Synthesis and characterization of polycation block copolymer Poly(l-lysine)-b-poly[N-(N′,N′-diisopropyl-aminoethyl)aspartamide] as potential pH responsive gene delivery system

A series of Poly(l-lysine)_m-b-poly[N-(N′,N′-diisopropylaminoethyl) aspartamide]_n copolymers, abbreviated as PLL_m-b-P[Asp(DIP)]_n were designed and synthesized via ring-opening polymerization(ROP), click chemistry, aminolysis and hydrolysis. Using ¹H NMR, FT-IR and GPC, the structures and compositions of these copolymers have been verified. Through feed ratio control, block copolymer PLL_m-b-P[Asp(DIP)]_n with different PLL and PAsp(DIP) block lengths were obtained, which can be modified to adjust the pH responsiveness and the self-assembling behaviors of the PLL_m-b-P[Asp(DIP)]_n. From the results of DLS, TEM and ¹H NMR, these block copolymers can form stable micelles with a partially hydrated PAsp(DIP) core and a PLL corona at pH 7.4. While as demonstrated by ¹H NMR and TEM, these PLL_m-b-P[Asp(DIP)]_n micelle was disassembled due to further protonation of the tertiary amine in the PAsp(DIP) block at pH 5.4. These pH responsive character of the PLL_m-b-P[Asp(DIP)]_n micelles made them as potential pH responsive gene delivery system which may co-deliver drug and DNA simultaneously.     

INTRAPARTICLE MASS TRANSFER IN THERMALLY REGENERABLE ION EXCHANGER

An intraparticle mass transfer model was developed for a thermally regenerable ion exchanger which is coagulated by weak acidic and basic microspheres. It was assumed that salt diffuses (hrough macropore and microspheres in the radial direction of a resin particle. Uptake curves were measured not only in [R_aCOOH + R_bN] + NaCl ) [R_aCOONa + R_bNHCl] system but also in [R_aCOO²²Na⁺ + R_aN] + Na⁺ )[R_aCOONa⁺ + R_bN] + ²²Na⁺ and [R_aCOOH + R_aN] + HCl ) [R_aCOOH + R_bNHCl] systems. Macropore diffusivity D_p.Na, tortuosity factor τ_p and diffusivity through weak acidic microspheres D_a,Na were obtained from the isotopic ion exchange. The uptake curves of HC1 gave diffusivity through weak basic microspheres.D_b,Hcl The experimental uptake and desorption curves of NaCl agreed fairly well with the theoretical values. Diffusions through both macropore and microspheres were significant. The diffusivity through microspheres D_b,Nacl NaCI are smaller than D_a,Na. and can be estimated by D_bHcl approximately.     

Synthesis of (ABCB)n type ternary amphiphilic multiblock copolymer via poly(ethylene oxide) macro-chain transfer agent

A novel (ABCB)_n type ternary amphiphilic multiblock copolymer was synthesized by stepwise insertion of monomers into the trithiocarbonate-embedded poly(ethylene oxide) (PEO) macro-chain transfer agent (PEO-CTA)_n. (PEO-CTA)_n was synthesized first by coupling of α,ω-dihydroxyl PEO with dicarboxylic trithiocarbonate, then styrene (St) and t-butyl acrylate (^tBA) were inserted into the (PEO-CTA)_n successively to yield (PEO-b-PS)_n and (PEO-b-PS-b-P^tBA-b-PS)_n, respectively. After hydrolysis of the (PEO-b-PS-b-P^tBA-b-PS)_n, the final product (PEO-b-PS-b-PAA-b-PS)_n was obtained.     

Thermal stresses and birefringence in quenched tubes and rods: Simulation and experiment

Measurements and simulations of the radial distribution of the thermal birefringence components, Δn and n_θθ ? n_rr, and the average birefringence, <n_zz ? n_θθ>, in free quenched tubes and rods of polystyrene (PS) and polycarbonate (PC) at different initial temperatures were carried out. The thermal stress and birefringence components were simulated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the Young's relaxation modulus and strain‐optical coefficient functions of polymers. The numerical procedures used to discretize the governing equations using finite difference method were described. The obtained numerical results provided the evolution of stress and birefringence components with time during and after quenching and an explanation of the measured residual birefringence distribution in quenched tubes and rods. It was also found that the thickness of the slices removed from the samples to measure the thermal birefringence components, Δn and n_θθ ? n_rr, was critical, in particular, when the initial temperatures were close to the glass transition temperature of polymers. With an increase of the initial temperature during quenching, a better agreement between the simulated and measured birefringence components was obtained. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Thermodynamical approach to polymer rheology

