2-Cyanopropan-2-yl versus 1-Cyanocyclohex-1-yl Leaving Group: Comparing Reactivities of Symmetrical Trithiocarbonates in RAFT Polymerization.

This study introduces bis(1-cyanocyclohex-1-yl)trithiocarbonate (TTC-bCCH) as a novel trithiocarbonate chain transfer agent and compares its reactivity with the previously described bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St), n-butyl acrylate (nBA), and methyl methacrylate (MMA). Significant findings include the effective control of Mn and low dispersities from the onset of polymerization of St and nBA showing swift addition-fragmentation kinetics, leading to similar behaviors between the two RAFT agents. In contrast, a fourfold decrease of the chain transfer constant to MMA is established for TTC-bCCH over TTC-bCP. This trend is confirmed through density functional theory (DFT) calculations. Finally, the study compares thermoplastic elastomer properties of all-(meth)acrylic ABA block copolymers produced with both RAFT agents. The impact of dispersity of PMMA blocks on thermomechanical properties evaluated via rheological analysis reveals a more pronounced temperature dependence of the storage modulus (G') for the triblock copolymer synthesized with TTC-bCCH, indicating potential alteration of the phase separation.

Bioinspired zwitterionic triblock copolymers designed for colloidal drug delivery: 2 - Biological evaluation.

In this work, poly(lactide) nanoparticles were equipped with a bioinspired coating layer based on poly[2-(methacryloyloxy)ethyl phosphorylcholine] and then evaluated when administered to the lungs and after intravenous injection. Compared to the plain counterparts, the chosen zwitterionic polymer shell prevented the coated colloidal formulation from aggregation and conditioned it for lower cytotoxicity, protein adsorption, complement activation and phagocytic cell uptake. Consequently, no interference with the biophysical function of the lung surfactant system could be detected accompanied by negligible protein and cell influx into the bronchoalveolar space after intratracheal administration. When injected into the central compartment, the coated formulation showed a prolonged circulation half-life and a delayed biodistribution to the liver. Taken together, colloidal drug delivery vehicles would clearly benefit from the investigated poly[2-(methacryloyloxy)ethyl phosphorylcholine]-based polymer coatings.

Bioinspired zwitterionic triblock copolymers designed for colloidal drug delivery: 1 - Synthesis and characterization.

This study describes the synthesis and characterization of triblock copolymers composed of poly[2-(methacryloyloxy)ethyl phosphorylcholine]-block-poly(propylene glycol)-block-poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC-b-PPG-b-PMPC) intended for, but not limited to, applications in colloidal drug delivery. Atom transfer radical polymerization led to a library of well-defined PMPC-b-PPG-b-PMPC triblock copolymers with varying overall molecular weight (ranging from ∼5 to ∼25 kDa) and composition (weight fraction of the hydrophobic PPG block ranged from ∼10 to ∼50 wt%). The properties of the synthesized triblock copolymers were linked to the PPG to bioinspired PMPC block(s) ratio, where the more hydrophilic species showed adequate aqueous solubility, surface activity and biocompatibility (non-toxicity) in in vitro cell culture. Their amphiphilic nature makes them adsorb efficiently onto polymer nanoparticles, what improves colloidal stability under stress conditions and, furthermore, depletes proteins from unwanted adsorption to the underlying surface. The current findings strengthen our insights into structure-function relationships of PMPC-based coatings leading to protecting shells on relevant polymer nanoparticle formulations. PMPC-b-PPG-b-PMPC triblock copolymers composed of a hydrophobic PPG block of 2-4 kDa flanked by two hydrophilic PMPC blocks each of 5-10 kDa seem to be most promising to enhance colloidal drug delivery vehicles.

Ursolic acid loaded tri-block copolymer nanoparticles based on triphenylphosphine for mitochondria-targeted cancer therapy.

