Synthesis and characterization of (S)-amino alcohol modified M41S as effective material for the enantioseparation of racemic compounds

A new chiral stationary phase (CSP) was synthesized based on (S)-1-anilino-3-propyl-2-propanol covalently bonded to the mesoporous semi-crystalline material M41S. Direct semipreparative enantioseparation of mandelic acid could be achieved using medium pressure chromatography. Partly separated could also be the enantiomers of 2,2'-dihydroxy-1,1'-binaphthalene, cyanochromene oxide, diethyl tartrate and 2-phenyl propionic acid. The characterization of CSP was accomplished by microanalysis, cross polarized magic angle spinning (CP-MAS) 13C NMR, powder X-ray diffraction (XRD), FTIR, thermo-gravimetric analysis (TGA), N2 adsorption-desorption isotherm, scanning electron microscopy (SEM) and solid reflectance UV-vis spectroscopy. Furthermore the stability of CSP was satisfactory as it could withstand three washing and reuse experiments of enantioseparation of mandelic acid without loss in its performance.     

Simulative investigation of nonlinear distortion in single- and two-tone RoF systems using direct- and external-modulation techniques

In this paper, we investigated a Radio-over-Fiber (RoF) system consisting of two different system set-ups using direct- and external-laser modulation techniques to study frequency response. Further, second- and third-harmonic generations of single- and two-tone RoF systems have been studied. In this work, we also measured the electric Rf power of two receiving channels and BER at received optical power at different modulating Rf frequencies up to 20 GHz using EDFA or SOA amplifiers. The results have been compared for the electric Rf power of receiving channels obtained using a sin² Mach Zehnder modulator and a linear modulator, and an improvement in the received Rf power with linear modulator in comparison with the sin² modulator is observed.     

Evaluation of initiator systems for controlled and sequentially curable free‐radical/cationic hybrid photopolymerizations

Free‐radical/cationic hybrid photopolymerizations of acrylates and epoxides were initiated using a three‐component initiator system comprised of camphorquinone as the photosensitizer, an amine as the electron donor, and a diaryliodonium salt. Thermodynamic considerations revealed that the oxidation potential of the electron donor must be less than 1.34 V relative to SCE for electron transfer with the photoexcited camphorquinone to take place. This electron transfer leads to the production of the active centers for the hybrid polymerization (two radicals and a cation). Further investigation revealed that only a subset of electron donors that meet the oxidation potential requirement resulted in polymerization of the epoxide monomer; therefore, a second requirement for the electron donor (pK_b higher than 8) was established. Experiments performed using a combination of electron donors revealed that the onset of the hybrid system's cationic polymerization can be advanced or delayed by controlling the concentration and composition of the electron donor(s). These studies demonstrate that a single three‐component initiator system can be used to initiate and chemically control the sequential curing properties of a free‐radical/cationic hybrid photopolymerization and is a viable alternative to separate photoinitiators for each type of polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1747–1756, 2005     

Transition Metal–Free Sodium Borohydride Promoted Controlled Hydration of Nitriles to Amides

A transition metal–free process, promoted by sodium borohydride, has been developed for convenient and selective hydration of nitriles to corresponding amides. The present process converts the aromatic, aliphatic, and heteroaromatic nitriles with wide functional group tolerance. The regioselective hydration of one nitrile moiety in the presence of an other nitrile group makes high impact in the present protocol.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

Versatile Synthetic Strategy for Coating Upconverting Nanoparticles with Polymer Shells through Localized Photopolymerization by Using the Particles as Internal Light Sources

We present a straightforward and generic strategy for coating upconverting nanoparticles (UCPs) with polymer shells for their protection, functionalization, conjugation, and for biocompatibility. UCPs are attracting much attention for their potential use as fluorescent labels in biological applications. However, they are hydrophobic and non‐compatible with aqueous media; thus prior surface modification is essential. Our method uses the internal UV or visible light emitted from UCPs upon photoexcitation with near‐infrared radiation, to locally photopolymerize a thin polymer shell around the UCPs. In this way, a large variety of monomers with different chemical functionalities can be incorporated. If required, a second layer can be added on top of the first. Our method can provide a large spectrum of surface functional groups rapidly and in one pot, hence offering a platform for the preparation of libraries of functional polymer‐encapsulated UCPs for applications in bioassays, biosensing, optical imaging, and theranostics.     

