ABSTRACT
OBJECTIVES: Clinical guidelines for acute non-specific low back pain (LBP) recommend avoiding imaging studies or invasive treatments and to advise patients to stay active. The aim of this study was to evaluate the management of acute non-specific LBP in the emergency departments (ED). SETTING: We invited all department chiefs of Swiss EDs and their physician staff to participate in a web-based survey using two clinical case vignettes of patients with acute non-specific LBP presenting to an ED. In both cases, no neurological deficits or red flags were present. Guideline adherence and low-value care was defined based on current guideline recommendations. RESULTS: In total, 263 ED physicians completed at least one vignette, while 212 completed both vignettes (43% residents, 32% senior/attending physicians and 24% chief physicians). MRI was considered in 31% in vignette 1 and 65% in vignette 2. For pain management, non-steroidal anti-inflammatory drugs, paracetamol and metamizole were mostly used. A substantial proportion of ED physicians considered treatments with questionable benefit and/or increased risk for adverse events such as oral steroids (vignette 1, 12% and vignette 2, 19%), muscle relaxants (33% and 38%), long-acting strong opioids (25% and 33%) and spinal injections (22% and 43%). Although guidelines recommend staying active, 72% and 67% of ED physicians recommended activity restrictions. CONCLUSION: Management of acute non-specific LBP in the ED was not in agreement with current guideline recommendations in a substantial proportion of ED physicians. Overuse of imaging studies, the use of long-acting opioids and muscle relaxants, as well as recommendations for activity and work restrictions were prevalent and may potentially be harmful.
Subject(s)
Acute Pain , Low Back Pain , Physicians , Humans , Low Back Pain/therapy , Analgesics, Opioid , Cross-Sectional Studies , Acute Pain/diagnosis , Acute Pain/therapy , Magnetic Resonance Imaging , Emergency Service, HospitalABSTRACT
Histoplasmosis is a well-known endemic fungal infection but experience in non-endemic regions is often limited, which may lead to delayed diagnosis and extensive testing. The diagnosis can be especially challenging, typically when the disease first presents with pulmonary nodules accompanied by hilar and mediastinal lymphadenopathy, suggesting a much more common malignant disease. In this situation, a greater FDG uptake in draining lymph nodes in comparison with the associated lung nodule seen in [18F]FDG-PET/CT, the so-called "flip-flop fungus" sign, can help to orientate further diagnostic measures. We report a case of a 56-year-old woman living in Switzerland, a non-endemic region, whose diagnosis of imported histoplasmosis was delayed since the findings had been initially misinterpreted as pulmonary malignancy. Further, histological workup was inconclusive due to lack of specific fungal staining, leading to ineffective treatment and non-resolving disease. This paper intends to highlight the pitfalls in diagnosing Histoplasma capsulatum and presents images of particularities of fungal infections in [18F]FDG-PET/CT, which in our case showed a "flip-flop fungus" sign.
ABSTRACT
UHDpulse - Metrology for advanced radiotherapy using particle beams with ultra-high pulse dose rates is a recently started European Joint Research Project with the aim to develop and improve dosimetry standards for FLASH radiotherapy, very high energy electron (VHEE) radiotherapy and laser-driven medical accelerators. This paper gives a short overview about the current state of developments of radiotherapy with FLASH electrons and protons, very high energy electrons as well as laser-driven particles and the related challenges in dosimetry due to the ultra-high dose rate during the short radiation pulses. We summarize the objectives and plans of the UHDpulse project and present the 16 participating partners.