A novel biodegradable amphiphilic triblock copolymer, polyphosphate, polyethylene glycol, and polylactic acid (PAEEP-PEG-PLLA), was synthesized by twice ring-opening polymerization and triphenylphosphine (TPP) was grafted onto the block copolymer to synthesize a carrier material TPP-PAEEP-PEG-PLLA, which was identified by1H-nuclear magnetic resonance (1H-NMR) spectroscopy. The TPP-PAEEP-PEG-PLLA nanoparticles encapsulated with ursolic acid (UA) were prepared by the emulsion-solvent evaporation method and characterized by dynamic light scattering. The mitochondrial targeting ability of fluorescently labeled nanoparticles was evaluated by laser confocal microscopy. The average particle size and surface charge of the UA -loaded nanoparticle solution were 180.07 ± 1.67 nm and +15.57 ± 1.33 mV, respectively. The biocompatibility of nanoparticles was briefly evaluated by erythrocyte hemolysis assay.In vitrocell proliferation assay and scratch migration assay were performed to compare the difference in anti-tumor effect between UA and UA nanoparticles. The results showed that TPP-modified triblock copolymers had good mitochondrial targeting and improved the low bioavailability of UA, and UA nanoparticles exhibited more pronounced anti-tumor capabilities. In summary, the results suggested that our UA nanoparticles were a promising drug-targeted delivery system for the treatment of tumors.

Comparing PVP and Polymeric Micellar Formulations of a PEGylated Photosensitizing Phthalocyanine by NMR and Optical Techniques.

Phthalocyanines are ideal candidates as photosensitizers for photodynamic therapy (PDT) of cancer due to their favorable chemical and photophysical properties. However, their tendency to form aggregates in water reduces PDT efficacy and poses challenges in obtaining efficient forms of phthalocyanines for therapeutic applications. In the current work, polyvinylpyrrolidone (PVP) and micellar formulations were compared for encapsulating and monomerizing a water-soluble zinc phthalocyanine bearing four non-peripheral triethylene glycol chains (Pc1). 1H NMR spectroscopy combined with UV-vis absorption and fluorescence spectroscopy revealed that Pc1 exists as a mixture of regioisomers in monomeric form in dimethyl sulfoxide but forms dimers in an aqueous buffer. PVP, polyethylene glycol castor oil (Kolliphor RH40), and three different triblock copolymers with varying proportions of polyethylene and polypropylene glycol units (termed P188, P84, and F127) were tested as micellar carriers for Pc1. 1H NMR chemical shift analysis, diffusion-ordered spectroscopy, and 2D nuclear Overhauser enhancement spectroscopy was applied to monitor the encapsulation and localization of Pc1 at the polymer interface. Kolliphor RH40 and F127 micelles exhibited the highest affinity for encapsulating Pc1 in the micellar core and resulted in intense Pc1 fluorescence emission as well as efficient singlet oxygen formation along with PVP. Among the triblock copolymers, efficiency in binding and dimer dissolution decreased in the order F127 > P84 > P188. PVP was a strong binder for Pc1. However, Pc1 molecules are rather surface-attached and exist as monomer and dimer mixtures. The results demonstrate that NMR combined with optical spectroscopy offer powerful tools to assess parameters like drug binding, localization sites, and dynamic properties that play key roles in achieving high host-guest compatibility. With the corresponding adjustments, polymeric micelles can offer simple and easily accessible drug delivery systems optimizing phthalocyanines' properties as efficient photosensitizers.

Effect of 3-Carene and the Micellar Formulation on Leishmania (Leishmania) amazonensis.

