Hydrogen exchange between the alkyl hydrogens of 1-amino-5, 5-dimethylhexane and sulfuric acid

The hydrogen exchange between 1-amino-5,5-dimethylhexane and sulfuric acid has been studied. In 97.5 wt.% sulfuric acid the exchange of methyl hydrogens with acidic protons can be observed at 175°C. The exchange of only one hydrogen atom takes place in one activation step.

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1--5,5- . 97,5 . %- . , .

     

High-resolution infrared spectrum of the nu1 Ba nd of eta5-C5H5NiNO

Gas-phase rotational constants and distortion constants have been determined for the nu1 (v=1) excited vibrational state of cyclopentadienylnickel nitrosyl (C5H5NiNO) using a high-resolution Fourier transform spectrometer system at Kitt Peak, Arizona. The rotationally resolved lines have been measured for the C-H symmetric stretch vibration (nu1=3110 cm(-1)). In the present analysis, over 150 lines have been assigned and fitted using a rigid-rotor Hamiltonian with centrifugal distortion. The vibrational band center, excited-state rotational constants, and distortion constants derived from the measured spectrum for this prolate symmetric-top molecule are nuo=3110.4129(4) cm(-1), A'=0.14328(8) cm(-1), B'=C'=0.041285(1) cm(-1), DJ'=0.078(1) kHz, DJK'=2.23(4) kHz, and DK'=-2.63(2) kHz, respectively. Several different combination differences, with a common upper state, were calculated for different K stacks for the observed spectra, and the consistency of the lower state rotational constants obtained provided further support for the current assignment. The ground-state rotational constant (B') derived from this combination differences analysis agrees with the previously obtained Fourier transform microwave value to within 0.15%. However, ground-state rotational constants, A' and B', have been fixed in the present analysis to avoid correlation effects and to get more accurate results. The new measured parameters are compared with the previously obtained results from Fourier transform microwave and infrared spectroscopy measurements. The C-H vibration stretching frequency and rotational constants were calculated using density functional theory calculations, and these were quite helpful in resolving ambiguities in the fitting procedure and for initial assignments of measured lines.     

Chemical Modification of Saccharomycopsis fibuligera R64 α-Amylase to Improve its Stability Against Thermal, Chelator, and Proteolytic Inactivation

α-Amylase catalyzes hydrolysis of starch to oligosaccharides, which are further degraded to simple sugars. The enzyme has been widely used in food and textile industries and recently, in generation of renewable energy. An α-amylase from yeast Saccharomycopsis fibuligera R64 (Sfamy) is active at 50 °C and capable of degrading raw starch, making it attractive for the aforementioned applications. To improve its characteristics as well as to provide information for structural study ab initio, the enzyme was chemically modified by acid anhydrides (nonpolar groups), glyoxylic acid (GA) (polar group), dimethyl adipimidate (DMA) (cross-linking), and polyethylene glycol (PEG) (hydrophilization). Introduction of nonpolar groups increased enzyme stability up to 18 times, while modification by a cross-linking agent resulted in protection of the calcium ion, which is essential for enzyme activity and integrity. The hydrophilization with PEG resulted in protection against tryptic digestion. The chemical modification of Sfamy by various modifiers has thereby resulted in improvement of its characteristics and provided systematic information beneficial for structural study of the enzyme. An in silico structural study of the enzyme improved the interpretation of the results.