Subject(s)
Electrons , Radiometry , Lasers , Particle Accelerators , Protons , Radiotherapy , Radiotherapy Dosage , Radiotherapy, High-EnergyABSTRACT
The decay mechanism of S0 â S1 excited cytosine (Cyt) and the effect of substitution are studied combining jet-cooled spectroscopy (nanosecond resonant two-photon ionization (R2PI) and picosecond lifetime measurements) with CASPT2//CASSCF computations for eight derivatives. For Cyt and five derivatives substituted at N1, C5, and C6, rapid internal conversion sets in at 250-1200 cm-1 above the 000 bands. The break-off in the spectra correlates with the calculated barriers toward the "C5-C6 twist" conical intersection, which unambiguously establishes the decay mechanism at low S1 state vibrational energies. The barriers increase with substituents that stabilize the charge shifts at C4, C5, and C6 following (1ππ*) excitation. The R2PI spectra of the clamped derivatives 5,6-trimethyleneCyt (TMCyt) and 1-methyl-TMCyt (1M-TMCyt), which decay along an N3 out-of-plane coordinate, extend up to +3500 and +4500 cm-1.
ABSTRACT
In magnetic resonance guided radiotherapy (MRgRT) radiation dose measurements needs to be performed in the presence of a magnetic field. In this study, the influence of magnetic fields on the readings of a Fricke detector, a chemical dosimeter, have been investigated in 6 MV photon beams. This type of detector has been chosen, as the Federal Office of Metrology (METAS, Switzerland) has great experience with Fricke dosimetry and since it is not expected that this detector is greatly affected by the presence of a magnetic field. Magnetic fields with field strengths between 0 T and 1.42 T were applied during the detector irradiation. In a 5 × 10 cm2 irradiation field, the Fricke readings are affected less than 0.9% by the applied magnetic fields. Taking the altered dose distribution due to the magnetic field ([Formula: see text]) into account, the magnetic field correction factors ([Formula: see text]) for the Fricke detector at 0.35 T and 1.42 T are determined to be 0.9948 and 0.9980, respectively. These small corrections hardly exceed the measurement uncertainties. Hence, we could proof that the Fricke detector is not significantly influenced by the presence of a magnetic field. The Fricke detector was also tested for the feasibility of measuring output factors in the presence of magnetic fields. For irradiation field sizes larger than the detector (>2 × 2 cm2), comparable results were obtained as for other detectors. The output factors decrease when a magnetic field is applied. This effect is more pronounce for larger magnetic field strengths and smaller irradiation fields due to shifts of the depth dose curves and asymmetry of lateral dose profiles.
Subject(s)
Magnetic Fields , Photons/therapeutic use , Radiometry/methods , Particle Accelerators , UncertaintyABSTRACT
The S1 excited-state lifetime of jet-cooled 1-ethylcytosine (1ECyt) is â¼1 ns, one of the longest lifetimes for cytosine derivatives to date. Here, we analyze its S0 â S1 vibronic spectrum using two-color resonant two-photon ionization and UV/UV holeburning spectroscopy. Compared to cytosine and 1-methylcytosine, the S0 â S1 spectrum of 1ECyt shows a progression in the out-of-plane "butterfly" mode ν1 ', identified by spin-component scaled-second-order coupled-cluster method ab initio calculations. We also report time-resolved S1 state nonradiative dynamics at â¼20 ps resolution by the pump/delayed ionization technique. The S1 lifetime increases with the number of ν1 ' quanta from τ = 930 ps at v1 '=0 to 1030 ps at v1 '=2, decreasing to 14 ps at 710 cm-1 vibrational energy. We measured the rate constants for S1 â S0 internal conversion and S1 â T1 intersystem crossing (ISC): At the v' = 0 level, kIC is 8 × 108 s-1 or three times smaller than 1-methylcytosine. The ISC rate constant from v' = 0 to the T1(3ππ*) state is kISC = 2.4 × 108 s-1, 10 times smaller than the ISC rate constants of cytosine, but similar to that of 1-methylcytosine. Based on the calculated S1(1ππ*) state radiative lifetime τrad = 12 ns, the fluorescence quantum yield of 1ECyt is Φfl â¼ 7% and the intersystem crossing yield is ΦISC â¼ 20%. We measured the adiabatic ionization energy of 1-ethylcytosine via excitation of the S1 state as 8.353 ± 0.008 eV, which is 0.38 eV lower than that of amino-keto cytosine. Measurement of the ionization energy of the long-lived T1(ππ*) state formed via ISC reveals that it lies 3.2-3.4 eV above the S0 ground state.
