Ultrahurtig Tidsløst Nær-IR stimuleret Raman Målinger af funktionelle π-konjugatsystemer
Summary
Nærmere oplysninger om signalgenerering og optimering, måling, dataindsamling og datahåndtering for en femtosekund tidsløst nær-IR stimuleret Raman spektrometer er beskrevet. En nær infrarød stimuleret Raman undersøgelse af ophidset-state dynamik β-caroten i toluen er vist som en repræsentativ ansøgning.
Abstract
Femtosekund tidsløst stimuleret Raman spektroskopi er en lovende metode til at observere den strukturelle dynamik kortlivede transienter med nær infrarøde (nær-IR) overgange, fordi det kan overvinde den lave følsomhed spontane Raman spektrometre i nær-IR-regionen. Her beskriver vi tekniske detaljer om en femtosekund tidsløst nær-IR multiplex stimuleret Raman spektrometer, at vi for nylig har udviklet. Der gives også en beskrivelse af signalgenerering og optimering, måling, dataindsamling og kalibrering og korrektion af registrerede data. Vi præsenterer en anvendelse af vores spektrometer til at analysere den ophidsede-state dynamik β-caroten i toluen løsning. En C = C stretch band af β-caroten i den næstlaveste ophidset singlet (S2)tilstand og den laveste ophidset singlet (S1)tilstand er klart observeret i den registrerede tidsløst stimuleret Raman spektre. Den femtosekund tidsløse nær-IR stimuleret Raman spektrometer gælder for den strukturelle dynamik π-konjugat systemer fra simple molekyler til komplekse materialer.
Introduction
Raman spektroskopi er et kraftfuldt og alsidigt værktøj til at undersøge molekylernes strukturer i en lang række prøver fra simple gasser, væsker og faste stoffer til funktionelle materialer og biologiske systemer. Raman spredning er væsentligt forbedret, når foton energi excitation lys falder sammen med den elektroniske overgang energi af et molekyle. ResonansRaman effekt gør det muligt for os selektivt at observere Raman spektrum af en art i en prøve, der består af mange slags molekyler. Near-IR elektroniske overgange trækker en masse opmærksomhed som en sonde til at undersøge ophidset-state dynamik molekyler med store π-konjugerede strukturer. Energien og levetiden for den laveste ophidsede singlet tilstand er blevet bestemt for flere carotenoider, som har en lang endimensional polyenkæde1,2,3. Dynamikken i neutrale og ladede excitationer er blevet grundigt undersøgt for forskellige fotoledende polymerer i film4,5,6,7, nanopartikler8, ogopløsninger 9,10,11. Detaljerede oplysninger om transienternes strukturer kan fås, hvis der anvendes tidsløst nær-IR Raman-spektroskopi på disse systemer. Kun få undersøgelser, dog, er blevet rapporteret om tidsløst nær-IR Raman spektroskopi12,13,14,15,16, fordi følsomheden af nær-IR Raman spektrometre er ekstremt lav. Den lave følsomhed stammer hovedsageligt fra den lave sandsynlighed for næsten-IR Raman spredning. Sandsynligheden for spontan Raman spredning er proportional med ωiωs3, hvor ωi og ωs er frekvenserne af excitation lys og Raman spredning lys, henholdsvis. Hertil kommer, kommercielt tilgængelige nær-IR detektorer har meget lavere følsomhed end CCD detektorer fungerer i UV og synlige områder.
Femtosekund tidsløst stimuleret Raman spektroskopi er opstået som en ny metode til at observere tidsafhængige ændringer af Raman aktive vibrationelle bånd ud over den tilsyneladende Fourier-transformer grænse for en laserpuls17,18,19,20,21,22,23,24,25,26,27,28 ,29,30,31,32,33. Stimuleret Raman spredning genereres ved bestråling af to laser impulser: Raman pumpe og sonde impulser. Her antages det, at Raman pumpepulsen har en større frekvens end sondepulsen. Når forskellen mellem frekvenserne af Raman-pumpen og sondeimpulserne falder sammen med hyppigheden af en Raman aktiv molekylær vibration, er vibrationen sammenhængende spændt for et stort antal molekyler i det bestrålede volumen. Ikke-lineær polarisering fremkaldt af den sammenhængende molekylære vibration forbedrer det elektriske felt af sondepulsen. Denne teknik er især kraftfuld til nær-IR Raman spektroskopi, fordi stimuleret Raman spredning kan løse problemet med følsomheden af tidsløst nær-IR spontanraman spektrometre. Stimuleret Raman spredning registreres som intensitet ændringer af sonden puls. Selv hvis en nær-IR detektor har en lav følsomhed, stimuleret Raman spredning vil blive opdaget, når sonden intensitet er tilstrækkeligt øget. Sandsynligheden for stimuleret Raman spredning er proportional med ωRPωSRS, hvor ωRP og ωSRS er frekvenserne af Raman pumpepuls og stimuleret Raman spredning, henholdsvis20. Frekvenserne til stimuleret Raman spredning, ωRP og ωSRS, svarer til ωi og ωs for spontan Raman spredning, hhv. Vi har for nylig udviklet en femtosekund tidsløst nær-IR Raman spektrometer ved hjælp af stimuleret Raman spredning til at undersøge strukturer og dynamik kortlivede transienter fotogenereret i π-konjugat systemer2,3,7,10. I denne artikel præsenterer vi de tekniske detaljer i vores femtosekund tidsløst nær-IR multiplex stimuleret Raman spektrometer. Optisk justering, erhvervelse af tidsløst stimuleret Raman spektre, og kalibrering og korrektion af registrerede spektre er beskrevet. Den ophidsede tilstanddynamik i β-caroten i toluenopløsning undersøges som en repræsentativ anvendelse af spektrometeret.
