Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P₅₅₅C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH₂PO₄/K₂HPO₄ salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution.     

Role of chloronium complex in the electrochemical chlorination of c-hexene in nitromethane

The anodic chlorination of c-hexene in NM solution having 150 ppm water content involves three charge-transfer reactions. The effect of potential on change in product distribution is more effective at the beginning of electrolysis. A mechanism for the process is suggested.     

Isothermal crystallization study on aqueous solution of poly(vinyl methyl ether) by DSC method

A study on the isothermal crystallization of water in aqueous solutions of poly(vinyl methyl ether) (PVME) was carried out by the differential scanning calorimetry (DSC). The influence of PVME concentration (49.5, 44.5 and 39.5 v%) and the crystallization temperature (T_c) on crystallization rate G, crystallization enthalpy (ΔH_c) and melting enthalpy (ΔH_m) was investigated. Avrami equation cannot be used to describe the crystallization process of water in aqueous PVME solution. Within the measured temperature range, the crystallization rate G increases with the crystallization temperature T_c and with the decreasing PVME content. The crystallization enthalpy ΔH_c linearly increases with the degree of supercooling. The influence of T_c on the ΔH_c becomes more marked with increasing PVME concentration. For 49.5 and 44.5 v% PVME solutions, the amount of water arrested in solution during the isothermal crystallization and the final concentration of PVME-rich phase increase linearly with the T_c, whereas for 39.5 v% PVME solution, these two values almost do not change with T_c. The amount of frozen water in the subsequent cold crystallization is approximately proportional to the initial T_c. The approximately constant ΔH_m for a given concentration at the different initial isothermal crystallization temperatures suggests that the total amount of ice from the first isothermal crystallization and the second cold crystallization is same. The quantitative relation of the amount of frozen water in the cold crystallization and the initial T_c demonstrates that PVME/water complexes are thermodynamically unstable.     

Sorption of methane in moist coal

The dependence on moisture content of the methane sorption capacity of four American coals has been investigated. Bituminous coals from Virginia, West Virginia, Oklahoma and Pennsylvania were studied at a temperature of 30 °C, and at pressures up to 60 atm. Methane capacity decreased with increasing moisture content up to a certain value of moisture content that was characteristic for each coal. Moisture present in excess of the critical value had no further effect on methane sorption. The critical values of moisture content, m_c (wt %), were related to coal oxygen content, x_o (wt %), by the expression m_c = (X_O + 1.51 )/(3.98 ? 0.229 X_O).     

Phase transition in swollen gels: 7. Effect of charge concentration on the temperature collapse of poly(N,N-diethylacrylamide) networks in water

The swelling and mechanical behaviour of gels of the copolymer of diethylacrylamide (DEAAm) with a small quantity of sodium methacrylate (mole fraction x_MNa = 0–0.067) swollen in water was investigated in the temperature range 1–80°C. For networks in the range x_MNa > 0.0095 phase transition was observed; both the critical transition temperature T_c,c and the extent of the collapse Δ_c increase with increasing x_MNa. The formation of associations in the collapsed state contributes to the overall extent of the transition; these structures give rise to stable turbid gels at elevated temperatures. Evidence for the formation of ‘associated’ structures is also supported by the observed independence of cloud temperature of the concentration of DEAAm, c, in the polymerization DEAAm-water mixture without the crosslinking agent in the range c = 0.5–80 vol%. While PDEAAm solutions are formed in the range c < 4.5–6 vol%, physical gels arise at higher concentrations.     

The onset of instability in the flow induced by an impulsively started rotating cylinder

The onset of initial instability in a developing Couette flow following the impulsive starting of an inner rotating cylinder is analyzed using linear theory. It is well known that there is a critical Taylor number Ta_c at which Taylor vortices first appear between two concentric cylinders. For Ta>Ta_c Taylor-like vortices occur at a certain elapsed time. In the present study, the critical time t_c to represent the onset of this initiating instability, which then grows as toroidal vortices, is analyzed using propagation theory. For this purpose a self-similar transformation is forced through scaling analysis. The resulting stability criteria compare well with the available experimental data for vortices in water. The new measures represent the onset of the fastest growing instability and also suggest the detection time for the manifestation of secondary flow in the primary time-dependent Couette flow.     