ABSTRACT
We measure the S0 â S1 spectrum and time-resolved S1 state nonradiative dynamics of the "clamped" cytosine derivative 5,6-trimethylenecytosine (TMCyt) in a supersonic jet, using two-color resonant two-photon ionization (R2PI), UV/UV holeburning, and ns time-resolved pump/delayed ionization. The experiments are complemented with spin-component scaled second-order approximate coupled cluster (SCS-CC2), time-dependent density functional theory, and multi-state second-order perturbation-theory (MS-CASPT2) ab initio calculations. While the R2PI spectrum of cytosine breaks off â¼500 cm-1 above its 000 band, that of TMCyt extends up to +4400 cm-1 higher, with over a hundred resolved vibronic bands. Thus, clamping the cytosine C5-C6 bond allows us to explore the S1 state vibrations and S0 â S1 geometry changes in detail. The TMCyt S1 state out-of-plane vibrations ν1', ν3', and ν5' lie below 420 cm-1, and the in-plane ν11', ν12', and ν23' vibrational fundamentals appear at 450, 470, and 944 cm-1. S0 â S1 vibronic simulations based on SCS-CC2 calculations agree well with experiment if the calculated ν1', ν3', and ν5' frequencies are reduced by a factor of 2-3. MS-CASPT2 calculations predict that the ethylene-type S1 â S0 conical intersection (CI) increases from +366 cm-1 in cytosine to >6000 cm-1 in TMCyt, explaining the long lifetime and extended S0 â S1 spectrum. The lowest-energy S1 â S0 CI of TMCyt is the "amino out-of-plane" (OPX) intersection, calculated at +4190 cm-1. The experimental S1 â S0 internal conversion rate constant at the S1(v'=0) level is kIC=0.98-2.2â 108 s-1, which is â¼10 times smaller than in 1-methylcytosine and cytosine. The S1(v'=0) level relaxes into the T1(3ππ*) state by intersystem crossing with kISC=0.41-1.6â 108 s-1. The T1 state energy is measured to lie 24 580±560 cm-1 above the S0 state. The S1(v'=0) lifetime is τ=2.9 ns, resulting in an estimated fluorescence quantum yield of Φfl=24%. Intense two-color R2PI spectra of the TMCyt amino-enol tautomers appear above 36 000 cm-1. A sharp S1 ionization threshold is observed for amino-keto TMCyt, yielding an adiabatic ionization energy of 8.114±0.002 eV.
ABSTRACT
We have investigated the S0 â S1 UV vibronic spectrum and time-resolved S1 state dynamics of jet-cooled amino-keto 1-methylcytosine (1MCyt) using two-color resonant two-photon ionization, UV/UV holeburning and depletion spectroscopies, as well as nanosecond and picosecond time-resolved pump/delayed ionization measurements. The experimental study is complemented with spin-component-scaled second-order coupled-cluster and multistate complete active space second order perturbation ab initio calculations. Above the weak electronic origin of 1MCyt at 31 852 cm-1 about 20 intense vibronic bands are observed. These are interpreted as methyl group torsional transitions coupled to out-of-plane ring vibrations, in agreement with the methyl group rotation and out-of-plane distortions upon 1ππ∗ excitation predicted by the calculations. The methyl torsion and ν1' (butterfly) vibrations are strongly coupled, in the S1 state. The S0 â S1 vibronic spectrum breaks off at a vibrational excess energy Eexc â¼ 500 cm-1, indicating that a barrier in front of the ethylene-type S1âS0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm-1. The S1âS0 internal conversion rate constant increases from kIC = 2 â 109 s-1 near the S1(v = 0) level to 1 â 1011 s-1 at Eexc = 516 cm-1. The 1ππ∗ state of 1MCyt also relaxes into the lower-lying triplet T1 (3ππ∗) state by intersystem crossing (ISC); the calculated spin-orbit coupling (SOC) value is 2.4 cm-1. The ISC rate constant is 10-100 times lower than kIC; it increases from kISC = 2 â 108 s-1 near S1(v = 0) to kISC = 2 â 109 s-1 at Eexc = 516 cm-1. The T1 state energy is determined from the onset of the time-delayed photoionization efficiency curve as 25 600 ± 500 cm-1. The T2 (3nπ∗) state lies >1500 cm-1 above S1(v = 0), so S1âT2 ISC cannot occur, despite the large SOC parameter of 10.6 cm-1. An upper limit to the adiabatic ionization energy of 1MCyt is determined as 8.41 ± 0.02 eV. Compared to cytosine, methyl substitution at N1 lowers the adiabatic ionization energy by ≥0.32 eV and leads to a much higher density of vibronic bands in the S0 â S1 spectrum. The effect of methylation on the radiationless decay to S0 and ISC to T1 is small, as shown by the similar break-off of the spectrum and the similar computed mechanisms.