Protocol
Representative Results
Discussion
Afgørende faktorer i femtosekund tidsløst nær-IR multiplex stimuleret Raman måling
For at opnå tidsløst nær-IR stimuleret Raman spektre med et højt signal-til-støj-forhold, bør sondespektret ideelt set have ensartet intensitet i hele bølgelængdeområdet. Produktion af kontinuum med hvidt lys (afsnit 2.5) er derfor en af de mest afgørende dele af tidsløst nær-IR stimuleret Raman eksperimenter. Generelt bliver sondespektret bredt og fladt, efterhånden som intensiteten af hændelsesstrål…
Divulgazioni
The authors have nothing to disclose.
Acknowledgements
Dette arbejde blev støttet af JSPS KAKENHI Grant Numbers JP24750023, JP24350012, MEXT KAKENHI Grant Numbers JP26104534, JP16H00850, JP26102541, JP16H00782 og MEXT-Supported Program for Strategic Research Foundation ved Private Universities, 2015-2019.
Materials
| 1-Axis Translational Stage | OptSigma | TSD-401S | Products equivalent to this are used as well; for M22, L9, and CM in Figure 1A |
| 20-cm Optical Delay Line | OptSigma | SGSP26-200 | ODL1 in Figure 1A |
| 3-Axis Translational Stage | OptSigma | TSD-405SL | For L8 in Figure 1A |
| 3-Axis Translational Stage | Suruga Seiki | B72-40C | For FC in Figure 1A |
| 5-cm Optical Delay Line | PMT | HRS-0050 | ODL2 in Figure 1A |
| Al Concave Mirror | Thorlabs | CM254-050-G01 | Focal length: 50 mm; CM in Figure 1A |
| Base Plate | Suruga Seiki | A21-6 | Products equivalent to this are used as well; for M1-M32, BS1-BS3, L1-L10, I1-I17, P1-P2, HWP1-3, F1-F3, VND1-VND2, OC, BPF, HS, BBO, SP, CM, and FC in Figure 1A |
| BBO Crystal | EKSMA Optics | – | Type 1, θ = 23.2 deg; BBO in Figure 1A |
| BK7 Plano-Concave Lens | OptSigma | SLB-25.4-50NIR2 | Focal length: 50 mm; IR anti-reflection coating; L6 in Figure 1A |
| BK7 Plano-Convex Lens | OptSigma | SLB-25.4-150PIR2 | Focal length: 150 mm; IR anti-reflection coating; L2, L3, L5 in Figure 1A |
| BK7 Plano-Convex Lens | OptSigma | SLB-25.4-100PIR2 | Focal length: 100 mm; IR anti-reflection coating; L4 in Figure 1A |
| BK7 Plano-Convex Lens | OptSigma | SLB-25.4-200PIR2 | Focal length: 200 mm; IR anti-reflection coating; L7 in Figure 1A |
| Broadband Dielectric Mirror | OptSigma | TFMS-25.4C05-2/7 | M22-M25, M28, M29 in Figure 1A |
| Broadband Dielectric Mirror | Precision Photonics (Advanced Thin Films) | – | M26, M27, M30-M32 in Figure 1A |
| Broadband Half-Wave Plate | CryLight | – | HWP3 in Figure 1A |
| Color Glass Filter | HOYA | IR85 | F1 in Figure 1A |
| Color Glass Filter | HOYA | RM100 | F2 in Figure 1A |
| Color Glass Filter | Schott | BG39 | F3 in Figure 1A |
| Computer | Dell | Vostro 200 Mini Tower | OS: Windows XP |
| Cyclohexane | Kanto Kagaku | 07547-1B | HPLC grade |
| Data Analysis Software | Wavemetrics | Igor Pro 8 | |
| Dielectric Beamsplitter | LAYERTEC | – | Reflection : Transmission = 2 : 1; BS1 in Figure 1A |
| Dielectric Beamsplitter | LAYERTEC | – | Reflection : Transmission = 1 : 1; BS2, BS3 in Figure 1A |
| Dielectric Mirror | Precision Photonics (Advanced Thin Films) |
– | M1-M8 in Figure 1A |
| Digital Oscilloscope | Tektronix | TDS3054B | 500 MHz, 5 GS/s |
| Elastomer Tube | – | – | Figure 1E |
| Femtosecond Ti:sapphire Oscillator | Coherent | Vitesse 800-2 | Wavelength: 800 nm, pulse duration: 100 fs, average power: 280 mW, repetition rate: 80 MHz; included in Ti:S in Figure 1A |