Structural Determination of an Unusual CuI-Porphyrin-π-Bond in a Hetero-Pacman Cu-Zn-Complex

The synthesis and characterization of a hetero-dinuclear compound is presented, in which a copper(I) trishistidine type coordination unit is positioned directly above a zinc porphyrin unit. The close distance between the two coordination fragments is secured by a rigid xanthene backbone, and a unique (intramolecular) copper porphyrin-π-bond was determined for the first time in the molecular structure. This structural motif was further analyzed by temperature-dependent NMR studies: In solution at room temperature the coordinative bond fluctuates, while it can be frozen at low temperatures. Preliminary reactivity studies revealed a reduced reactivity of the copper(I) moiety towards dioxygen. The results adumbrate why nature is avoiding metal porphyrin-π-bonds by fixing reactive metal centers in a predetermined distance to each other within multimetallic enzymatic reaction centers.     

Liquid–liquid extraction of uranium(VI) from weak sodium acetate medium using 2-octylaminopyridine: real sample analysis

Journal of Radioanalytical and Nuclear Chemistry - The analytical technique has been developed for the extraction and determination of uranium(VI). This process is based on the ion-pair complex...     

Registration temperature effect on sensitivity of CR-39(DOP) and SR-90 polymer track detectors

The samples of CR-39(DOP) and SR-90 polymer track detectors have been exposed to -particles from ²⁴¹Am source in an exposure unit. The temperature of the detectors during irradiation has been varied from −30°C to 70°C. These exposed samples have been etched in 6.25 N NaOH solution at 60°C for various etching times. The variation of sensitivity of these detectors as a function of registration temperature has been studied. It has been observed that at the fixed registration temperature, the sensitivity of SR-90 is more than CR-39(DOP) polymer track detector. However, the enhancement in sensitivity with the decrease in registration temperature is more pronounced in case of CR-39(DOP) than SR-90.     

Dark‐cure studies of cationic photopolymerizations of epoxides: Characterization of the active center lifetime and kinetic rate constants

We have characterized the effective rate constants for termination/trapping (k_t/t) and propagation (k_p) for solvent‐free cationic photopolymerizations of phenyl glycidyl ether for conversions up to 50%. We have performed dark‐cure experiments in which active centers are produced photochemically for a specified period of time until the initiating light is shuttered off, and then the polymerization rate is monitored in the dark. This method is especially well suited for characterizing cationic polymerizations because of the long active center lifetimes. Our analysis provides profiles of the instantaneous kinetic rate constants as functions of conversion (or time). For photopolymerizations of phenyl glycidyl ether initiated with iodonium photoinitiators, k_t/t and k_p remain essentially invariant for conversions up to 50%. For the photoinitiator (tolycumyl) iodonium tetrakis (pentafluorophenyl) borate (IPB), the values of k_t/t at 50 and 60 °C are 0.027 and 0.033 min^?1, respectively. The corresponding values of k_t/t for diaryliodonium hexafluoroantimonate (IHA) are 0.041 and 0.068 min^?1. The values of k_p at 50 °C for IPB and IHA are 0.6 and 0.4 L mol^?1 s^?1, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2064–2072, 2003     

Analysis of a Disc-Loaded Circular Waveguide for Interaction Impedance of a Gyrotron Amplifier

A rigorous electromagnetic analysis of a circular waveguide loaded with axially periodic annular discs was developed in the fast-wave regime, considering finite axial disc thickness and taking into account the effect of higher order space harmonics in the disc-free region and higher order modal harmonics in the disc-occupied region of the structure. The quality of the disc-loaded circular waveguide was evaluated with respect to its azimuthal interaction impedance that has relevance to the gain of a gyrotron millimeter-wave amplifier (gyro-traveling-wave tube) in which such a loaded waveguide finds application as a wideband interaction structure. The results of electromagnetic analysis of the structure with respect to both the dispersion and azimuthal interaction impedance characteristics were validated against the commercially available code: high frequency structure simulator (HFSS). The analysis predicts that the value of the interaction impedance at a given frequency decreases with the increase of the disc hole radius and disc periodicity. The change of the axial disc thickness does not significantly change the value of the interaction impedance though it shifts the frequency range over which appreciable interaction impedance is obtained. Out of the three disc parameters, namely the disc hole radius, thickness and periodicity, the lattermost is most effective in controlling the value of the azimuthal interaction impedance. However, the passband of frequencies and the center frequency of the passband both decrease with the increase of the disc periodicity. Moreover, the disc periodicity that provides large azimuthal interaction impedance would in general be different from that giving the desired dispersion shape for wideband interaction in a gyro-TWT, suggesting a trade-off in the value of the disc periodicity to be chosen.