ABSTRACT
Ultraviolet radiative damage to DNA is inefficient because of the ultrafast S1 â S0 internal conversion of its nucleobases. Using picosecond pump-ionization delay measurements, we find that the S1((1)ππ*) state vibrationless lifetime of gas-phase keto-amino cytosine (Cyt) is τ = 730 ps or â¼ 700 times longer than that measured by femtosecond pump-probe ionization at higher vibrational excess energy, Eexc. N1-Alkylation increases the S1 lifetime up to τ = 1030 ps for N1-ethyl-Cyt but decreases it to 100 ps for N1-isopropyl-Cyt. Increasing the vibrational energy to Eexc = 300-550 cm(-1) decreases the lifetimes to 20-30 ps. The nonradiative dynamics of S1 cytosine is not solely a property of the amino-pyrimidinone chromophore but is strongly influenced by the N1-substituent. Correlated excited-state calculations predict that the gap between the S2((1)nOπ*) and S1((1)ππ*) states decreases along the series of N1-derivatives, thereby influencing the S1 state lifetime.
Subject(s)
Cytosine/chemistry , DNA Damage , Molecular StructureABSTRACT
We observe the weak S0 â S2 transitions of the T-shaped benzene dimers (Bz)2 and (Bz-d6)2 about 250 cm(-1) and 220 cm(-1) above their respective S0 â S1 electronic origins using two-color resonant two-photon ionization spectroscopy. Spin-component scaled (SCS) second-order approximate coupled-cluster (CC2) calculations predict that for the tipped T-shaped geometry, the S0 â S2 electronic oscillator strength fel(S2) is â¼10 times smaller than fel(S1) and the S2 state lies â¼240 cm(-1) above S1, in excellent agreement with experiment. The S0 â S1 (ππ(∗)) transition is mainly localized on the "stem" benzene, with a minor stem â cap charge-transfer contribution; the S0 â S2 transition is mainly localized on the "cap" benzene. The orbitals, electronic oscillator strengths fel(S1) and fel(S2), and transition frequencies depend strongly on the tipping angle ω between the two Bz moieties. The SCS-CC2 calculated S1 and S2 excitation energies at different T-shaped, stacked-parallel and parallel-displaced stationary points of the (Bz)2 ground-state surface allow to construct approximate S1 and S2 potential energy surfaces and reveal their relation to the "excimer" states at the stacked-parallel geometry. The fel(S1) and fel(S2) transition dipole moments at the C2v-symmetric T-shape, parallel-displaced and stacked-parallel geometries are either zero or â¼10 times smaller than at the tipped T-shaped geometry. This unusual property of the S0 â S1 and S0 â S2 transition-dipole moment surfaces of (Bz)2 restricts its observation by electronic spectroscopy to the tipped and tilted T-shaped geometries; the other ground-state geometries are impossible or extremely difficult to observe. The S0 â S1/S2 spectra of (Bz)2 are compared to those of imidazole â (Bz)2, which has a rigid triangular structure with a tilted (Bz)2 subunit. The S0 â S1/ S2 transitions of imidazole-(benzene)2 lie at similar energies as those of (Bz)2, confirming our assignment of the (Bz)2 S0 â S2 transition.