Leishmaniases are neglected tropical diseases caused by obligate intracellular protozoa of the genus Leishmania. The drugs used in treatment have a high financial cost, a long treatment time, high toxicity, and variable efficacy. 3-Carene (3CR) is a hydrocarbon monoterpene that has shown in vitro activity against some Leishmania species; however, it has low water solubility and high volatility. This study aimed to develop Poloxamer 407 micelles capable of delivering 3CR (P407-3CR) to improve antileishmanial activity. The micelles formulated presented nanometric size, medium or low polydispersity, and Newtonian fluid rheological behavior. 3CR and P407-3CR inhibited the growth of L. (L.) amazonensis promastigote with IC50/48h of 488.1 ± 3.7 and 419.9 ±1.5 mM, respectively. Transmission electron microscopy analysis showed that 3CR induces multiple nuclei and kinetoplast phenotypes and the formation of numerous cytosolic invaginations. Additionally, the micelles were not cytotoxic to L929 cells or murine peritoneal macrophages, presenting activity on intracellular amastigotes. P407-3CR micelles (IC50/72 h = 0.7 ± 0.1 mM) increased the monoterpene activity by at least twice (3CR: IC50/72 h >1.5 mM). These results showed that P407 micelles are an effective nanosystem for delivering 3CR and potentiating antileishmanial activity. More studies are needed to evaluate this system as a potential therapeutic option for leishmaniases.

Reversible Thermo-Optical Response Nanocomposites Based on RAFT Symmetric Triblock Copolymers (ABA) of Acrylamide and N-Isopropylacrylamide and Gold Nanoparticles.

The development of composite materials with thermo-optical properties based on smart polymeric systems and nanostructures have been extensively studied. Due to the fact of its ability to self-assemble into a structure that generates a significant change in the refractive index, one of most attractive thermo-responsive polymers is poly(N-isopropylacrylamide) (PNIPAM), as well as its derivatives such as multiblock copolymers. In this work, symmetric triblock copolymers of polyacrylamide (PAM) and PNIPAM (PAMx-b-PNIPAMy-b-PAMx) with different block lengths were prepared by reversible addition-fragmentation chain-transfer polymerization (RAFT). The ABA sequence of these triblock copolymers was obtained in only two steps using a symmetrical trithiocarbonate as a transfer agent. The copolymers were combined with gold nanoparticles (AuNPs) to prepare nanocomposite materials with tunable optical properties. The results show that copolymers behave differently in solution due to the fact of variations in their composition. Therefore, they have a different impact on the nanoparticle formation process. Likewise, as expected, an increase in the length of the PNIPAM block promotes a better thermo-optical response.

Formation of Size-Controllable Tetragonal Nanoprisms by Crystallization-Directed Ionic Self-Assembly of Anionic Porphyrin and PEO-Containing Triblock Cationic Copolymer.

The creation of anisotropic nanostructures with precise size control is desirable for new properties and functions, but it is challenging for ionic self-assembly (ISA) because of the non-directional electrostatic interactions. Herein, the formation of size-controllable tetragonal nanoprisms is reported via crystallization-directed ionic self-assembly (CDISA) through evaporating a micellar solution on solid substrates. First, ISA is designed with a crystalline polyethylene oxide (PEO) containing cationic polymer poly(2-(2-guanidinoethoxy)ethyl methacrylate)-b-poly(ethyleneoxide)-b-poly(2-(2-guanidinoethoxy)-ethylmethacrylate) (PGn -PEO230 -PGn ) and an anionic 5,10,15,20-Tetrakis(4-sulfonatophenyl) porphyrin (TPPS) to form micelles in aqueous solution. The PG segments binds excessive TPPS with amplenet chargeto form hydrophilic corona, while the PEO segments are unprecedentedly dehydrated and tightly packed into cores. Upon naturally drying the micellar solution on a silicon wafer, PEO crystallizationdirects the micelles to aggregate into square nanoplates, which are further connected to nanoprisms. Length and width of the nanoprisms can be facilely tuned by varying the initial concentration. In this hierarchical process, the aqueous self-assembly is prerequisite and the water evaporation rate is crucial for the formation of nanostructures, which provides multiple factors for morphology regulating. Such precise size-control strategy is highly expected to provide a new vision for the design of advanced materials with size controllable anisotropic nanostructures.

Polymorphic Crystallization Behavior of a Poly(butylene adipate) Midblock within a Poly(L-lactide-butylene adipate-L-lactide) Triblock Copolymer.