The model of pseudocrosslink is extended to polymer rheology. There exist various sizes b of 4–16 between transition points A and B. Each link is connected with a chain having length n_b and relaxation time τ_b. n_b is equal to b² and τ_b is proportional to n_b². A, B, and C (polymer terminal) divide the stress-relaxation spectrum into four zones. In the AB zone, successive dissociation of links occurs from a small size to a large one and rigidity G is decreased with time t as G ∝? t^?0.5 and viscosity η is increased as G ∝? t^0.5. In the BC zone, dissociation of the B link proceeds along a molecule of length n in a mode of squeezing of molecule and η becomes constant, but G still decreases due to increase of unperturbed end-to-end distance of chain and G ∝? t^?0.5. However, dynamic elasticity becomes constant due to a small amplitude. At high shear, links are loosened and G and η are much decreased. Beyond C, molecule flows and η increases as η ∝? γ^?0.8 n^3.5, but high shear rate γ diminishes the effect of n due to extension of the molecule. Extensional viscosity η^* is affected by the change of shape as η^* ∝? t^1.5 and gives an overshoot. Under load, creep occurs and it is proportional to t^1/2–1/3. © 1995 John Wiley & Sons, Inc.     

Effect of irrigation and nitrogen fertilizer on yield,oil content,nitrogen accumulation and water use of canola (Brassica napus L.)

Effects of N application and water supply on yield, oil content and N accumulation by canola, cultivar Marnoo, grown on a heavy clay soil in the Goulburn Murray Irrigation Region were investigated. Treatments were rainfed (R_f) or watered at a deficit of 50 mm (40–60 mm, I₅₀) beginning in the spring. N treatments were 0, 50, 100 or 200 kg N ha^–1 at sowing or as split applications of 20/80, and 50/50 kg N ha^–1 at sowing and rosette, respectively.Yield (Y_g) ranged from 170 to 520 g m^–2. Irrigation and N increased yield in both years. Grain yields were increased by N application on the irrigated treatments when 100 or 200 kg N ha^–1 was applied. Oil concentrations ranged from a maximum of 46.4% in treatment N₀ to a minimum of 40.6% in treatment N₂₀₀ and was inversely related to seed N concentration. Although fertilizer N decreased oil concentration, it increased the yield of oil.Nitrogen accumulation (N_b) limited yield of all treatments and was described by the equation, Y_g = 806[1-EXP(–0.039*N_b)]. This implied a decrease in yield per unit of N_b at the higher rates of fertilizer addition with consequent increases in grain N concentration.The efficiency of water use in the production of grain (WUE_g) and biomass (WUE_b) were 7.5 and 23 kg ha^–1 mm^–1 respectively. Nitrogen additions increased WUE_g and WUE_b in both seasons. Maximum values of 8.9 (WUE_g 1986) and 26.8 (WUE_b 1987) were measured from treatment N₂₀₀. These data suggest that the crops made efficient use of the applied water.     

The potential of Cu(I)Cl/2,2′‐bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

The ability of atom transfer radical polymerization (ATRP) in the sequential synthesis of triblock copolymers was examined using Cu(I)Cl/2,2′‐bipyridine catalysis at 110°C in toluene, starting from PMMA macroinitiators terminated with the C‐Br group. The PMMAs were prepared by living anionic or group transfer polymerization (GTP), followed by bromination of the respective active site with Br₂ or N‐bromosuccinimide (NBS). The yield of the terminal bromination in the products of both living polymerizations was 60–64% at best, compared with the yield of the bromination of 1‐methoxy‐(1‐trimethylsilyloxy)prop‐1‐ene (a model of the GTP active site) with NBS, as found by ¹H‐NMR. The PMMA macroinitiators prepared were utilized to start the sequential ATRP, finally affording PMMA‐b‐PBuA‐b‐PSt (M_n 69,100), PMMA‐b‐PSt‐b‐PBuA (M_n 21,300) and PMMA‐b‐PSt‐b‐PMMA (M_n 35,200), which have not yet been synthesized by ATRP. After the second block has been formed, the Br‐unterminated part of PMMA macroinitiator was removed by extraction or repeated precipitation. In the third (last) sequence polymerization, induction periods were observed. The first two triblock copolymers were free of precursors and have M_w/M_n values 1.5–1.6 (SEC). In the course of the last step of PMMA‐b‐PSt‐b‐PMMA synthesis, the content of the PMMA‐b‐PSt precursor slowly decreased with increasing MMA conversion. Still, at ≈90% MMA conversion, about 10–15% of the precursor remained in the product. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3514–3522, 2001     

