Structure elucidation of fluorescent H1 antihistamines by ultraviolet resonance Raman spectroscopy: solvent structures of tripelennamine and mepyramine

Ultraviolet Resonance Raman (UVRR) spectroscopy—a Raman technique that combines high sensitivity with high selectivity and does not suffer from background fluorescence—is applied to the fluorescent H₁ antihistamines tripelennamine (TRP) and mepyramine (MEP) in aqueous solution to elucidate their molecular structure as a function of pH. In a previous investigation of these compounds (C. Tardioli, G. Gooijer G. van der Zwan, J. Phys. Chem. B, 113 , (2009), 6949), the presence of gauche conformers caused by intramolecular interaction of the protonated alkylamine tail with the pyridine nitrogen was assumed to explain the pH dependence of the fluorescence properties. In order to validate this assumption, use is made of the resonant excitation of the aminopyridine chromophore in TRP and MEP. In that way, structural information associated with the vibrations of that moiety can be obtained, and the changes it undergoes upon protonation can be monitored. Assignment of the vibrations was achieved with the help of a number of other compounds, and quantum chemical calculations. N,N‐Dimethylaminopyridine (2DMP) and its mono‐protonated form (2DMPH⁺) were investigated, since this molecule was shown to have optical properties closely resembling those of the aminopyridine moiety in TRP and MEP. Assignment of the vibrations of 2DMP was accomplished by comparison with the resonance Raman spectra of two other reference structures, 2‐aminopyridine and dimethylaniline—for which ordinary Raman data are available—and by Gaussian calculations. UVRR spectra of TRP and MEP could be readily interpreted on the basis of vibrational assignments of the parent chromophores, i.e. 2DMP and 2DMPH⁺. Vibrations of the aminopyridine chromophore in TRP and MEP at neutral pH, where the aminoalkyl chain is protonated, are modified when compared to the vibrational pattern recorded for a fully neutral molecule in alkaline solution. This implies an electronic redistribution in the ring originating from internal hydrogen bonding between the aminoalkyl tail and the aminopyridine chromophore. Copyright © 2010 John Wiley & Sons, Ltd.     

Amino‐Acid‐Based Zwitterionic Polymer and Its Cu(II)‐Induced Aggregation into Nanostructures: A Template for CuS and CuO Nanoparticles

A convenient and water‐based approach is described for the synthesis of an l ‐lysine‐based zwitterionic polymer, poly(ε−l ‐lysinyl acrylamide) (PLAM), without using protecting group chemistry, chromatographic purifications, and organic solvents as the reaction media. PLAM contains both amine and carboxylic acid groups in each repeating unit, which can either be protonated or deprotonated just by altering the pH of the solution to obtain overall positive or negative charge. PLAM is tested for its applicability as a zwitterionic polymeric buffer in water. Cu(II) ion‐induced aggregation of PLAM as a function of solution pH is studied. Spherical nanogel aggregates are formed at pH 9.5 due to aggregation of PLAM through its complexation with Cu(II) ion. Spherical aggregates appear to dissociate via breaking of the complexation at a pH < 5.5 resulting in molecular dissolution of PLAM. This aggregation process is pH reversible. The Cu(II)–PLAM aggregates are used as a template for fabrication of CuO and CuS nanoparticles.

     

pH‐Switchable Macroscopic Assembly through Host–Guest Inclusion

A novel pH‐switchable macroscopic assembly is reported using alginate‐based hydrogels functionalized with host (α‐cyclodextrin, αCD) and guest (diethylenetriamine, DETA) moieties. Since the interaction of αCD and DETA is pH sensitive, the host hydrogel and guest hydrogel could adhere together when the pH is 11.5 and separate when the pH is 7.0. Furthermore, this pH‐controlled adhesion and dissociation shows a good reversibility. The host and guest polymers have good biocompatibility; therefore, this pH‐sensitive macroscopic assembly shows great potential in biotechnological and biomedical applications.

     

pH-Induced Changes in the Secondary Structure of Cytochrome c: an Infrared Spectroscopic Study

The infrared spectra of 3mM solutions of horse heart cytochrome c were recorded as a function of pD(corresponding to acid high spin form, acidic low spin form, native form, lysine form, the so-termed “strained lysine form” as well as the so-termed “A state” of cytochrome c). An analysis of the pH-induced changes in the secondary structure was performed based on changes in the conformation-sensitive amide I bands of this protein. In lysine and strained lysine forms, the contents of random structure increase at the expense of α-helix. In acidic low. spin form (pH4–2.5), cytochrome c was almost unfolded. The proportion of α-helix had a substantial decrease while the contents of both random structure and 3₁₀-helices got a rise. In acidic high spin form (when pH is below 2.5), a further decrease of pD gave no rise to a continued unfolding in cytochrome c but made it refold to the “A state” with properties similar to those of a molten globular state. Adding enough KC1 to the cytochrome c solution(pD2.2 with 0.5MKC1 and pD3.0 with 1.5 MKCl) in which cytochrome c was nearly fully unfolded also led to the formation of A state of cytochrome c. The compositions of all types of secondary structures in A state were evaluated. The behavior of 3₁₀-helices in acidic high/low spin form indicated they might be intermediates between α-helices and random structure in acidic solution as proposed by Miick et al.     