New biodegradable aliphatic PLLA-PBA-PLLA copolymers with soft poly(butylene adipate) (PBA) and hard poly(l-lactide) (PLLA) building blocks were synthesized via ring-opening polymerization (ROP). Proton nuclear magnetic resonance (1HNMR) was utilized to confirm the volume fraction of PBA (fPBA) within PLLA-PBA-PLLA. It was found that a PBA midblock (PBA-mid) within PLLA-PBA-PLLA-s (PLLA-PBA-PLLA triblock copolymer with a short PLLA block length) might display lamellar domain structure. However, PBA-mid within PLLA-PBA-PLLA-l (PLLA-PBA-PLLA triblock copolymer with a long PLLA block length) might locate itself as a nanoscale cylindrical domain surrounded by a PLLA continuous phase. Polymorphic crystals of PBA-mid within the PLLA-PBA-PLLA copolymers were formed after melt crystallization at the given temperatures, which were studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis. According to the WAXD and DSC analyses, it was interesting to find that the α-type crystal of PBA-mid was favorable to develop in the lower temperature region regardless of the state (crystallization or amorphous) of the PLLA component. Additionally, when the PLLA component was held in its amorphous state, it was easier for PBA-mid within the PLLA-PBA-PLLA copolymers to transform from the metastable ß-form crystal to the stable α-form crystal. Furthermore, polarized optical microscopy (POM) photos provided direct evidence of the polymorphic crystals of PBA-mid within PLLA-PBA-PLLAs.

Skeletal Muscle Fibers Inspired Polymeric Actuator by Assembly of Triblock Polymers.

Inspired by the striated structure of skeletal muscle fibers, a polymeric actuator by assembling two symmetric triblock copolymers, namely, polystyrene-b-poly(acrylic acid)-b-polystyrene (SAS) and polystyrene-b-poly(ethylene oxide)-b-polystyrene (SES) is developed. Owing to the microphase separation of the triblock copolymers and hydrogen-bonding complexation of their middle segments, the SAS/SES assembly forms a lamellar structure with alternating vitrified S and hydrogen-bonded A/E association layers. The SAS/SES strip can be actuated and operate in response to environmental pH. The contraction ratio and working density of the SAS/SES actuator are approximately 50% and 90 kJ m-3 , respectively; these values are higher than those of skeletal muscle fibers. In addition, the SAS/SES actuator shows a "catch-state", that is, it can maintain force without energy consumption, which is a feature of mollusc muscle but not skeletal muscle. This study provides a biomimetic approach for the development of artificial polymeric actuators with outstanding performance.

Separation performance of pentiptycene-functionalized triblock copolymers towards the isomers of xylenes, phenols and anilines and the complex components in essential oil.

This work presents the investigation of two new pentiptycene (PP)-functionalized triblock copolymers (PEPE1, PEPE2) for gas chromatographic (GC) analyses with an aim to address the separation problems toward analytes of high resemblance in properties and a wide variety of components in complex samples. Up to date, these two materials are not reported in any fields. The PEPE1 and PEPE2 columns showed close column efficiency (above 4000 plates/m) but differed in polarity, morphology and separation performance. As testified by the challenging Grob test mixture, the PEPE1 column exhibited comprehensively higher separation capability than the PEPE2 column and the commercial reference columns. Also, the PEPE1 column achieved high-resolution performance for both apolar and polar isomers of high resemblance, such as xylenes, phenols and anilines. Moreover, it displayed high inertness towards carboxylic acids and excellent separation repeatability and reproducibility tested by the aniline isomers with the RSD values in the range of 0.01-0.04% for run-to-run, 0.09-0.13% for day-to-day and 1.2-2.0% for column-to-column, respectively. Its application to GC-MS analysis of the essential oil from tea flowers demonstrated its advantageous separation performance towards a wide range of components and proved its feasibility for practical analyses of complex samples.

One-Step Synthesis of Lignin-Based Triblock Copolymers as High-Temperature and UV-Blocking Thermoplastic Elastomers.