Fabrication of covalently bonded nanostructured thin films of epoxy resin and polydimethylsiloxane for oil adsorption

Thin films of architectures PEI(CNER_a/PDMS)_n, PEI(CNER_b/PDMS)_n, (PEI/CNER_b)_n and PEI(CNER_b/NH₂-MMT/PEI)_n have been fabricated via covalent layer-by-layer technique. Different film deposition parameters such as solvent type, polymer concentration, polymer ratio and dipping time have been optimized to achieve a uniform growth of layers. The effect of polymer concentration and dipping time on film thickness was also studied via ellipsometer. The optimized ratio of polymer concentration was 1:1 and 1:2 for PEI(CNER_a/PDMS)_n and PEI(CNER_b/PDMS)_n, respectively. AFM analysis indicated that the films were homogeneous while contact angle measurements revealed that although films were hydrophobic in nature yet they have wetting property due to the presence of hydroxyl groups formed during curing process. These epoxy-based multilayers have shown significant oil adsorption capacity. All the fabricated films qualify scotch tape test and were found resistant towards strong acids, bases and organic solvents.     

Measurement of Light Absorption Extinction in Denver

Simultaneous measurements of b _ext (teleradiometer), b _sp (integrating nephelometer), and b _ag (N0₂ monitor) were used to obtain particle absorption extinction coefficients b _ap for the Denver atmosphere during January 1982. The average of the ratio b _ap/b _sp was measured to be 0.185 ± 0.015 at 530 nm, which is 2–3 times smaller than previous measurements. Supplementary data included b _ap measurements by the integrating plate method, which yielded values systematically higher by about 35%, and elemental carbon (black soot) aerosol concentration, from which a value of 8.0±0.6 m² g^?1 was obtained for the mass-specific absorption coefficient of elemental carbon.     

Synthesis and crystal structure of a novel 2-D hybrid compound [(PbBr2)2(μ-Pyz)]n (Pyz=pyrazine)

A novel 2-D organic–inorganic hybrid compound [(PbBr₂)₂(μ-Pyz)]_n 1, has been prepared, and its X-ray structure shows that the supramolecular structure consists of organic–inorganic hybrid layers, each of which is constructed from two [PbBr₂]_n sheets and one pyrazine, via Pb–N bonding along the direction of the b-axis, and the divalent lead is penta-coordinated to form a hemidirected complex.     

Synthesis of amphiphilic triblock copolymers and application for morphology control of calcium carbonate crystals

A series of amphiphilic triblock copolymers poly(ethylene glycol)-block-poly(acrylic acid)-block-poly(n-butyl acrylate) (PEG-b-PAA-b-PnBA) differing only in the relative block lengths were synthesized by the acid-catalyzed elimination of the tert-butyl groups from poly(ethylene glycol)-block-poly(tert-butyl acrylate)-block-poly(n-butyl acrylate) (PEG-b-PtBA-b-PnBA), which was synthesized by atom-transfer radical polymerization (ATRP). The degree of polymerization, molecular weight and percentage of hydrolysis of the product PEG-b-PAA-b-PnBA were studied by gel permeation chromatography (GPC), NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF-MS). Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to study the aggregation states of copolymers in water solution. The radii of the copolymer micelles shrink as Ca²⁺ is introduced into the solutions. The crystallization behaviors of calcium carbonate controlled by copolymer 1 (PEG₁₁₂-b-PAA₈₆-b-PnBA₆₀) and copolymer 2 (PEG₁₁₂-b-PAA₄₀-b-PnBA₇₂) differing mainly in the length of PAA block were systematically studied. It was found that the crystallization products are composed of calcite and vaterite, and the ratio of vaterite to calcite increases with increasing the concentration of copolymer 1. For copolymer 2, however, only calcite is obtained at all the concentration range investigated in this work.     

