corp.), have been widely applied in medicine, biochemistry, and other fields because of their ability to form reversible micelles and physical gels in aqueous solution. Generally, for PEO–PPO–PEO block copolymers with higher ethylene oxide concentration, the micellization and gelation in aqueous solution are easier. However, if we introduce the reverse block copolymer PPO–PEO–PPO into PEO–PPO–PEO aqueous solutions, the micellization and gelation of the system will be more complex. In this work, the reverse block copolymer PO₁₄–EO₂₄–PO₁₄ (17R4) was added to the Pluronics EO₂₀–PO₇₀–EO₂₀ (P123), EO₁₀₀–PO₆₅–EO₁₀₀ (F127), and EO₁₃₃–PO₅₀–EO₁₃₃ (F108) aqueous solutions with different molar ratios. The rheological properties of different mixtures were measured to study the additive effect on the gelation behavior. The sol–gel transition temperature of the P123, F127, and F108 solutions shifted to a higher temperature when 17R4 was added to the solutions. In addition, the existence of 17R4 greatly affected the stability of gels. These results help to better understand the gelation of Pluronic aqueous solutions.     

Peculiarities of pluronic crystallization in thin films

The peculiarities of the crystallization of Pluronics from chloroform and aqueous polymer solution on mica surfaces are investigated with the atomic force microscopy method. It is shown that Pluronics in thin films form quasi two-dimensional crystalline structures of 10–12 nm thickness. Pluronic crystallization proceeds predominantly via the mechanism of diffusion-limited aggregation with the formation of dendrites. Three main morphological types of formed structures are identified including two types of dendrites (with 45° and 90° angles between branches) and elongated “needles.” It is shown that the film morphology depends on the polymer concentration, rate of solvent evaporation, and, probably, local gradients of concentration and temperature. Interaction with porphyrins establishes conditions for the local three-dimensional crystallization of Pluronics.     

Tailoring the wettability of nanocrystalline TiO2 films

The water contact angle (WCA) of nanocrystalline TiO₂ films was adjusted by fluoroalkylsilane (FAS) modification and photocatalytic lithography. FAS modification made the surface hydrophobic with the WCA up to ∼156°, while ultraviolet (UV) irradiation changed surface to hydrophilic with the WCA down to ∼0°. Both the hydrophobicity and hydrophilicity were enhanced by surface roughness. The wettability can be tailored by varying the concentration of FAS solution and soaking time, as well as the UV light intensity and irradiation time. Additionally, with the help of photomasks, hydrophobic-hydrophilic micropatterns can be fabricated and manifested via area-selective deposition of polystyrene particles.     

A simple swelling and anchoring method for preparing dense and stable poly(ethylene oxide) layers on polystyrene surfaces

In order to obtain dense and stable poly(ethylene oxide) (PEO) layers for reducing protein adsorption, polystyrene (PS) plates were first soaked in chloroform/methanol mixed organic solvent to swell the polymer. The swelled PS plates were then immersed into Pluronic F127 (amphiphilic block copolymer) aqueous solution, Pluronic F127 molecules were adsorbed favorably on the swelled PS surfaces. After evaporation of organic solvent, the adsorbed Pluronic F127 molecules were trapped and anchored permanently on the PS substrates. The dense and stable PEO layers anchored on the PS surfaces can effectively inhibit protein adsorption.     

Development of novel formulations for photodynamic therapy on the basis of amphiphilic polymers and porphyrin photosensitizers. Porphyrin-polymer complexes in model photosensitized processes

We have studied the effect of amphiphilic polymers with different structure (polyvinylpyrrolidone, polyethyleneoxide and a triblock copolymer of ethylene- and propyleneoxide—(Pluronic F127)) on the photoactivity of a hematoporphyrin derivative (dimegin). It has been shown that such polymers can cause a considerable increase in the porphyrin photosensitizer (PPS) activity both in the process of singlet oxygen photogeneration and in the reaction of a substrate photooxidation in D2O and water. Among the studied polymers, polyvinylpyrrolidone appeared to have a most significant influence onto the photoactivity of dimegin. We attribute the observed effect of the amphiphilic polymers on the photoactivity of dimegin to the presence of polymer-porphyrin interactions resulting in the porphyrin disaggregation in aqueous phase. Using 1H NMR spectroscopy, we have found that dimegin binds to the polymers via the PPS interaction mainly with the hydrophobic fragments of polymeric macromolecules. However, in the case of polyvinylpyrrolidone we observed also PPS interactions with the hydrophilic fragments of macromolecules.     