Solvent and pH Effects on the Sign of the ORD Spectrum of N-Methyl-4-phenyl-7-methoxy-1,2,3,4-tetrahydroisoquinoline in the Visible Spectral Range

It has been described in the literature¹ that the protonation of the nitrogen in 1-benzyl-1,2,3,4-tetraisoquinoline derivatives does not affect the sign of the ORD spectra. We have recently observed² that in the case of several (R) and (S) N-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinol ine derivatives this is true only for the three Cotton effects below 300 nm (the ¹L_b, ¹L_a and ¹B electronic transitions³ of the aromatic moiety), although appreciable variations in intensity and slight shifts in the positions of the extrema were also noticed. On the other hand, the sign of the rotation in the visible spectral range was reversed upon protonation in 0.1N methanolic HCl (or hydrochloride of 1 in methanol).     

Luminescence-Based Optical Fiber Chemical Sensors

Abstract

A scheme for the simultaneous determination of temperature and analyte concentration for application in luminescence-based chemical sensors is proposed. This scheme is applied to an optical oxygen sensor, which is based on the quenching of the fluorescence of a ruthenium complex. Temperature measurement is performed using the excitation radiation and an absorption long-pass filter. Preliminary results are presented that show the viability of an oxygen measurement that is independent of temperature and optical power level. The possibility of self-referenced temperature measurements with semiconductor nanoparticles is also investigated. In order to optimize the sensor design, several different optical fiber probe geometries for oxygen sensing are tested and compared, including different methods of coupling radiation into the optical fiber system. Polyvinyl alcohol (PVA) and polyacrylamide membranes are tested as supports for sensor immobilization in fiber-optical pH sensing devices in aqueous solution. Some results are presented that show the feasibility of using fiber-optical pH indicators for remote monitoring.     

Fiber-Optic pH Sensor

The new enhancement in the determination of pH using optical fiber system is described here. This work uses the membrane made of cellulose acetate membrane for reagent immobilization and congo red (pK _a 3.7) and neutral red (pK _a 7.2) as pH indicators. An effective covalent chemical binding procedure is used to immobilize the indicators. The response time, reversibility, linear range, reproducibility, and long-term stability of fiber optic sensor with congo red as well as neutral red have been determined. The linear range measured for the sensor based on the congo red and neutral red is 4.2–6.3 and 4.1–9.0, respectively. The response time of sensor membrane is measured by varying the substance pH values between 11.0 and 2.0.     

Surface‐enhanced Raman evidence for Rhodamine 6 G and its derivative with different adsorption geometry to colloidal silver nanoparticle

Some high‐affinity functional groups or resonant molecules were often used as probe molecules adsorbed on silver nanoparticles for Surface‐enhanced Raman scattering (SERS). However, it is still unclear how the attached molecules interact with the silver nanoparticles' surface, and how the anchoring groups affect the optical and electronic properties of molecules. Here, we report that surface‐enhanced Raman studies of two organic compounds; rhodamine 6G (R6G) and its aminated derivative (R‐NH₂) have very different functional groups for surface binding but nearly identical SERS spectroscopic properties at pH = 7 and UV–vis at pH = 3, respectively. A surprise was found that under the same experimental conditions, the SERS signal intensity for R6G is nearly 50‐fold higher than that of R‐NH₂. Furthermore, the pH‐dependent study reveals that the structure of R6G is irreversibly stabilized or ‘locked’ in its form and no longer responsive to pH changes. In contrast, R‐NH₂ is still sensitive to pH, and can be switched between its open‐ring and closed‐ring structures. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of pH and high pressure at sub-zero temperature on the viability of some bacteria

The objective of this study was to investigate the viability of Escherichia coli and Staphylococcus aureus in apple juice after treatment with high pressure at sub-zero temperature and during subsequent storage at 5 and 20 °C. The viability of E. coli and S. aureus cells suspended in the apple juice with a pH of 3.8 did not decrease considerably after pressure treatment at 193 MPa and?20 °C. However, viability losses occurred during storage of samples after pressure treatment. Living cells of both strains were not detected in pressurized samples of apple juice stored for 10 days at 20°C. The lethal effect was lower when the samples after pressure treatment were incubated at refrigerated temperature; the number of E. coli and S. aureus decreased by 6 log cycles when the juice was stored for 10 days at 5 °C.     

前驱液pH值对2ZnO·2.2B2O3·3H2O∶Eu3+荧光粉发光性能的影响

采用水热法,通过氨水调节前驱液的pH值,制备了一系列2ZnO.2.2B2O3.3H2O∶Eu3+样品。对所制备的样品进行X射线衍射和荧光光谱分析。研究结果表明:前驱液的pH值影响2ZnO.2.2B2O3.3H2O的结晶程度,在中性条件下制备的样品结晶度最好。当前驱液的pH=5.7时,激发光谱中的Eu-O电荷迁移带的峰位波长最大(262 nm),这可能是由于在此条件下合成的样品中Eu-O键长最长。发射光谱表明:当前驱液的pH>5.7时,Eu3+的发射光谱中的红橙比(I614/I589)随pH值的增大而增大,且当前驱液的pH值在5.7～6.9区间,红橙比(I614/I589)随pH值的增大的速率要比pH值在6.9～9.3之间增加的速率要快。另外,随着pH值的增大,样品的发光强度呈先增大后减小的变化趋势。当前驱溶液pH=8.1时,样品的发光强度最大。