Linear and Non-Linear Middle Infrared Spectra of Penicillin G in the CO Stretching Mode Region
<p>Penicillin G molecule (A) and its IR spectra (B) in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math> (blue line) and in <math display="inline"><semantics> <mrow> <mi>D</mi> <mi>M</mi> <mi>S</mi> <mi>O</mi> <mo>−</mo> <mi>d</mi> <mn>6</mn> </mrow> </semantics></math> (black line). Assignments are given: (1) <math display="inline"><semantics> <mrow> <mi>β</mi> <mo>−</mo> <mi>l</mi> <mi>a</mi> <mi>c</mi> <mi>t</mi> <mi>a</mi> <mi>m</mi> </mrow> </semantics></math><math display="inline"><semantics> <mrow> <mi>C</mi> <mi>O</mi> </mrow> </semantics></math> stretching; (2) <math display="inline"><semantics> <mrow> <mi>A</mi> <mi>m</mi> <mi>i</mi> <mi>d</mi> <mi>e</mi> <mi>I</mi> </mrow> </semantics></math>; (3) asymmetric stretching of carboxylate group. A large red shift of <math display="inline"><semantics> <mrow> <mi>A</mi> <mi>m</mi> <mi>i</mi> <mi>d</mi> <mi>e</mi> <mi>I</mi> <mi>I</mi> </mrow> </semantics></math> (A2), out of the frequency window, is observed upon proton exchange in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math>.</p> "> Figure 2
<p>Experimental (black) and calculated (red) IR spectra of Penicillin G in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math>.</p> "> Figure 3
<p>Experimental (black) and calculated (red) IR spectra of Penicillin G in <math display="inline"><semantics> <mrow> <mi>D</mi> <mi>M</mi> <mi>S</mi> <mi>O</mi> </mrow> </semantics></math>.</p> "> Figure 4
<p>Transient broadband parallel spectra in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math> (on the <b>left</b>) and in <math display="inline"><semantics> <mrow> <mi>D</mi> <mi>M</mi> <mi>S</mi> <mi>O</mi> <mo>−</mo> <mi>d</mi> <mn>6</mn> </mrow> </semantics></math> (on the <b>right</b>). The black dot lines represent simulations of the transient spectra obtained by summing the linear IR spectrum with its reversed one, shifted by the averaged value of anharmonicity (27 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math> for <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math> and 20 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math> for <math display="inline"><semantics> <mrow> <mi>D</mi> <mi>M</mi> <mi>S</mi> <mi>O</mi> <mo>−</mo> <mi>d</mi> <mn>6</mn> </mrow> </semantics></math>).</p> "> Figure 5
<p>Bi-exponential decay of excited state absorption and ground state recovery of <math display="inline"><semantics> <mrow> <mi>β</mi> <mo>−</mo> <mi>l</mi> <mi>a</mi> <mi>c</mi> <mi>t</mi> <mi>a</mi> <mi>m</mi> </mrow> </semantics></math> CO in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math>. Fitting is done starting from 200 fs. In the first 200 fs cross phase modulation phenomena due to temporal overlap between pump and probe occur.</p> "> Figure 6
<p>Narrowband experiment in <math display="inline"><semantics> <mrow> <msub> <mi>D</mi> <mn>2</mn> </msub> <mi>O</mi> </mrow> </semantics></math>: the dot line show the scaled intensities to the most intense signal recorded when the <math display="inline"><semantics> <mrow> <mi>β</mi> <mo>−</mo> <mi>l</mi> <mi>a</mi> <mi>c</mi> <mi>t</mi> <mi>a</mi> <mi>m</mi> </mrow> </semantics></math> at 1762 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math> is excited. In order to highlight cross peaks (black arrows) the spectrum has been 20 times enlarged. The presence of the cross peak due to the coupling between the <math display="inline"><semantics> <mrow> <mi>β</mi> <mo>−</mo> <mi>l</mi> <mi>a</mi> <mi>c</mi> <mi>t</mi> <mi>a</mi> <mi>m</mi> </mrow> </semantics></math> and the carboxylate is clearly visible while the cross peak with the amide I mode is hidden in the noise.</p> "> Figure 7
<p>Cross peaks in the CO stretching region of Penicillin G in DMSO-d6. Excitation frequencies are centred at 1767 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math>, 1678 cm<math display="inline"><semantics> <msup> <mrow/> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msup> </semantics></math> and 1622 <math display="inline"><semantics> <mrow> <mi>c</mi> <mi>m</mi> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </mrow> </semantics></math>. Black arrows indicate the position of cross peaks (four times enlarged).</p> ">
Abstract
:1. Introduction
2. Experimental Section
2.1. Materials
2.2. Instrumental Setup
2.3. Signal Acquisition, Data Treatment and Calculations
3. Results and Discussion
3.1. FT-IR Spectra
3.2. Broadband Pump/Probe Experiments
3.3. Vibrational Relaxation
3.4. Evaluation of the Coupling Constants
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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1762 | 1762 | 1767 | 1767 | carbonyl stretching |
1640 | 1655 | 1674 | 1674 | amide I |
1601 | 1580 | 1615 | 1588 | carboxylate asymmetric stretching |
Amide I | Carboxylate | |||
---|---|---|---|---|
ESA | 1.1 exp(-t/550) | 0.2 exp(-t/324) | 0.3 exp(-t/490) | 0.9 exp(-t/136) |
0.4 exp(-t/1750) | 0.3 exp(-t/2040) | 0.3 exp(-t/2125) | 1.2 exp(-t/2195) | |
= 0.9 ± 0.1 ps | = 1.4 ± 0.1 ps | = 1.3 ± 0.1 ps | = 1.3 ± 0.1 ps | |
GSR | 1.5 exp(-t/550) | 0.4 exp(-t/512) | 0.5 exp(-t/580) | 0.5 exp(-t/154) |
0.5 exp(-t/1850) | 0.4 exp(-t/2940) | 0.5 exp(-t/2100) | 1.3 exp(-t/2200) | |
= 0.9 ± 0.1 ps | = 1.7 ± 0.1 ps | = 1.3 ± 0.1 ps | = 1.6 ± 0.1 ps |
/Amide I | 6.7 | |
/carboxylate | 9.2 | 19 |
Amide I/carboxylate | 8.3 |
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Ragnoni, E.; Catalini, S.; Becucci, M.; Lapini, A.; Foggi, P. Linear and Non-Linear Middle Infrared Spectra of Penicillin G in the CO Stretching Mode Region. Symmetry 2021, 13, 106. https://doi.org/10.3390/sym13010106
Ragnoni E, Catalini S, Becucci M, Lapini A, Foggi P. Linear and Non-Linear Middle Infrared Spectra of Penicillin G in the CO Stretching Mode Region. Symmetry. 2021; 13(1):106. https://doi.org/10.3390/sym13010106
Chicago/Turabian StyleRagnoni, Elena, Sara Catalini, Maurizio Becucci, Andrea Lapini, and Paolo Foggi. 2021. "Linear and Non-Linear Middle Infrared Spectra of Penicillin G in the CO Stretching Mode Region" Symmetry 13, no. 1: 106. https://doi.org/10.3390/sym13010106