Photochemical switching of hydrogel film properties

A copolymer of N-isopropyl acrylamide and acrylic acid was modified in a polymer analogous reaction by an acridizinium chromophore capable of reversible photochemical dimerization. The acridizinium chromophore allows a faster and more complete photocrosslinking and a better photoreversibility as compared to stilbene and stilbazolium chromophores. Due to its hydrophilic nature the chromophore only moderately affected cloud points T_c of the copolymer and lower critical solution temperatures (LCST) of photocrosslinked films of the copolymer, even at high chromophore content (3.5% w/w). Such films can be swollen in water to form hydrogels. LCST and T_c depend on the content and on the counterion of the chromophore, on the solvent from which films are prepared, and on the degree of crosslinking. The latter dependence allows the exploitation for isothermal switching of film properties by exposure to light.     

Isothermal and non-isothermal crystallization behavior of poly(l-lactic acid): Effects of stereocomplex as nucleating agent

The effects of incorporated poly(d-lactic acid) (PDLA) as poly(lactic acid) (PLA) stereocomplex crystallites on the isothermal and non-isothermal crystallization behavior of poly(l-lactic acid) (PLLA) from the melt were investigated for a wide PDLA contents from 0.1 to 10 wt%. In isothermal crystallization from the melt, the radius growth rate of PLLA spherulites (crystallization temperature (T_c)≥125 °C), the induction period for PLLA spherulite formation (t_i) (T_c≥125 °C), the growth mechanism of PLLA crystallites (90 °C≤T_c≤150 °C), and the mechanical properties of the PLLA films were not affected by the incorporation of PDLA or the presence of stereocomplex crystallites as a nucleating agent. In contrast, the presence of stereocomplex crystallites significantly increased the number of PLLA spherulites per unit area or volume. In isothermal crystallization from the melt, at PDLA content of 10 wt%, the starting, half, and ending times for overall PLLA crystallization (t_c(S), t_c(1/2), and t_c(E), respectively) were much shorter than those at PDLA content of 0 wt%, due to the increased number of PLLA spherulites. Reversely, at PDLA content of 0.1 wt%, the t_c(S), t_c(1/2), and t_c(E) were longer than or similar to those at PDLA content of 0 wt%, probably due to the long t_i and the decreased number of spherulites. This seems to have been caused by free PDLA chains, which did not form stereocomplex crystallites. On the other hand, at PDLA contents of 0.3-3 wt%, the t_c(S), t_c(1/2), and t_c(E) were shorter than or similar to those at PDLA content of 0 wt% for the T_c range below 95 °C and above 125 °C, whereas this inclination was reversed for the T_c range of 100-120 °C. In the non-isothermal crystallization of as-cast or amorphous-made PLLA films during cooling from the melt, the addition of PDLA above 1 wt% was effective to accelerate overall PLLA crystallization. The X-ray diffractometry could trace the formation of stereocomplex crystallites in the melt-quenched PLLA films at PDLA contents above 1 wt%. This study revealed that the addition of small amounts of PDLA is effective to accelerate overall PLLA crystallization when the PDLA content and crystallization conditions are scrupulously selected.     

On the zinc-chloride complex formation

The complex formation between zinc and chloride ions has been investigated by emf measurements on the cell Ag,AgCl¦x M NaCl + y M NaClO₄ + 0.025 M ZnCl₂¦Zn(Hg),Pt.The total concentration was varied between 1 and 4.6 mol·1^?1. Three mononuclear complexes with 1,3 and 4 chloride ligands were found to be present. The complex constants based on the concentrations of the unhydrated species ?β_n(c)? showed a pronounced increase with decreasing water activity. A set of concentration independent constants is obtained when the solution is treated as an ideal mixture of hydrated ions and free water. The number of water molecules in the hydration shell replaced by one chloride ligand was estimated to four and the complex constants to:

Where Σc_i is the total concentration of hydrated ions and free water, and x_H2O is the mole fraction of free water.     

Effect of solids on homogeneous-heterogeneous flow regime transition in bubble columns

Experiments were conducted to study the effect of the presence of the solid phase on the homogeneous-heterogeneous flow regime transition in a bubble column 0.14 m diameter. Air, distilled water and calcium alginate beads (2.1 mm, ) at concentrations c=0-30% (vol.) were the phases. The basic data were the voidage-gas flow rate dependences. The critical point, where the homogeneous regime loses stability and the transition begins, was evaluated by the drift flux model. The critical values of voidage and gas flow rate were the quantitative measures of the homogeneous regime stability. These were plotted against the solid phase concentration. It was found, that both the voidage and the critical values increased with the solid content at low solid loading, approx. c=0-3%, and decreased at higher loading, c>3%. The homogeneous regime was thus first stabilized and then destabilized. To explain this dual effect, possible physical mechanisms of the solid phase influence on the uniform bubble bed were discussed.     