This work utilizes frustrated Lewis pairs consisting of tethered bis-organophosphorus superbases and a bulky organoaluminum to furnish the highly efficient synthesis of well-defined triblock copolymers via one-step block copolymerization of lignin-based syringyl methacrylate and n-butyl acrylate, through di-initiation and compounded sequence control. The resulting thermoplastic elastomers (TPEs) exhibit microphase separation and much superior mechanical properties (elongation at break up to 2091 %, tensile strength up to 11.5 MPa, and elastic recovery up to 95 % after 10 cycles) to those of methyl methacrylate-based TPEs. More impressively, lignin-based tri-BCPs can maintain TPEs properties up to 180 °C, exhibit high transparency and nearly 100 % UV shield, suggesting potential applications in temperature-resistant and optical devices.

Dendrimer-Based Polyion Complex Vesicles: Loops Make Loose.

Associations of amphiphiles assume their various morphologies according to the so-called packing parameter under thermodynamic control. However, one may raise the question of whether polymers can always relax fast enough to obey thermodynamic control, and how this may be checked. Here, a case of polyion complex (PIC) assemblies where the morphology appears to be subject to kinetic control is discussed. Poly (ethylene oxide)-b-(styrene sulfonate) block copolymers are combined with cationic PAMAM dendrimers of various generations (2-7). The PEO-PSS diblocks, and the corresponding PSS-PEO-PSS triblocks should have nearly identical packing parameters, but surprisingly creat different assemblies, namely core-shell micelles and vesicles, respectively. Moreover, the micelles are very stable against added salt, whereas the vesicles are not only much more sensitive to added salt, but also appear to exchange matter on relevant time scales. The small and largely quenched early-stage precursor complexes are responsible for the morphological and dynamic differences, implying that kinetic control may also be a way to obtain particles with well-defined and useful properties. The exciting new finding that triblocks produce more "active" vesicles will hopefully trigger the exploration of more pathways, and so learn how to tune PICsomes toward specific applications.

A thermodynamic study of F108 and F127 block copolymer interactions with liposomes at physiological temperature.

The interactions of egg yolk phosphatidylcholine liposomes with F108 and F127 triblock copolymers, in the monomer state, were analyzed by isothermal titration calorimetry (ITC) at 37 °C. According to the results, the critical micelle concentration was determined to be 0.4 and 0.04 wt.% for F108 and F127, respectively, by surface tension at 37 °C. According to the results, liposomes/poloxamers were not favoured energetically, since endothermic interactions were observed. However, positive changes in entropy promoted a spontaneous process. F127 had a greater partition coefficient (51.97 ± 1.77 × 104), stronger affinity, than F108 (8.19 ± 0.37 × 104) towards the vesicle lipid bilayer due to its larger hydrophobic block. After the ITC experiments, an increased vesicle size (within about 1-3 nm average) by dynamic light scattering and the formation of bilayer discs by electron microscopy (EM) was observed at low copolymer concentrations (0.57 mol% of F108 and 1.01 mol% of F127). The EM and ITC results confirmed the intimate association of the copolymers with the membrane instead of being simply absorbed onto the bilayer surface. Our results indicate that the temperature of the system (37 °C), the copolymer concentration and hydrophobic chain length are important factors for the interaction of poloxamers with lipid bilayers and the stability of liposomes.

Gas-Responsive Self-Assemblies for Mimicking the Alveoli.

In human body, alveoli are the primary sites for gas exchange which are formed by the dilation and protrusion of bronchioles at the end of the lung, and the rapid gas-exchanging process in the alveoli ensures normal life activities. Based on the unique structures and functions of alveoli, it is necessary to study the regulation mechanism of its formation, respiration, and apoptosis. Herein, a class of reversible addition-fragmentation chain transfer (RAFT)-derived amphiphilic triblock copolymers, PEO-b-P(DEAEMA-co-FMA)-b-PS is designed and synthesized. Due to the amphiphilic and gas-responsive segments, these triblock copolymers can self-assemble in aqueous solution and undergo the morphological transition from nanotubes to vesicles under gas stimulation; meanwhile, in the cycles of CO2 /O2 stimulation, these vesicles can further realize the volume expansion and contraction, eventually rupture. The gas-driven morphological transformations of these aggregates successfully imitate the formation, respiration, and apoptosis of alveoli, and provide an essential basis for revealing the life phenomena.