Small angle neutron scattering study on the aggregation behaviour of PEO-PPO-PEO copolymers in the presence of a hydrophobic diol

Small angle neutron scattering (SANS) measurements on aqueous solutions of four polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymers (commercially known as Pluronic®)F88, P85, F127 and P123 in the presence of hydrophobic C14Diol (also known as Surfynol® 104) reveal information on micellization, micellar size and micellar transitions. While most hydrophilic F88 (with least PPO/PEO ratio) remained unimers in water at 30°C, other copolymers formed micellar solutions. Surfynol® 104 is sparingly soluble in water to only about ～0.1 wt%, but on addition to pluronic solution, it gets incorporated in the micellar region of block copolymer which leads to increase in aggregation number and transformation of spherical to ellipsoidal micelles. The added diol-induced micellization in F88, though hydrophilic copolymers F88 and F127 did not show any appreciable micellar growth or shape changes as observed for P85 and P123 (which are comparatively more hydrophobic). The SANS results on copolymer pairs with same molecular weight PPO but different % PEO (viz. F88 and P85, F127 and P123) and with same molecular weight PEO but different PPO (F88 and F127) reveal that the copolymer with large PPO/PEO ratio facilitate micellar transition in the presence of diol. An increase in temperature and presence of added electrolyte (sodium chloride) in the solution further enhances these effects. The micellar parameters for these systems were found out using available software and are reported.     

Study of PEO—PPO—PEO Copolymers Conformational Changes: Viscosity and Dynamic Light Scattering Measurements

The self-assembly behaviour of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly (ethylene oxide) copolymers, (EO)₁₃(PO)₃₀(EO)₁₃ (Pluronic L64), and (EO)₇₀ (PO)₃₀(EO)₇₀ (Pluronic F68) in water and in p-xylene has been elucidated by using viscosity and dynamic light scattering measurements to investigate the effects of hydrophilic chains length on their conformational changes. The viscosity measurements were performed for a range of temperature varying from 27°C to 60°C and concentration from 4 to 60 mg/ml. The variation of the viscosity and the conformational changes in aqueous solution depends on the kinds of interactions and the balance between excluded volume effects and hydrophobic interactions. Some dynamic light scattering measurements were also performed at room temperature for the same range of concentration to provide more information on the micellar structures in aqueous and organic solution.     

硫和银共掺杂介孔TiO2的制备、表征及其对染料的光催化降解活性

以P123为模板,以钛酸四正丁酯、硝酸银和硫脲为原料采用模板法制备了一系列硫和银共掺杂介孔TiO₂光催化材料．利用SEM、XRD、BET和紫外-可见光谱等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征．以甲基橙溶液的光催化降解为模型反应,考察了不同掺杂量的样品在紫外和可见光下的光催化性能．结果表明,用模板法制备的共掺杂介孔TiO₂光催化材料在紫外和可见光条件下较纯介孔TiO₂和单掺杂介孔TiO₂对甲基橙溶液具有更好的光催化降解效果, 且硫和银的掺杂量及样品焙烧温度显著影响该材料的催化性能．当硫掺杂量为2mol%和银掺杂量为1mol%,在500 oC 焙烧2 h所得光催化材料的催化性能最佳,4 h即可使甲基橙的降解率达98.8%,重复使用4次仍可使甲基橙的降解率保持在87.5%以上     

Preparation and photocatalytic properties of platelike NaNbO3 based photocatalysts

Two kinds of plate-like NaNbO₃ were separately prepared by the one- and two-step molten salt processes via topochemical micro-crystal conversion methods. Meanwhile, the composite photocatalysts were obtained via heating the mixture of corresponding NaNbO₃ powders and urea. Their photocatalytic activities were evaluated from the photodegradation of Rhodamine B under full arc and visible light irradiation of Xe lamp. The sample containing NaNbO₃ prepared by the one-step molten salt process and carbon nitride displays the highest activity. The enhancement of photocatalytic activity was attributed to the surface properties and the state of the carbon nitride.     

Co-precipitation of asiatic acid and poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) using rapid expansion of subcritical solutions into liquid solvents