ABSTRACT
NH···π hydrogen bonds occur frequently between the amino acid side groups in proteins and peptides. Data-mining studies of protein crystals find that â¼80% of the T-shaped histidine···aromatic contacts are CH···π, and only â¼20% are NH···π interactions. We investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet-cooled imidazole·benzene (Im·Bz) complex as a model for the NH···π interaction between histidine and phenylalanine. Ground- and excited-state dispersion-corrected density functional calculations and correlated methods (SCS-MP2 and SCS-CC2) predict that Im·Bz has a Cs-symmetric T-shaped minimum-energy structure with an NH···π hydrogen bond to the Bz ring; the NH bond is tilted 12° away from the Bz C6 axis. IR depletion spectra support the T-shaped geometry: The NH stretch vibrational fundamental is red shifted by -73 cm(-1) relative to that of bare imidazole at 3518 cm(-1), indicating a moderately strong NH···π interaction. While the S0(A1g) â S1(B2u) origin of benzene at 38â¯086 cm(1) is forbidden in the gas phase, Im·Bz exhibits a moderately intense S0 â S1 origin, which appears via the D(6h) â Cs symmetry lowering of Bz by its interaction with imidazole. The NH···π ground-state hydrogen bond is strong, De=22.7 kJ/mol (1899 cm1). The combination of gas-phase UV and IR spectra confirms the theoretical predictions that the optimum Im·Bz geometry is T shaped and NH···π hydrogen bonded. We find no experimental evidence for a CH···π hydrogen-bonded ground-state isomer of Im·Bz. The optimum NH···π geometry of the Im·Bz complex is very different from the majority of the histidine·aromatic contact geometries found in protein database analyses, implying that the CH···π contacts observed in these searches do not arise from favorable binding interactions but merely from protein side-chain folding and crystal-packing constraints. The UV and IR spectra of the imidazole·(benzene)2 cluster are observed via fragmentation into the Im·Bz+ mass channel. The spectra of Im·Bz and Im·Bz2 are cleanly separable by IR hole burning. The UV spectrum of Im·Bz2 exhibits two 000 bands corresponding to the S0 â S1 excitations of the two inequivalent benzenes, which are symmetrically shifted by -86/+88 cm(-1) relative to the 000 band of benzene
Subject(s)
Histidine/chemistry , Models, Chemical , Phenylalanine/chemistry , Benzene/chemistry , Computer Simulation , Gases/chemistry , Hydrogen Bonding , Imidazoles/chemistry , Spectrum AnalysisABSTRACT
The S0 â S1 vibronic spectrum and S1 state nonradiative relaxation of jet-cooled keto-amino 5-fluorocytosine (5FCyt) are investigated by two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(1) resolution. The 0(0)(0) rotational band contour is polarized in-plane, implying that the electronic transition is (1)ππ*. The electronic transition dipole moment orientation and the changes of rotational constants agree closely with the SCS-CC2 calculated values for the (1)ππ* (S1) transition of 5FCyt. The spectral region from 0 to 300 cm(1) is dominated by overtone and combination bands of the out-of-plane ν1' (boat), ν2' (butterfly), and ν3' (HNC6H twist) vibrations, implying that the pyrimidinone frame is distorted out-of-plane by the (1)ππ* excitation, in agreement with SCS-CC2 calculations. The number of vibronic bands rises strongly