Baroplastic behavior of miscible block copolymer blends

Pressure dependence of various phase transitions for the miscible block copolymer (BCP) blends was evaluated by depolarized light scattering (DPLS) and small-angle neutron scattering (SANS) measurements, in which the blends consist of a polystyrene-b-poly(n-butyl methacrylate) (PS-b-PnBMA) and a deuterated polystyrene-b-poly(n-hexyl methacrylate) (dPS-b-PnHMA). Excellent baroplasticity was observed in nearly symmetric blends of PS-b-PnBMA/dPS-b-PnHMA, leading to the most outstanding pressure coefficients, |dT/dP|, in a closed-loop type phase behavior between a lower disorder-to-order transition (LDOT) and an order-to-disorder transition (ODT) type phase behavior. Together with the estimated pressure coefficients based on the values of enthalpic and volumetric changes at phase transitions, we demonstrate that the entropic compressibility for the miscible BCP blends is a baroplastic indicator, which was characterized by the negative volume change on mixing (ΔV_mix) at transitions.     

A Method for Determining Bulk Density,Material Density,and Porosity of Melter Feed During Nuclear Waste Vitrification

Glassmelting efficiency largely depends on heat transfer to reacting glass batch (melter feed), which in turn is influenced by the bulk density (ρ_b) and porosity (?) of the reacting feed as functions of temperature (T). Neither ρ_b(T) nor ?(T) functions are readily accessible from direct measurements. For the determination of ρ_b, we monitored the profile area of heated feed pellets and calculated the pellet volume using numerical integration. For the determination of ?, we measured the material density of feeds quenched at various stages of conversion via pycnometry and then computed the feed density at heat‐treatment temperature using thermal expansion values of basic feed constituents.     

Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2] n

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G^* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP₂NCl₅ and OP₃N₂Cl₅) were compared with those derived fromab initio quantum mechanics using the 6–31G^* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; β=111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.     

Swelling behavior of ordered miktoarm star block copolymer-homopolymer blends

We report the morphological characterization of asymmetric miktoarm star block copolymers of the (PS-b-PI)_nPS type where n=2,3 (denoted 2DB and 3DB miktoarm stars, respectively) and a symmetric super H-shaped block copolymer of the (PS-b-PI)₃PS(PI-b-PS)₃ type (denoted SH) which were synthesized by anionic polymerization. The initial volume fraction of PS (φ_PS) for each copolymer was 0.51-0.56, giving a lamellar morphology. Addition of homopolystyrene (hPS) with a molecular weight lower than the respective PS blocks in the neat materials lead to a transition from the lamellar structure to hexagonally packed cylinders. Addition of low molecular weight homopolyisoprene (hPI) on the other hand, only resulted in swollen lamellae even when the overall composition was highly asymmetric (80/20). Changes in the lamellar spacing as well as in the respective PS and PI layer thickness were measured by SAXS. The transition from lamellae to cylinders with increased PS content occurred without the observation of an intervening cubic morphology for the 2DB and 3DB miktoarm stars. However, blends with 30 and 35% hPS ((φ_PS)_total=0.68-0.70) with the super H-shaped block copolymer lead to the observation of lamellar-catenoid structures.     

Preparation of poly(styrene‐b‐2‐hydroxyethyl acrylate) block copolymer using reverse iodine transfer polymerization

Reverse iodine transfer polymerizations (RITP) of 2‐h‐ydroxyethyl acrylate (HEA) were performed in N,N‐dimethylformamide at 75°C using AIBN as initiator. Poly(2‐hydroxyethyl acrylate) (PHEA) with M_n = 3300 g mol^?1 and M_w/M_n <1.5 were obtained. Homopolymerization of styrene in RITP was also carried out under similar conditions using toluene as solvent. The resulting iodo‐polystyrene (PS‐I) with (M_{n, SEC} = 607 g mol^?1, polydispersity index (PDI) = 1.31) was used as a macroinitiator for the synthesis of amphiphilic block copolymers based on HEA with controlled well‐defined structure. Poly(styrene‐b‐2‐hydroxyethyl acrylate) (PS‐b‐PHEA) with M_n = 13,000 g mol^?1 and polydispersity index (M_w/M_n) = 1.4 was obtained, copolymer composition was characterized using ¹H‐NMR and FTIR, whereas SEC and gradient HPLC were used to confirm the formation of block copolymer and the living character of polymer chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phosphorus and potassium soil test and nitrogen leaf analysis as a base for citrus fertilization