Poly(l-lactide) (PLLA) nanoparticles loaded with asiatic acid (AA) were successfully produced by rapid expansion of a subcritical solution into an aqueous receiving solution containing a dispersing agent. A mixture of carbon dioxide (CO₂) and ethanol (EtOH) with a weight ratio of 1:1 was used as the solvent for AA and PLLA. Two surfactants, Pluronic F127 and sodium dodecyl sulfate were employed. The former was found to be more effective for stabilizing AA-loaded PLLA nanoparticles, as a rapid expansion into a 0.1 wt% Pluronic F127 solution produced a stable nanosuspension consisting mainly of well-dispersed, individual nanoparticles. The effects of rapid expansion-processing conditions—AA to PLLA weight ratio and pre-expansion temperature (T_pre)—on the size and morphology of composite nanoparticles, and the loading capacity and entrapment efficiency of AA in PLLA nanoparticles, were systematically investigated. It was found that AA-loaded PLLA nanoparticles with a size range of 30–100 nm were consistently fabricated by rapid expansion at T_pre of 70–100 °C and AA to PLLA weight ratios of 1:2 and 1:4, and with a constant pre-expansion pressure of 330 bar. The T_pre and AA to PLLA weight ratio had no significant effects on the size of the nanoparticles. The AA to PLLA weight ratio is a controlling parameter for both the loading capacity and the entrapment efficiency of AA in PLLA nanoparticles. The loading capacity and entrapment efficiency increased from 8–11 to 16–21 wt%, and 38–57 to 50–62 wt%, respectively, when the AA to PLLA weight ratio changed from 1:4 to 1:2. However, increasing the T_pre from 70 to 100 °C decreased both the loading capacity and entrapment efficiency of AA in PLLA nanoparticles by ~20–30%.     

Synergetic effects of hydrophilic surface modification and N-doping for visible light response on photocatalytic activity of TiO2

We made attempts to improve photocatalytic activity of TiO₂ nanoparticles under visible light exposure by combining additional treatments. N-doping of TiO₂ by ammonia gas treatment increased absorbance of visible light. By coating thin film of polydimethylsiloxane, and subsequently vacuum-annealing, TiO₂ surface became more hydrophilic, thereby enhancing photocatalytic activity of TiO₂. These two treatments were combined for the first time in this work and photocatalytic activity under visible light irradiation exceeded sum of individual effects of N-doping and hydrophilic modification.     

Electrospun polystyrene fibres on TiO<Subscript>2</Subscript> nanostructured film to enhance the hydrophobicity and corrosion resistance of stainless steel substrates

A dual layer of dip-coated TiO₂ film (top layer) and electrospun polystyrene (bottom layer) was coated on stainless steel (SS) substrates. The morphological and structural studies were performed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Their hydrophobicity and corrosion resistance were also investigated using contact angle (CA) and electrochemical corrosion tests in acidic and salt solutions, respectively. Contact angle results showed that the naturally hydrophilic TiO₂/SS sample (CA ～ 66^°) turned into a superhydrophic surface (CA ～ 148^°) when it was covered by polystyrene fibres (PS /TiO₂ /SS). This observation can be attributed to the intrinsic hydrophobicity of organic polystyrene fibres (due to their low surface energy) and also to the existence of trapped air bubbles between fibres. Electrochemical corrosion tests showed that the corrosion rate was substantially decreased by using a protective bilayer (PS /TiO₂) from 33 to 0.39 mV /y for bare SS sample and from 0.01 to 0.003 mV /y for PS /TiO₂ /SS sample in 1 M salt and acidic solutions, respectively. The superhydrophobic protective layer forms an obstacle against ionic exchange interactions. Therefore, it slows down the breaking of the surface oxidic layer on the metal substrate and prevents the metallic surface underneath from further corrosion.     

Hydrophobic Functionalization of ZnO Nanosheets by In Situ Center‐Substituted Synthesis for Selective Photocatalysis under Visible Irradiation

The selective degradation of specific substances in mixed contaminants is quite challenging. And a general approach for sensitized oxide semiconductor relies on dip‐coating method with sensitizer. Here, hydrophilic 2D, nest‐like architecture ZnO (ZnO NA) was hydrophobicly functioned by monomolecular–layer tetraphenylporphyrin zinc (ZnTPP), where ZnTPP was synthesized by means of an in situ center‐substituted (ISCS) process., i.e., the hydrogen atoms in the core of metal‐free tetraphenylporphyrin (H₂TPP) are substituted by the unsaturated zinc ions in ZnO NAs. ZnTPP/ZnO NA was exhibited with significant hydrophobicity, benefitting to absorb hydrophobic phenol (PL). Further, it is realized to selectively photodegradate PL in the mixture by ZnTPP/ZnO NAs under visible irradiation. Note that the rate of degradation to hydrophobic PL by ZnTPP/ZnO NA is 9.17 times of that for ZnO NA within 150 min; on the contrary, the degradation rate of hydrophilic rhodamine B (RhB) by ZnTPP/ZnO is reduced by 40%. Radiative lifetime of photogenerated charges is obviously increased by ZnTPP/ZnO NA compared with that of ZnTPP, indicating the effective charge separation for ZnTPP/ZnO NAs. In addition, ZnTPP/ZnO NA produced more superoxide radicals (·O₂^?) in comparison to ZnO NA. With surface functionalization, the feasibility of selective photocatalysis under visible irradiation is demonstrated.     