around +350 cm(1); this is attributed to the (1)ππ* state barrier to planarity that corresponds to the central maximum of the double-minimum out-of-plane vibrational potentials along the ν1', ν2', and ν3' coordinates, which gives rise to a high density of vibronic excitations. At +1200 cm(1), rapid nonradiative relaxation (k(nr) ≥ 10(12) s(1)) sets in, which we interpret as the height of the (1)ππ* state barrier in front of the lowest S1/S0 conical intersection. This barrier in 5FCyt is 3 times higher than that in cytosine. The lifetimes of the ν' = 0, 2ν1', 2ν2', 2ν1' + 2ν2', 4ν2', and 2ν1' + 4ν2' levels are determined from Lorentzian widths fitted to the rotational band contours and are τ ≥ 75 ps for ν' = 0, decreasing to τ ≥ 55 ps at the 2ν1' + 4ν2' level at +234 cm(1). These gas-phase lifetimes are twice those of S1 state cytosine and 10100 times those of the other canonical nucleobases in the gas phase. On the other hand, the 5FCyt gas-phase lifetime is close to the 73 ps lifetime in room-temperature solvents. This lack of dependence on temperature and on the surrounding medium implies that the 5FCyt nonradiative relaxation from its S1 ((1)ππ*) state is essentially controlled by the same ~1200 cm(1) barrier and conical intersection both in the gas phase and in solution.
Subject(s)
Cold Temperature , Flucytosine/chemistry , Models, Molecular , Quantum Theory , Vibration , Gases , Molecular Structure , Phase Transition , Solutions , Ultraviolet RaysABSTRACT
The UV spectrum of the adenine analogue 9-methyl-2-aminopurine (9M-2AP) is investigated with one- and two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(-1) resolution in a supersonic jet. The electronic origin at 32,252 cm(-1) exhibits methyl torsional subbands that originate from the 0A1'' (l = 0) and 1E(â³) (l = ±1) torsional levels. These and further torsional bands that appear up to 00 (0)+230 cm(-1) allow to fit the threefold (V3) barriers of the torsional potentials as |V3''|=50 cm(-1) in the S0 and |V3'|=126 cm(-1) in the S1 state. Using the B3LYP density functional and correlated approximate second-order coupled cluster CC2 methods, the methyl orientation is calculated to be symmetric relative to the 2AP plane in both states, with barriers of V3''=20 cm(-1) and V3'=115 cm(-1). The 00 (0) rotational band contour is 75% in-plane (a/b) polarized, characteristic for a dominantly long-axis (1)ππ(*) excitation. The residual 25% c-axis polarization may indicate coupling of the (1)ππ(*) to the close-lying (1)nπ(*) state, calculated at 4.00 and 4.01 eV with the CC2 method. However, the CC2 calculated (1)nπ oscillator strength is only 6% of that of the (1)ππ(*) transition. The (1)ππ(*) vibronic spectrum is very complex, showing about 40 bands within the lowest 500 cm(-1). The methyl torsion and the low-frequency out-of-plane ν1' and ν2' vibrations are strongly coupled in the (1)ππ(*) state. This gives rise to many torsion-vibration combination bands built on out-of-plane fundamentals, which are without precedence in the (1)ππ(*) spectrum of 9H-2-aminopurine [S. Lobsiger, R. K. Sinha, M. Trachsel, and S. Leutwyler, J. Chem. Phys. 134, 114307 (2011)]. From the Lorentzian broadening needed to fit the 00 (0) contour of 9M-2AP, the (1)ππ(*) lifetime is τ ⩾ 120 ps, reflecting a rapid nonradiative transition.