Hard and tough ultrafine-grained B4C-cBN composites prepared by high-pressure sintering

Tough and hard ultrafine-grained B₄C-cBN composites were firstly fabricated by high-pressure sintering mixed B₄C and cBN nanopowders at 6 GPa and 1700 °C. The phase transition from cBN to hBN is avoided by high pressure during the sintering process. The effects of the cBN content on the densification and mechanical properties of B₄C-cBN composites were evaluated. The results indicated that the hardness of the as-fabricated composites increased gradually with the increase of cBN content. The composite composed of 50 wt.% cBN exhibited excellent comprehensive mechanical properties with relative density of 98.6 %, density of 2.9 g/cm³, Vickers hardness of 36.2 GPa and fracture toughness of 6.7 MPa·m^1/2. The introduction of superhard cBN maintained the lightweight and high hardness while enhancing the fracture toughness of the B₄C. The main toughening mechanisms were crack bridging, crack deflection and pull-out of homogeneously dispersed cBN grains.     

Investigation of the carbonation mechanism of CH and C-S-H in terms of kinetics,microstructure changes and moisture properties

The purpose of this article is to investigate the carbonation mechanism of CH and C-S-H within type-I cement-based materials in terms of kinetics, microstructure changes and water released from hydrates during carbonation. Carbonation tests were performed under accelerated conditions (10% CO₂, 25 °C and 65 ± 5% RH). Carbonation profiles were assessed by destructive and non-destructive methods such as phenolphthalein spray test, thermogravimetric analysis, and mercury intrusion porosimetry (destructive), as well as gamma-ray attenuation (non-destructive). Carbonation penetration was carried out at different ages from 1 to 16 weeks of CO₂ exposure on cement pastes of 0.45 and 0.6 w/c, as well as on mortar specimens (w/c = 0.50 and s/c = 2). Combining experimental results allowed us to improve the understanding of C-S-H and CH carbonation mechanism. The variation of molar volume of C-S-H during carbonation was identified and a quantification of the amount of water released during CH and C-S-H carbonation was performed.     

Iron Deficiency Promotes the Lack of Photosynthetic Cytochrome c550 and Affects the Binding of the Luminal Extrinsic Subunits to Photosystem II in the Diatom Phaeodactylum tricornutum

In the diatom Phaeodactylum tricornutum, iron limitation promotes a decrease in the content of photosystem II, as determined by measurements of oxygen-evolving activity, thermoluminescence, chlorophyll fluorescence analyses and protein quantification methods. Thermoluminescence experiments also indicate that iron limitation induces subtle changes in the energetics of the recombination reaction between reduced Q_B and the S₂/S₃ states of the water-splitting machinery. However, electron transfer from Q_A to Q_B, involving non-heme iron, seems not to be significantly inhibited. Moreover, iron deficiency promotes a severe decrease in the content of the extrinsic PsbV/cytochrome c₅₅₀ subunit of photosystem II, which appears in eukaryotic algae from the red photosynthetic lineage (including diatoms) but is absent in green algae and plants. The decline in the content of cytochrome c₅₅₀ under iron-limiting conditions is accompanied by a decrease in the binding of this protein to photosystem II, and also of the extrinsic PsbO subunit. We propose that the lack of cytochrome c₅₅₀, induced by iron deficiency, specifically affects the binding of other extrinsic subunits of photosystem II, as previously described in cyanobacterial PsbV mutants.     

Dynamic viscoelastic behavior of triple helical Lentinan in water: Effects of concentration and molecular weight

The dynamic viscoelasitc behavior of Lentinan, one triple helical β-(1 → 3)-d-glucan from the fruiting body of Lentinus edodes, in water was investigated as a function of concentration and molecular weight at 25 °C by using dynamic rheology. It was revealed that the shear storage moduli (G′), viscous loss moduli (G″), and the dynamic complex viscosity (η^∗) exhibited strong dependence on concentration and molecular weight. At low concentrations, the Lentinan/water systems displayed liquid-like behavior with G′ lower than G″ at low frequencies and crossing-over at high frequencies. With increasing concentration, the elastic response of the Lentinan/water system was stronger than the viscous response, leading to the conclusion that the Lentinan/water systems displayed a predominantly solid-like behavior. The gel point (c_gel) was determined from Winter-Chambon method (frequency-independence of tan δ). The most important point is that the c_gel was much lower than some synthesized polymers and other flexible polysaccharides, which may be attributable to the high stiffness of triple helical Lentinan and strong intra- and intermolecular interactions among polysaccharide chains. Furthermore, a decrease in molecular weight leads to a sharp increase of c_gel. The dynamic strain sweep measurements proved that the gelation of Lentinan in water is induced by the extremely entangled and stiff triple helices forming continuous network, and the Lentinan gel is structurally more like a solution that is unable to flow within a timescale of usual observation.     