Synthesis, Properties, and Biodegradability of Thermoplastic Elastomers Made from 2-Methyl-1,3-propanediol, Glutaric Acid and Lactide.

An innovative type of biodegradable thermoplastic elastomers with improved mechanical properties from very common and potentially renewable sources, poly(L-lactide)-b-poly(2-methyl-1,3-propylene glutarate)-b-poly(L-lactide) (PLA-b-PMPG-b-PLA)s, has been developed for the first time. PLA-b-PMPG-b-PLAs were synthesized by polycondensation of 2-methyl-1,3-propanediol and glutaric acid and successive ring-opening polymerization of L-lactide, where PMPG is an amorphous central block with low glass transition temperature and PLA is hard semicrystalline terminal blocks. The copolymers showed glass transition temperature at lower than -40 °C and melting temperature at 130-152 °C. The tensile tests of these copolymers were also performed to evaluate their mechanical properties. The degradation of the copolymers and PMPG by enzymes proteinase K and lipase PS were investigated. Microbial biodegradation in seawater was also performed at 27 °C. The triblock copolymers and PMPG homopolymer were found to show 9-15% biodegradation within 28 days, representing their relatively high biodegradability in seawater. The macromolecular structure of the triblock copolymers of PLA and PMPG can be controlled to tune their mechanical and biodegradation properties, demonstrating their potential use in various applications.

Application of Poloxamers for the Development of Drug Delivery System to Treat Leishmaniasis: A Review.

Leishmaniasis is a neglected tropical disease affecting more than 1.5 million people annually, with an annual mortality of over 20.000. The drugs used for its treatment are toxic, expensive, require extended treatment times and present variable efficacy. The disease severity and therapy limitations suggest the need for new antileishmanial agents. In this context, in order to identify new options for treatment, a number of studies based on nanotechnological strategies have been carried out. Poloxamers are triblock copolymers very often utilized for nanotherapeutic solutions, resulting in products with better solubility, higher stability, superior therapeutic efficacy and less toxicity. This review will discuss the physicochemical properties of the copolymers, as well as describe the use of poloxamers for the development of therapeutic formulations to treat leishmaniasis.

Biocompatible Nanocomposites Based on Poly(styrene-block-isobutylene-block-styrene) and Carbon Nanotubes for Biomedical Application.

In this study, we incorporated carbon nanotubes (CNTs) into poly(styrene-block-isobutylene-block-styrene) (SIBS) to investigate the physical characteristics of the resulting nanocomposite and its cytotoxicity to endothelial cells. CNTs were dispersed in chloroform using sonication following the addition of a SIBS solution at different ratios. The resultant nanocomposite films were analyzed by X-ray microtomography, optical and scanning electron microscopy; tensile strength was examined by uniaxial tension testing; hydrophobicity was evaluated using a sessile drop technique; for cytotoxicity analysis, human umbilical vein endothelial cells were cultured on SIBS-CNTs for 3 days. We observed an uneven distribution of CNTs in the polymer matrix with sporadic bundles of interwoven nanotubes. Increasing the CNT content from 0 wt% to 8 wt% led to an increase in the tensile strength of SIBS films from 4.69 to 16.48 MPa. The engineering normal strain significantly decreased in 1 wt% SIBS-CNT films in comparison with the unmodified samples, whereas a further increase in the CNT content did not significantly affect this parameter. The incorporation of CNT into the SIBS matrix resulted in increased hydrophilicity, whereas no cytotoxicity towards endothelial cells was noted. We suggest that SIBS-CNT may become a promising material for the manufacture of implantable devices, such as cardiovascular patches or cusps of the polymer heart valve.