Subject(s)
Adenine/analogs & derivatives , Adenine/chemistry , Rotation , Spectrum Analysis , Torsion, Mechanical , Ultraviolet Rays , VibrationABSTRACT
We have measured the mass- and tautomer-specific S0 â S1 vibronic spectra and S1 state lifetimes of the ketoamino tautomer of cytosine cooled in supersonic jets, using two-color resonant two-photon ionization (R2PI) spectroscopy at 0.05 cm(1) resolution. The rotational contours of the 0(0)(0) band and nine vibronic bands up to +437 cm(1) are polarized in the pyrimidinone plane, proving that the electronic excitation is to a 1ππ* state. All vibronic excitations up to +437 cm(1) are overtone and combination bands of the low-frequency out-of-plane ν1' (butterfly), ν2' (boat), and ν3' (HNC6H twist) vibrations. UV vibronic spectrum simulations based on approximate second-order coupled-cluster (CC2) calculations of the ground and 1ππ* states are in good agreement with the experimental R2PI spectrum, but only if the calculated ν1' and ν2' frequencies are reduced by a factor of 4 and anharmonicity is included. Together with the high intensity of the ν1' and ν2' overtone vibronic excitations, this implies that the 1ππ* potential energy surface is much softer and much more anharmonic in the out-of-plane directions than predicted by the CC2 method. The 1ππ* state lifetime is determined from the Lorentzian line broadening necessary to reproduce the rotational band contours: at the 0(0)(0) band it is τ = 44 ps, remains at τ = 3545 ps up to +205 cm(1), and decreases to 2530 ps up to +437 cm(1). These lifetimes are 2040 times longer than the 0.51.5 ps lifetimes previously measured with femtosecond pumpprobe techniques at higher vibrational energies (15003800 cm(1)). Thus, the nonradiative relaxation rate of ketoamino cytosine close to the 1ππ* state minimum is k(nr) 2.5 × 10(10) s(1), much smaller than at higher energies. An additional nonradiative decay channel opens at +500 cm(1) excess energy. Since high overtone bands of ν1' and ν2' are observed in the R2PI spectrum but only a single weak 2ν3' band, we propose that ν3' is a promoting mode for nonradiative decay, consistent with the observation that the ν3' normal-mode eigenvector points toward the "C6-puckered" conical intersection geometry.
Subject(s)
Cytosine/chemistry , Isomerism , Models, Molecular , Molecular Conformation , PhotonsABSTRACT
We investigate the UV vibronic spectrum and excited-state nonradiative processes of jet-cooled 5-methylcytosine (5MCyt) using two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(1) resolution. In contrast to cytosine, which shows only five bands above its electronic origin, the lowest electronic transition of 5MCyt exhibits about 25 low-frequency vibronic bands that extend to 0(0)(0) + 450 cm(1), allowing to extract detailed information on the excited-state electronic and nuclear structure. Most bands are overtones and combinations of the out-of-plane vibrations ν'(1), ν'(2), and ν'(3). Their large intensities reflect butterfly-, boat-, and twist-deformations of the 5MCyt framework upon electronic excitation. From the rotational contours of the 0(0)(0), 1(0)(2), 2(0)(2), and 3(0)(2) bands, the transition is found to be polarized along the in-plane a/b axes, characteristic of a (1)ππ* transition. Approximate second-order coupled-cluster (CC2) and time-dependent B3LYP calculations both predict that 5MCyt undergoes an out-of-plane deformation in its (1)ππ* (S(2)) state but both methods overestimate the out-of-plane ν'(1), ν'(2), and ν'(3) vibrational frequencies by a factor of 35. The TD-B3LYP (1)ππ* transition dipole moment direction is 10%:90% a:b, in good agreement with experiment. From the Lorentzian line shape contributions needed to fit the rotational contours, a lower limit to the 5MCyt (1)ππ* state lifetime at the 0(0)(0), 1(0)(2), 2(0)(2), and 3(0)(2) bands is determined as τ ≥ 30 ps. These values are in stark contrast to the ultrafast (picosecond) lifetimes measured for jet-cooled cytosine by femtosecond pumpprobe techniques. They also confirm the observation from the R2PI spectrum that 5-methylation of cytosine increases its excited-state lifetime. The higher out-of-plane overtone and combination bands disappear from the spectrum by ~460 cm(1), signaling the onset of lifetimes τ < 0.5 ps, induced by excitation of the ν'(1), ν'(2), and ν'(3) modes. Above 460 cm(1) the in-plane fundamentals 9(0)(1), 10(0)(1), and 17(0)(1) are weakly observed, implying that the in-plane vibrations couple weakly to the out-of-plane modes and have lifetimes τ > 3 ps up to 720 cm(1) excess vibrational energy.