Electrospinning of linear homopolymers of poly(methyl methacrylate): exploring relationships between fiber formation, viscosity, molecular weight and concentration in a good solvent

A series of seven linear homopolymers of poly(methylmethacrylate) ranging from 12,470 to 365,700 g/mol M_w, were utilized to further explore scaling relationships between viscosity and concentration in a good solvent at 25 °C and to investigate the impact of these relationships on fiber formation during electrospinning. For each of the polymers investigated, chain dimensions (hydrodynamic radius and radius of gyration) were measured by dynamic light scattering to determine the critical chain overlap concentration, c^*. The experimentally determined c^*, was found to be in good agreement with the theoretically determined value that was calculated by the criteria c^*∼1/[η], where the intrinsic viscosity was estimated from the Mark-Houwink parameters, K and a (at 25 °C in dimethyl formamide) obtained from the literature. The plot of the zero shear viscosity vs. c/c^* distinctly separated into different solution regimes, viz. dilute (c/c^*<1), semidilute unentangled (1<c/c^*<3) and semidilute entangled (c/c^*>3). The crossover between semidilute unentangled and semidilute entangled regimes in the present investigation occurred at c/c^*∼3, which, therefore, marked the onset of the critical chain entanglement concentration, c_e, according to the procedure utilized by Colby and co-workers [Colby RH, Rubinstein M, Daoud M. J de Phys II 1994;4(8):1299-310. [52]]. Electrospinning of all solutions was carried out at identical conditions to ascertain the effects of solution concentration, molecular weight, molecular weight distribution and viscosity on fiber formation and morphological features of the electrospun material. Only polymer droplets were observed to form from electrospinning of solutions in the dilute concentration regime due to insufficient chain overlap. As the concentration was increased, droplets and beaded fibers were observed in the semidilute unentangled regime; and beaded as well as uniform fibers were observed in the semidilute entangled regime. Uniform fiber formation was observed at c/c^*∼6 for all the narrow MWD polymers (M_w of 12,470-205,800 g/mol) but for the relatively broad MWD polymers (M_w of 34,070 and 95,800 g/mol), uniform fibers were not formed until higher concentrations, c/c^*∼10, were utilized. Dependence of fiber diameter on concentration and viscosity was also determined, viz. fiber dia∼(c/c^*)^3.1 and respectively. These scaling relationships were in general agreement with that observed by Mckee et al. [McKee MG, Wilkes GL, Colby RH, Long TE. Macromolecules 2004;37(5):1760-67. [33]].     

Critical role of the conformation of comonomer units in isomorphic crystallization of poly(hexamethylene adipate-co-butylene adipate) forming Poly(hexamethylene adipate) type crystal

The isothermal crystallization of isomorphic Poly(hexamethylene adipate-co-butylene adipate) [P(HA-co-BA)], with the HA unit content ranged from 100 to 45 mol%, forming the Poly(hexamethylene adipate) [PHA] type crystal was investigated with DSC, FTIR and WAXD. The BA units were found adopting their all-trans conformation in the crystalline phase of PHA type crystal. The inclusion of the BA units into the PHA type crystal was highly preferred in the isothermal crystallization at 25 °C. The exclusion of the BA units from the crystalline phase of the PHA type crystal was enhanced by elevating the crystallization temperature (T_c), depending on the content of comonomer units. Increasing the HA unit content enhances the formation of the all-trans conformation of the BA units in the PHA type crystal. At low T_c, such an enhancement significantly helps in retarding the exclusion of the BA units from the PHA type crystalline lattice. On the other hand, at high T_c, the difficulty for forming the stable all-trans conformation of the BA units in cocrystal increased and hence the exclusion of the BA units from the cocrystal was accelerated. In conclusion, the all-trans conformation of the BA units can also play a critical role in the isomorphic crystallization of the P(HA-co-BA)s forming the PHA type crystal.     

A Common Target of Nitrite and Nitric Oxide for Respiration Inhibition in Bacteria

Nitrite and nitric oxide (NO) are well-known bacteriostatic agents with similar biochemical properties. However, many studies have demonstrated that inhibition of bacterial growth by nitrite is independent of NO. Here, with Shewanella oneidensis as the research model because of its unusually high cytochrome (cyt) c content, we identify a common mechanism by which nitrite and NO compromise cyt c biosynthesis in bacteria, and thereby inhibit respiration. This is achieved by eliminating the inference of the cyclic adenosine monophosphate-catabolite repression protein (cAMP-Crp), a primary regulatory system that controls the cyt c content and whose activity is subjected to the repression of nitrite. Both nitrite and NO impair the CcmE of multiple bacteria, an essential heme chaperone of the System I cyt c biosynthesis apparatus. Given that bacterial targets of nitrite and NO differ enormously and vary even in the same genus, these observations underscore the importance of cyt c biosynthesis for the antimicrobial actions of nitrite and NO.     

