Single-layer one-dimensional nonpolarizing guided-mode resonance filters under normal incidence

We demonstrate that properly designed one-dimensional guided-mode resonance filters (GMRFs) with only one grating layer can exhibit a nonpolarizing resonant filtering effect under normal incidence. A sinusoidal profile nonpolarizing GMRF is realized by photoinduced surface-relief grating formation on thin films of polymer-azobenzene complexes and subsequent atomic layer deposition, showing the feasibility of fabrication of such compact GMRFs.     

Effect of Physical Properties and Emulsification Conditions on the Microsphere Size Prepared Using a Solvent Extraction Process

Microspheres were prepared using a hydrocarbon-perfluorocarbon solvent extraction process. The effect of the physical properties and the emulsification conditions on the mean microsphere size was investigated. The viscosity of the dispersed and the continuous phase greatly affected the microsphere size. Smaller microspheres were produced at the same mixing intensity when the viscosity of the dispersed phase decreased. Increased continuous phase viscosity reduced the coalescenceof the droplets and hence smaller microspheres were produced. The mean microsphere size first decreased as the volume ratio of the dispersed phase to the continuous phase increased but upon further increase the mean microsphere size increased. The effect of the volume ratio on the microsphere size was linked to the surfactant concentration. The stability of the studied hydrocarbon-in-fluorocarbon emulsion is poor. One reason for the poor stability is the high density difference between the phases. The emulsion droplets were solidified by siphoning part of the emulsion in the fresh continuous phase, which extracted the solvent from the dispersed phase. The effect of emulsion transfer time between the emulsification and solidification steps on the particle size was studied but no significant effect was observedduring the controlled time interval.     

Frustrated Lewis Pair Chemistry of Chiral (+)‐Camphor‐Based Aminoboranes

Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C₆F₅)₂, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C₆F₅)₂ N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C₆F₅)₂ adduct. When the starting enamine is present in excess over HB(C₆F₅)₂, the produced bornylamine–HB(C₆F₅)₂ adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C₆F₅)₂ pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion.     

Palladium and Platinum Complexes from Methyl(2-Thienyl) Chalcogenides and BIS(2-Thienyl) Dichalcogenides

The preparation of [M(C₄H₃SECH₃)₂Cl₂] (M = Pd, Pt; E = Se, Te) and [Pd₆Te₆(C₄H₃S)₂(PPh₃)₆Cl₂] from methyl(2-thienyl)chalcogenides and bis(2-thienyl) ditelluride is reported. The products are identified and characterized by X-ray crystallography and by ⁷⁷Se and ¹²⁵Te NMR spectroscopy.     

Bank branch sales evaluation using extended value efficiency analysis

This article results from our collaborative project with a Finnish bank aiming to evaluate the sales performance of bank branches. The management wishes to evaluate the branches’ ability to generate profit, which rules out the pure technical efficiency considerations. The branches operate in heterogeneous environments. We deal with the heterogeneity by subdividing the branches according to the bank specification into overlapping clusters and analyze each cluster separately. The prices of the branch outputs are hard to assess as the results from the sales efforts can only be observed with long delays. We employ benchmark units similarly as in value efficiency analysis (VEA). However, we extend VEA in two ways. First, in standard VEA the benchmark unit is assumed to yield the maximum profit among the set of feasible technologies; instead, our benchmark technology may or may not be in the feasible set. Second, we consider efficiency tests employing a benchmark with respect to both profit and return. We propose a solution strategy for these extensions. The bank uses the study to support decisions concerning new branches, changes in the operations of inefficient branches, and actions aiming to more flexible deployment of the staff.     

Molecular tweezers for hydrogen: synthesis, characterization, and reactivity

The first ansa-aminoborane N-TMPN-CH2C6H4B(C6F5)2 (where TMPNH is 2,2,6,6-tetramethylpiperidinyl) which is able to reversibly activate H2 through an intramolecular mechanism is synthesized. This new substance makes use of the concept of molecular tweezers where the active N and B centers are located close to each other so that one H2 molecule can fit in this void and be activated. Because of the fixed geometry of this ansa-ammonium-borate it forms a short N-H...H-B dihydrogen bond of 1.78 A as determined by X-ray analysis. Therefore, the bound hydrogen can be released above 100 degrees C. In addition, the short H...H contact and the N-H...H (154 degrees) and B-H...H (125 degrees) angles show that the dihydrogen interaction in N-TMPNH-CH2C6H4BH(C6F5)2 is partially covalent in nature. As a basis for discussing the mechanism, quantum chemical calculations are performed and it is found that the energy needed for splitting H2 can arise from the Coulomb attraction between the resulting ionic fragments, or "Coulomb pays for Heitler-London". The air- and moisture-stable N-TMPNH-CH2C6H4BH(C6F5)2 is employed in the catalytic reduction of nonsterically demanding imines and enamines under mild conditions (110 degrees C and 2 atm of H2) to give the corresponding amines in high yields.     