Subject(s)
5-Methylcytosine/chemistry , Models, Molecular , Quantum Theory , Spectrum Analysis , Stereoisomerism , ThermodynamicsABSTRACT
We have investigated the UV vibronic spectra and excited-state nonradiative processes of the 7H- and 9H-tautomers of jet-cooled 2-aminopurine (2AP) and of the 9H-2AP-d(4) and -d(5) isotopomers, using two-color resonant two-photon ionization spectroscopy at 0.3 and 0.045 cm(-1) resolution. The S(1) â S(0) transition of 7H-2AP was observed for the first time. It lies â¼1600 cm(-1) below that of 9H-2AP, is â¼1000 times weaker and exhibits only in-plane vibronic excitations. In contrast, the S(1) â S(0) spectra of 9H-2AP, 9H-2AP-d(4), and 9H-2AP-d(5) show numerous low-frequency bands that can be systematically assigned to overtone and combinations of the out-of-plane vibrations ν(1)', ν(2)', and ν(3)'. The intensity of these out-of-plane bands reflects an out-of-plane deformation in the (1)ππ∗(L(a)) state. Approximate second-order coupled-cluster theory also predicts that 2-aminopurine undergoes a "butterfly" deformation in its lowest (1)ππ∗ state. The rotational contours of the 9H-2AP, 9H-2AP-d(4), and 9H-2AP-d(5) 0(0)(0) bands and of eight vibronic bands of 9H-2AP up to 0(0)(0) + 600 cm(-1) exhibit 75%-80% in-plane (a∕b) polarization, which is characteristic for a (1)ππ∗ excitation. A 20%-25% c-axis (perpendicular) transition dipole moment component may indicate coupling of the (1)ππ∗ bright state to the close-lying (1)nπ∗ dark state. However, no (1)nπ∗ vibronic bands were detected below or up to 500 cm(-1) above the (1)ππ∗ 0(0)(0) band. Following (1)ππ∗ excitation, 9H-2AP undergoes a rapid nonradiative transition to a lower-lying long-lived state with a lifetime ≥5 µs. The ionization potential of 9H-2AP was measured via the (1)ππ∗ state (IP = 8.020 eV) and the long-lived state (IP > 9.10 eV). The difference shows that the long-lived state lies ≥1.08 eV below the (1)ππ∗ state. Time-dependent B3LYP calculations predict the (3)ππ∗ (T(1)) state 1.12 eV below the (1)ππ∗ state, but place the (1)nπ∗ (S(1)) state close to the (1)ππ∗ state, implying that the long-lived state is the lowest triplet (T(1)) and not the (1)nπ∗ state.
Subject(s)
2-Aminopurine/chemistry , Adenine/chemistry , Adenine/analogs & derivatives , Algorithms , Electrons , Isomerism , Photons , Quantum Theory , Rotation , Spectrum Analysis/methods , VibrationABSTRACT
For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine·H(2)O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift δν of the S(1) â S(0) transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm(-1)), while that of isomer B is much larger (δν = -889 cm(-1)). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H(2)O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy D(e) = 56.4 kJ/mol. Isomers B and C are H-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest (1)ππ* states of A and B in excellent agreement with the observed 0(0)(0) bands; also, the relative intensities of the A and B origin bands agree well with the calculated S(0) state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited (1)ππ* state to the lower-lying (1)nπ* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the (1)ππ* state of B is planar and decoupled from the (1)nπ* state. These observations agree with the calculations, which predict the (1)nπ* above the (1)ππ* state for isomer B but below the (1)ππ* for both 9H-2AP and isomer A.