| Femtosecond Ti:sapphire Regenerative Amplifier | Coherent | Legend-Elite-F-HE | Wavelength: 800 nm, pulse duration: 100 fs, pulse energy: 3.5 mJ, repetition rate: 1 kHz; included in Ti:S in Figure 1A |
| Film Polarizer | OptSigma | SPFN-30C-26 | P1 in Figure 1A |
| Glan-Taylor Prism | OptSigma | GYPB-10-10SN-3/7 | P2 in Figure 1A |
| Gold Mirror | OptSigma | TFG-25C05-10 | M9-M21 in Figure 1A |
| Half-Wave Plate | OptSigma | WPQ-7800-2M | HWP1 in Figure 1A |
| Harmonic Separator | Coherent | TOPAS-C HRs 410-540 nm | HS in Figure 1A |
| InGaAs Array Detector | Horiba | Symphony-IGA-512X1-50-1700-1LS | 512 ch, Liquid nitrogen cooled |
| InGaAs PIN Photodiode | Hamamatsu Photonics | G10899-01K | |
| IR Half-Wave Plate | OptiSource | – | HWP2 in Figure 1A |
| Iris | Suruga Seiki | F74-3N | Products equivalent to this are used as well; I1-I17 in Figure 1A |
| Lens Holder | OptSigma | LHF-25.4S | Products equivalent to this are used as well; for L1-L10 in Figure 1A |
| Magnetic Gear Pump | Micropump | 184-415 | |
| Mirror Mount | Siskiyou | IM100.C2M6R | Products equivalent to this are used as well; for M1-M32, BS1-BS3, BBO, CM in Figure 1A |
| near-IR phosphor card | Thorlabs | VRC2 | |
| Nut | – | – | Figure 1E, M4; purchased from a DIY store |
| Optical Chopper | New Focus | 3501 | OC in Figure 1A |
| Optical Parametric Amplifier | Coherent | OPerA-F | OPA1 in Figure 1A |
| Optical Parametric Amplifier | Coherent | TOPAS-C | OPA2 in Figure 1A |
| Polarizer Holder | OptSigma | PH-30-ARS | Products equivalent to this are used as well; for P1-P2 and HWP1-3 In Figure 1A |
| Polyfluoroacetate Tube | – | – | Figure 1E |
| Post Holder | OptSigma | BRS-12-80 | Products equivalent to this are used as well; for M1-M32, BS1-BS3, L1-L10, I1-I17, P1-P2, HWP1-3, F1-F3, VND1-VND2, OC, BPF, HS, BBO, SP, CM, and FC in Figure 1A |
| Quartz Flow Cell | Tosoh Quartz | T-70-UV-2 | FC in Figure 1A |
| Quartz Plano-Concave Lens | OptSigma | SLSQ-25-50N | Focal length: 50 mm; L8 in Figure 1A |
| Quartz Plano-Convex Lens | OptSigma | SLSQ-25-100P | Focal length: 100 mm; L1, L9 in Figure 1A |
| Quartz Plano-Convex Lens | OptSigma | SLSQ-25-220P | Focal length: 220 mm; L10 in Figure 1A |
| Sapphire Plate | Pier Optics | – | 3 mm thick; SP in Figure 1A |
| Si PIN Photodiode | Hamamatsu Photonics | S3883 | |
| Single Spectrograph | Horiba Jobin Yvon | iHR320 | Focal length: 32 cm |
| Stainless Steel Rod | Suruga Seiki | A41-100 | Products equivalent to this are used as well; for M1-M32, BS1-BS3, L1-L10, I1-I17, P1-P2, HWP1-3, F1-F3, VND1-VND2, OC, BPF, HS, BBO, SP, CM, and FC in Figure 1A |
| Stainless Steel Rod | Newport | J-SP-2 | Figure 1E |
| Toluene | Kanto Kagaku | 40180-1B | HPLC grade |
| U-Shaped Steel Plate | – | – | Figure 1E; purchased from a DIY store |
| Variable Neutral Density Filter (with a holder) | OptSigma | NDHN-100 | VND1 in Figure 1A |
| Variable Neutral Density Filter (with a holder) | OptSigma | NDHN-U100 | VND2 in Figure 1A |
| Visual Programming Language | National Instruments | LabVIEW 2009 | The control software in this study is programmed in LabVIEW 2009 |
| Volume-Grating Bandpass Filter | OptiGrate | BPF-1190 | BPF in Figure 1A |
| β-Carotene | Wako Pure Chemical Industries | 035-05531 |
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