Platinum and Palladium Complexes Bearing New (1R,2R)‐(–)‐1,2‐Diaminocyclohexane (DACH)‐Based Nitrogen Ligands: Evaluation of the Complexes Against L1210 Leukemia

The reaction of (1R,2R)‐(–)‐1,2‐diaminocyclohexane ( 1 ) [DACH] with the aldehyde (1R)‐(–)‐myrtenal ( 2 ) in MeOH afforded the bidentate diimine ligand, (1R,2R)‐(–)‐N¹,N²‐bis{(1R)‐(–)myrtenylidene}‐1,2‐diaminocyclohexane ( 3 ) in a high yield. Reduction of 3 using LiAlH₄ led to the formation of the desired ligand ( 4 ) (1R,2R)‐(–)‐N¹,N²‐bis{(1R)‐(–)myrtenyl}‐1,2‐diaminocyclohexane. Treatment of compound 4 with K₂PtCl₄ or K₂PdCl₄ yielded the corresponding platinum(II) and palladium(II) complexes, Pt‐5 and Pd‐6 , respectively. The reaction of compound 3 with K₂PtCl₄ gave the diimine complex Pt‐7 . The cytotoxic activity of the complexes Pt‐5 , Pd‐6 and Pt‐7 was tested and compared to the approved drugs, cisplatin ( Cis ‐Pt ) and oxaliplatin ( Ox‐Pt ). The complexes ( Pt‐5 , Pd‐6 and Pt‐7 ) inhibit L1210 cell line proliferation with an IC₅₀ of 0.6, 4.2, and 0.7 μL, respectively as evidenced by measuring thymidine incorporation.     

Self-assembled carbon nanotubes on gold: polarization-modulated infrared reflection-absorption spectroscopy, high-resolution X-ray photoemission spectroscopy, and near-edge X-ray absorption fine structure spectroscopy study

Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk.     

Water dynamics--the effects of ions and nanoconfinement

Hydrogen bond dynamics of water in highly concentrated NaBr salt solutions and reverse micelles are studied using ultrafast 2D-IR vibrational echo spectroscopy and polarization-selective IR pump-probe experiments performed on the OD hydroxyl stretch of dilute HOD in H(2)O. The vibrational echo experiments measure spectral diffusion, and the pump-probe experiments measure orientational relaxation. Both experimental observables are directly related to the structural dynamics of water's hydrogen bond network. The measurements performed on NaBr solutions as a function of concentration show that the hydrogen bond dynamics slow as the NaBr concentration increases. The most pronounced change is in the longest time scale dynamics which are related to the global rearrangement of the hydrogen bond structure. Complete hydrogen bond network randomization slows by a factor of approximately 3 in approximately 6 M NaBr solution compared to that in bulk water. The hydrogen bond dynamics of water in nanoscopically confined environments are studied by encapsulating water molecules in ionic head group (AOT) and nonionic head group (Igepal CO 520) reverse micelles. Water dynamics in the nanopools of AOT reverse micelles are studied as a function of size by observing orientational relaxation. Orientational relaxation dynamics deviate significantly from bulk water when the size of the reverse micelles is smaller than several nm and become nonexponential and slower as the size of the reverse micelles decreases. In the smallest reverse micelles, orientational relaxation (hydrogen bond structural randomization) is almost 20 times slower than that in bulk water. To determine if the changes in dynamics from bulk water are caused by the influence of the ionic head groups of AOT or the nanoconfinement, the water dynamics in 4 nm nanopools in AOT reverse micelles (ionic) and Igepal reverse micelles (nonionic) are compared. It is found that the water orientational relaxation in the 4 nm diameter nanopools of the two types of reverse micelles is almost identical, which indicates that confinement by an interface to form a nanoscopic water pool is a primary factor governing the dynamics of nanoscopic water rather than the presence of charged groups at the interface.