Determining Equilibrium Fluctuations Using Temperature-Dependent 2D-IR

2013 ◽  
Vol 117 (49) ◽  
pp. 15346-15355 ◽  
Author(s):  
Adam D. Hill ◽  
Matthew C. Zoerb ◽  
Son C. Nguyen ◽  
Justin P. Lomont ◽  
Miriam A. Bowring ◽  
...  
1997 ◽  
Vol 51 (4) ◽  
pp. 526-535 ◽  
Author(s):  
Yukihiro Ozaki ◽  
Yongliang Liu ◽  
Isao Noda

This paper demonstrates the potential of generalized two-dimensional (2D) Fourier transform (FT) infrared (IR) and near-infrared (NIR) correlation spectroscopy in the studies of temperature-dependent spectral variations of self-associated molecules. Three examples of the 2D correlation analysis are discussed in this paper. The first two are concerned with the temperature-dependent IR and NIR spectral changes of N-methylacetamide (NMA) in the pure liquid state. The 2D IR correlation approach revealed that almost all the peaks of NMA in the 3400–1100-cm−1 region consist of two to four separate bands. For example, the amide I band contains contributions from at least four distinct bands at 1685, 1665, 1650, and 1635 cm−1. The analysis of the asynchronous 2D IR spectrum in the amide I region showed that the sequence of spectral intensity change in the ascending order of temperature was given by 1635<1650<1665<1685 cm−1. These bands at 1635, 1650, 1665, and 1685 cm−1 were assigned to the amide I modes of chain oligomers of various sizes and dimer of NMA; the longer the chain, the lower the frequency. The closeup view of 2D NIR correlation spectra of NMA obtained at narrow spectral and temperature windows enabled us to propose not only band assignments in the 6800–6050-cm−1 region but also a detailed mechanistic picture of the thermally induced dissociation of NMA for each temperature range. We also applied the generalized 2D correlation approach to the analysis of a set of FT NIR spectra of oleyl alcohol under temperature variations. The 2D NIR analysis enhanced the spectral resolution and simplified the spectra with overlapped bands. For example, it was found that a band at 7090 cm−1 arising from the first overtone of an OH stretching mode of the monomeric alcohol consists of two bands due to the rotational isomerism of the free OH group. An intriguing possibility of correlating various overtone and fundamental bands to establish unambiguous assignments was also suggested from the 2D NIR study on oleyl alcohol.


2010 ◽  
Vol 1 (7) ◽  
pp. 1068-1072 ◽  
Author(s):  
Rebecca A. Nicodemus ◽  
Krupa Ramasesha ◽  
Sean T. Roberts ◽  
Andrei Tokmakoff

Author(s):  
T.E. Pratt ◽  
R.W. Vook

(111) oriented thin monocrystalline Ni films have been prepared by vacuum evaporation and examined by transmission electron microscopy and electron diffraction. In high vacuum, at room temperature, a layer of NaCl was first evaporated onto a freshly air-cleaved muscovite substrate clamped to a copper block with attached heater and thermocouple. Then, at various substrate temperatures, with other parameters held within a narrow range, Ni was evaporated from a tungsten filament. It had been shown previously that similar procedures would yield monocrystalline films of CU, Ag, and Au.For the films examined with respect to temperature dependent effects, typical deposition parameters were: Ni film thickness, 500-800 A; Ni deposition rate, 10 A/sec.; residual pressure, 10-6 torr; NaCl film thickness, 250 A; and NaCl deposition rate, 10 A/sec. Some additional evaporations involved higher deposition rates and lower film thicknesses.Monocrystalline films were obtained with substrate temperatures above 500° C. Below 450° C, the films were polycrystalline with a strong (111) preferred orientation.


1990 ◽  
Vol 64 (03) ◽  
pp. 402-406 ◽  
Author(s):  
M D Oethinger ◽  
E Seifried

SummaryThe present in vitro study investigated dose-, time- and temperature-dependent effects of two-chain urokinase plasminogen activato(u-PA, urokinase) on normal citrated plasma. When 10 μg/ml u-PA wereadded to pooled normal plasma and incubated for 30 min at an ambient temperature (25° C), α2-antiplas-min decreased to 8% of the control value. Incubation on ice yielded a decrease to 45% of control,whereas α2-antiplasmin was fully consumed at 37° C. Fibrinogen and plasminogen fell to 46% and 39%, respectively, after a 30 min incubation at 25° C. Thrombin time prolonged to 190% of control.Various inhibitors were studied with respect to their suitability and efficacy to prevent these in vitro effects. Aprotinin exhibited a good protective effect on fibrinogen at concentrations exceeding 500 KlU/ml plasma. Its use, however, was limited due to interferences with some haemostatic assays. We could demonstrate that L-Glutamyl-L-Glycyl-L-Arginyl chloromethyl ketone (GGACK) and a specific polyclonal anti-u-PA-antibody (anti-u-PA-IgG) effectively inhibited urokinase-induced plasmin generation without interfering with haemostatic assays. The anti-u-PA-antibody afforded full protection ofα2-antiplasmin at therapeutic levels of u-PA.It is concluded that u-PA in plasma samples from patients during thrombolytic therapy may induce in vitro effects which should be prevented by the use of a suitable inhibitor such as GGACK or specific anti-u-PA-antibody.


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