Polymer Gel Electrolytes Based on PEG-Functionalized ABA Triblock Copolymers for Quasi-Solid-State Dye-Sensitized Solar Cells: Molecular Engineering and Key Factors.

The molecular weights and structural properties of polymers play key roles in the efficiency of gelators in polymer gel electrolytes (PGEs) for quasi-solid-state dye-sensitized solar cells (QSS-DSSCs). To find an appropriate gelator, we synthesized well-defined poly(acrylonitrile-co-N,N-dimethylacrylamide)-block-poly(ethylene glycol)-block-poly(acrylonitrile-co-N,N-dimethylacrylamide) ABA triblock copolymers with various molecular weights and copolymer compositions by reversible addition-fragmentation chain-transfer polymerization. The ratio of acrylonitrile (AN)/N,N-dimethylacrylamide (DMAA) in the triblock copolymers influences their solubility in liquid electrolytes (LEs) and thermal stability. The highest thermal stability was up to 360 °C, and this was achieved by the polymer with an AN/DMAA ratio of ≤4. The thermal stability was related to excessive randomness in the P(AN-co-DMAA) block that hinders cyclization among nitrile groups. Both the molecular weights and the AN/DMAA ratios enabled gel formation by controlling the amount of the polymer, and hence, they influence the ionic conductivity and diffusion as well. Based on the electrochemical properties, polymers with molecular weights above 100 kg/mole were efficient as PGEs in QSS-DSSCs. The overall power conversion efficiency (PCE) of 14 wt % SGT-626 PGE-based QSS-DSSCs was 9.72% under AM 1.5G solar illumination, comparable with an overall PCE of 9.79% for LE DSSCs. The overall PCE of the QSS-DSSCs further increased to 10.02% by incorporating 3 wt % TiO2 nanoparticles in the 14 wt % SGT-626 PGE. The SGT-626 PGE-based QSS-DSSC was also tested under indoor light conditions, and the best PCE of 21.26% was achieved under a white LED light of 1000 lux, which is higher than the PCE of 19.94% for the LE DSSC. The long-term device stability test under adverse conditions (50 °C and 1 sun illumination) reveals the improved stability of PGE-based QSS-DSSCs over LE DSSCs. In terms of PCE and long-term device stability, our PGE QSS-DSSCs have great potential over LE DSSCs for future indoor and outdoor applications.

Hydrophilic Dual Layer Hollow Fiber Membranes for Ultrafiltration.

In this study, a triblock copolymer was used as additive to fabricate new dual layer hollow fiber membranes with a hydrophilic active inner surface in order to improve their fouling resistance. The polymeric components of the solutions for membrane fabrication were poly(ether sulfone), poly(N-vinyl pyrrolidone), and the triblock copolymer. The additive consists of three blocks: a middle hydrophobic poly(ether sulfone) block and two outer hydrophilic alkyl poly(ethylene glycol) blocks. By varying the additive concentration in the solutions, it was possible to fabricate dual layer hollow fiber membranes that are characterized by a hydrophilic inner layer, a pure water permeance of over 1800 L/(m2 bar h) and a molecular weight cut-off of 100 kDa similar to commercial membranes. Contact angle and composition determination by XPS measurements revealed the hydrophilic character of the membranes, which improved with increasing additive concentration. Rheological, dynamic light scattering, transmission, and cloud point experiments elucidated the molecular interaction, precipitation, and spinning behavior of the solutions. The low-molecular weight additive reduces the solution viscosity and thus the average relaxation time. On the contrary, slow processes appear with increasing additive concentration in the scattering data. Furthermore, phase separation occurred at a lower non-solvent concentration and the precipitation time increased with increasing additive content. These effects revealed a coupling mechanism of the triblock copolymer with poly(N-vinyl pyrrolidone) in solution. The chosen process parameters as well as the additive solutions provide an easy and inexpensive way to create an antifouling protection layer in situ with established recipes of poly(ether sulfone) hollow fiber membranes. Therefore, the membranes are promising candidates for fast integration in the membrane industry.