Enhanced photoactivity of CuPp-TiO2 photocatalysts under visible light irradiation

Three novel porphyrins, 5,10,15-tri-phenyl-20-[4-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-phenyl-10,20-di-[4-(3-phenoxy)-propoxy]phenyl porphyrin and 5-phenyl-10,15,20-tri- [4-(3-phenoxy)-propoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and characterized spectroscopically. The photocatalytic effects of TiO₂ samples impregnated with copper(II) porphyrins was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution under visible light. The photocatalysts were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectra and FT-IR spectra. The results indicated that CuPps were successfully loaded and interacted with the surface of TiO₂ microsphere, which is crucial to enhance the activity of the catalytic composite under visible light.     

Improved aging performance of vapor phase deposited hydrophobic self-assembled monolayers

A hydrophobic self-assembled monolayer (SAM) of fluoro-octyl-trichloro-silane (FOTS) was deposited on silicon using a vapor phase technique. The aging of the hydrophobic layer was examined using water contact angle measurements. It has been found that while such monolayer films suffer from a loss of hydrophobicity with time, pre-immersion nitrogen annealing can significantly improve the aging characteristics of these monolayers. The effect of nitrogen annealing on the improved aging properties of SAM coatings has been investigated by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The hydrolytic stability and the effect of nitrogen annealing were studied by morphological evolution during immersion. A spontaneous formation of silane mounds on the surface of the monolayers was found by AFM. These mounds have been irreversibly transformed from initially uniform hydrophobic surface layers. It is highly probable that the compliance of these mounds can reasonably allow hydrophilic sites to be located around the mounds. Interestingly, the density of these mounds formation is very less on the annealed samples. XPS reveals a higher level of coverage by the N₂-annealed film due to agglomeration. A relative abundance of CF₃ and CF₂ moieties in the annealed film may explain the enhancement of the hydrophobicity as revealed by higher level of water contact angle. This hydrophobicity was found to be significantly stable in water. This novel finding explains the improved hydrophobic stability of FOTS monolayers as primarily a morpho-chemical effect that originates from the densification of the monolayers upon annealing.     

A facile route for rapid synthesis of cubic mesoporous silica

Ordered SBA-16-type mesoporous silica materials (MSMs) have been rapidly synthesized under weak acidic media in the presence of phosphomolybdic acid (abbreviated to HPMo) and inorganic salts (NaCl, Na₂SO₄, KCl and K₂SO₄) by using nonionic triblock copolymer F127 as a structure directing agent and tetraethylorthosilicate (TEOS) as a silica source. Both HPMo and inorganic salts play a crucial role in promoting SBA-16-type MSMs formation, and the reaction products have still retained an ordered body-centered cubic (Im3m) mesostructure after treated with 100 °C water for 120 h. The high hydrothermal stability of reaction products might be attributed to the higher degree of polymerization and condensation of silanol groups, arisen from the synergistic effect of rapid nucleation with the aid of HPMo and salt effect during the crystallization process.     

Europium-doped mesoporous anatase with enhanced photocatalytic activity toward elimination of gaseous methanol

Mesoporous anatase doped with various amounts of Eu were synthesized via a sol-gel route using Pluronic P123 as template. The XRD and TEM results show that Eu doping favors the formation of anatase with smaller crystal size. The photocatalytic activity of the mesoporous anatase was tested in photocatalytic elimination of gaseous methanol. The photocatalysts exhibited higher activity than that of the commercial photocatalyst (Degussa, P25) under either ultraviolet or visible light irradiation. The superior activity of the mesoporous anatase may be attributed to the synergic effects of the surface area, crystal size and doped Eu species.     

The effect of ultrasound treatment on the interaction of brine with pork meat proteins

The objective of the study is to elucidate the effect of ultrasound treated salt solution on curing of pork meat. The interactions of salt (NaCl) solutions of 3 and 25% with the proteins of pork meat are studied. High intensity ultrasound operating at 20 kHz was used. The differential scanning calorimetry (DSC), NMR spin-spin relaxation time, unfrozen water and water diffusion coefficient measurements were carried out in meat cured with ultrasound treated and untreated salt solutions. The effect of ultrasonication was most evident from measured spin-spin relaxation times T₂₁, the rate of chemical exchange of water protons k and the amount of unfrozen water W_unf in the meat. The measured diffusion coefficient of water D_w in meat cured with ultrasound treated and control salt solution did not show significant difference. The nuclear magnetic resonance (NMR) relaxation data, differential scanning calorimetry (DSC) and the diffusion coefficient data reliably show that the possible action of ultrasound to salt solution was manifested on the first 2 days of the experiment with a 3% salt solution.