Fracture toughness of autoclaved portland cement/silica mixtures

Fracture toughness measurements made at 11% RH on autoclaved cement/silica mixtures having a wide range of silica contents and porosities yielded a series of curves for K_c versus porosity and K_c versus silica content. Those for preparations having low porosity and silica content were unique. Apparently αC₂S-hydrate, unreacted silica and pores having specific size distribution can act as crack arrestors. K_c versus hardness curves were similar to those for K_c versus porosity. Simple microhardness tests may be useful in predicting fracture toughness of autoclaved cementitious systems.     

Choked flow and importance of Mach I in freeze-drying process design

Occasionally the freeze drying cycle conditions are developed on a small scale dryer that result in a water vapor flux during primary drying that the full-scale equipment cannot handle, resulting in loss of the ability to control chamber pressure. A primary cause of loss of pressure control is a phenomenon commonly described as “choked flow”, where the required mass transfer through the duct connecting the drying and condenser chamber cannot be maintained at the control pressure. Water vapor flow rate increases as the condenser pressure decreases, but it can continue to do so only until the velocity of water vapor reaches speed of sound (i.e., Mach I) at the duct exit. The flow is then said to be choked, and any further increase in water vapor flow rate results in an increase in chamber pressure (i.e., loss in chamber pressure control). Sublimation tests were carried out in Lyostar II freeze-dryer (SP Industries, NY) to predict the occurrence of choked flow. A capacitance manometer was installed in the “condenser chamber” and differential pressure (P_c?P_cd) was measured as a function of sublimation rate (P_c=chamber pressure and P_cd=condenser pressure). Water vapor flow rate was measured by Tunable Diode Laser Absorption Spectroscopy (TDLAS) methodology, with a check by gravimetric data. Flow of water vapor in the duct connecting chamber and the condenser was modeled using computational fluid dynamics software (Fluent 6.3). The critical pressure ratio (K?=P_c/P_cd) has been identified as an important variable that determines the onset of choked flow during primary drying. This ratio can be calculated given the mass flux. For our freeze-dryer, K* greater than 2.5 (for P_c<150 mTorr) resulted in choked flow. The gas velocity indeed reaches Mach I limit at the duct exit under the choked flow conditions, as modeled by Fluent. Using the differential pressure measurements, the throat connecting the chamber and the condenser can be used as an “in process” mass flow meter to measure sublimation rate under non-choked flow conditions during primary drying without interrupting the process. Also, TDLAS is a useful tool for determination of sublimation rate even at very high mass flux.     

Selective Enrichment of Conjugated Linoleic Acid Isomers in Their Mixtures Using Combined Chemical and Enzymatic Methods

The aim of this study was to selectively enrich t10,c12-conjugated linoleic acid (t10,c12-CLA) and c9,t11-CLA in commercial CLA mixtures using a combination of urea crystallization and lipase-catalyzed esterification. The objective of the urea fractionation is to remove saturated and monounsaturated fatty acids (FA) from the CLA mixtures. CLA-enriched free FA (FFA) mixtures containing 53.8 wt% t10,c12-CLA and 39.1 wt% c9,t11-CLA were produced from the CLA mixtures containing ~34 wt% each of the two CLA isomers by a urea crystallization using methanol and the urea-to-FA weight ratio of 2.5:1. The CLA-enriched FFA mixtures were partially esterified with dodecan-1-ol in a recirculating packed-bed reactor using an immobilized lipase from Candida rugosa to further enrich the t10,c12-CLA and c9,t11-CLA in an FFA fraction and an FA dodecyl ester fraction, respectively, under the optimal conditions, i.e., temperature, 20 °C; FA-to-dodecan-1-ol molar ratio, 1:1; water content, 2 wt% of total substrates; residence time, 5 min; and reaction time, 24 h (for t10,c12-CLA enrichment) and 12 h (for c9,t11-CLA enrichment). After the reaction, an FFA fraction with 72.6 wt% t10,c12-CLA was obtained. Another FFA fraction with 62.0 wt% c9,t11-CLA was recovered after the saponification of the FA dodecyl ester fraction. The yields of t10,c12-CLA and c9,t11-CLA in the FFA fractions were 43.6 and 21.5 wt%, respectively, based on their initial weights in the CLA mixtures.