A network of six NPK long-term field trials was carried out on different soils of citrus-producing regions of São Paulo state, Brazil, in order to estimate quantitative relations of fruit yield to NPK fertilization and to determine parameters for fertilizer recommendation based on soil testing and leaf analysis. The experiments were set up in an incomplete factorial design 1/2 4³ with 32 treatments, with four yearly rates of N (30, 100, 170 and 240 kg N/ha), P (9, 27, 45 and 63 kg P/ha) and K (25, 91, 157 and 223 kg K/ha). Four to seven harvests were recorded for the six experiments. Response surfaces of the type y = bo + b₁N + b₁₁N² + b₂P + b₂₂P² + b₃K + b₃₃K² + b₁₂NP + b₁₃NK + b₂₃PK were adjusted to the average yields of each trial. Correlation were established for yield increases, expressed as relative yields, and results of soil analysis of P and K, and leaf analysis of N. Soil samples taken at 0-20 cm depth in the beginning of each experiment were analyzed for resin extractable P and exchangeable K using an ion-exchange resin procedure. Yield responses for phosphorus and potassium applications were observed respectively in soils with less than 20 mg dm^-3 of P and 20 mmol_c dm^-3 of K⁺. Yield responses to nitrogen were related to the total content of nitrogen in leaves, being largest for N values of 23 g kg^-1 and smallest for N of 28 kg^-1. With these field information, a practical approach for fertilizer recommendation for citrus, based on soil analysis for P and K and leaf analysis for N, was developed.     

Synthesis and surface properties of chemodegradable anionic surfactants: Diastereomeric (2-n-alkyl-1,3-dioxan-5-yl) sulfates with monovalent counter-ions

Sodium, potassium and ammonium cis- and trans-(2-n-alkyl-1,3-dioxan-5-yl) sulfates 6–8 (alkyl: n-C₉H₁₉, 6a–8a, and n-C₁₁H₂₃, 6b–8b) were synthesized in a reaction of aliphatic aldehydes 1a,b with glycerol 2 followed by separation in high yields of individual geometric isomers of cis-and trans-2-n-alkyl-5-hydroxy-1,3-dioxanes, cis-3a,b and trans-3a,b, followed by sulfation with sulfur trioxide-pyridine complex, and finally neutralization with NaOH, KOH, and NH₄OH, respectively. Physical data of the compounds and some surface properties of 2-n-nonyl derivatives, such as critical micelle concentration (CMC), effectiveness of aqueous surface tension reduction (Π_CMC), surface excess concentration Γ_CMC, and the surface area demand per molecule (A_CMC), were determined. It was shown that the surface activity of these compounds is influenced both by their geometric structure and by the monovalent counter-ion.     

Radial gas mixing in a fluidized bed using response surface methodology

Radial gas mixing in a fluidized bed was studied using response surface methodology (RSM), which enables effect examinations of parameters with a moderate number of experiments. All experiments were conducted in a 0.29-m ID fluidized-bed cold model. The gas dispersion process within the bed is described using the dispersed plug flow model. Pure carbon dioxide was used as the tracer gas, continuously injected into the center of the bed by a point source. The downstream radial tracer concentration profile was measured using a gas chromatograph.The radial gas dispersion coefficient, D_r, was well correlated with operating parameters and the particle and gas properties: (U−U_mf)/U_mf, H_s/d_b, φ_d, and Ar, with a determination coefficient R² of 0.966. Effect test indicates that the dimensionless characteristic velocity, (U−U_mf)/U_mf, has the most significant influence on D_r, while the static bed height to bed diameter ratio, H_s/d_b, is less remarkable. The interactions of (U−U_mf)/U_mf with the distributor open-area ratio, φ_d, and with the Archimedes number, Ar, both play important roles. An evolutive response surface model was proposed to describe the radial gas mixing in the bubbling/slugging fluidization regimes.