General Information to Obtain Spherical Particles with Ordered Mesoporous Structures

Conditions for the synthesis of aluminum organophosphonate (AOP) and aluminophosphate (AlPO) spheres containing periodic mesopores were optimized and demonstrated to be general morphological controls for the surfactant‐assisted synthesis of mesoporous materials. High‐quality AOP and AlPO spheres with uniform mesopores were obtained at low and high temperatures, respectively. The aerosol‐assisted synthesis of materials with uniform mesopores was categorized by using the difference in relative density of soluble AOP and AlPO oligomers that interact with ethylene oxide (EO) units in EO_nPO_mEO_n triblock copolymer (PO=propylene oxide). Then, ordered mesoporous structures are constructed with the adequate amount of species in resultant frameworks, and the number of interactive points in soluble species determines the resultant density of the frameworks after self‐assembly. Consequently, temperature‐dependent synthesis, which allows controlled infiltration of soluble species to match the density of resultant frameworks, is required for the formation of ordered mesoporous structures under morphological control.     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010     

Synthesis of well‐defined and end‐polymerizable star‐shaped polysulfides and their application to negative photoresist

Various star‐shaped poly(phenoxy propylene sulfide)s (PPSs) bearing curable end groups were synthesized by the functionalization of the propagating ends of star‐shaped poly(PPS) with various electrophilies. The functionalization with chloromethyl styrene proceeded quantitatively, and afforded polymers with M_n almost agreed with theoretical value and narrow M_w/M_n. The photocuring conditions were optimized, and the addition of 10 wt % of poly(ethylene glycol) diacrylate was effective to attain sufficient crosslinking. The photocuring reaction of the end‐functionalized poly(PPS) films cast on silicon wafers was conducted by UV irradiation. The cured poly (PPS)s became insoluble in THF, supporting the sufficient crosslinking. Developing of a cured polymer yielded a negative photoresist pattern. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Steady-State and Time-Resolved Fluorescence Spectroscopic Studies on Interaction of the N-terminal Region with the Hairpin Loop of the Phytocystain Scb

The steady-state and time-resolved fluorescece spectroscopy is one of the most powerful method to detect and analyze subtle conformation change and interaction between peptide elements in protein. Phytocystatin Scb isolated from sunflower seeds includes a single Trp residue at position 85. In an attempt to investigate the interaction of the N-terminal region of Scb with the first and second hairpin loops by fluorescence spectroscopy of Trp residue, two Scb mutants in which single Trp locates at position 52 and 58, respectively, and their N-terminal removed mutants were generated. The N-terminal truncation changed the fluorescence decay kinetics of Trp52 from the triple exponential to double. Furthermore, the time-resolved fluorescence anisotropy residue indicated that the segmental motion of Trp52 was significantly enhanced by its N-terminal truncation. In contrast, Trp58 and Trp85 had little influence. The N-terminal successive truncations of Scb and its mutants resulted in the weaken inhibitors to papain. These results suggested that the N-terminal region of Scb interacts with the peptide segment preceding the first hairpin loop, thereby stabilizing the conformation of the hairpin loop structure.     

Cycle time as a variable in CRAMPS NMR. Detection of minor impurities in solids to levels of ≤0.01 mol%

The use of varying multiple-pulse decoupling cycle times in homonuclear dipolar decoupling experiments with combined rotation and multipole-pulse spectroscopy proton nuclear magnetic resonance (NMR) is shown to be capable of quantitatively and qualitatively analyzing amounts of occluded residual liquid solvent, present as saturated solution, in some organic solids crystallized from solution. Lower limits of detection can be 0.01 mol%, as illustrated for the cases of durene,p-hydroxy benzoic acid, and adipic acid crystallized from ethanol, and alanine crystallized from water. Quantitative detection at this level depends upon the phase diagram of the system in question, and the ability to obtain a high-resolution proton NMR spectrum from that portion of the sample consisting of the occluded solvent impurity in the presence of a relatively large proton background from the probe. Determinations of spin diffusion may be used to infer the average size of the mobile domains containing the impurity. The variation of longitudinal relaxation time with temperature may be used as a check on the uniformity of saturated solvent occluded in the system studied. The classical case of using a cooling curve to detect the total amount of liquid protion remaining in the crystal after crystallization is discussed.     

Triggered single-photon emission and cross-correlation properties in InAlAs quantum dot

Triggered single-photon generation from InAlAs quantum dot (QD) was demonstrated for the first time. Emitted photon energy coincides with high detection efficiency range of Si single-photon detectors, which is highly suitable for free-space communication. Single-QD spectroscopy and crossed photon correlation measurements unambiguously revealed that several emitting lines observed in a single mesa structure originated from the identical QD, and two temporary competing decay processes associated with neutral states and charged states were identified. Presence of the competing process is also inferred from an analysis of steady-state photoluminescence intensities. Formation process of charged exciton in QD is also discussed.     

Photocontrollable cation extraction with crowned oligo(spirobenzopyran)s.

The photoinduced changes of metal-ion extractability of crown ether derivatives bearing three or four spirobenzopyran moieties and their analogues were studied using 1,2-dichloroethane as the organic solvent. Under dark conditions, these compounds extracted Cu2+, Ag+, and Pb2+ with their counteranions from the aqueous phase to the organic phase. The extraction equilibrium constants of the photochromic crown ether derivatives for Cu2+ and Ag+ were determined successfully. Under UV-light irradiation conditions, the extraction of Cu2+ by crowned tris(spirobenzopyran) was enhanced, while that of Ag+ was suppressed. During the competitive metal-ion extraction of crowned oligo(spirobenzopyran)s between Cu2+ and Ag+, the metal-ion selectivity was reversed explicitly by photoirradiation.     

A non‐linear k–ε model with realizability for prediction of flows around bluff bodies

The incompressible flow around bluff bodies (a square cylinder and a cube) is investigated numerically using turbulence models. A non‐linear k–ε model, which can take into account the anisotropy of turbulence with less CPU time and computer memory then RSM or LES, is adopted as a turbulence model. In tuning of the model coefficients of the non‐linear terms are adjusted through the examination of previous experimental studies in simple shear flows. For the tuning of the coefficient in the eddy viscosity (=C_μ), the realizability constraints are derived in three types of basic 2D flow patterns, namely, a simple shear flow, flow around a saddle and a focal point. C_μ is then determined as a function of the strain and rotation parameters to satisfy the realizability. The turbulence model is first applied to a 2D flow around a square cylinder and the model performance for unsteady flows is examined focussing on the period and the amplitude of the flow oscillation induced by Karman vortex shedding. The applicability of the model to 3D flows is examined through the computation of the flow around a surface‐mounted cubic obstacle. The numerical results show that the present model performs satisfactorily to reproduce complex turbulent flows around bluff bodies. Copyright © 2003 John Wiley & Sons, Ltd.