Gas-Phase Cytosine and Cytosine-N 1 -Derivatives Have 0.1–1 ns Lifetimes Near the S 1 State Minimum

Ultraviolet radiative damage to DNA is inefficient because of the ultrafast S1 ⇝ S0 internal conversion of its nucleobases. Using picosecond pump–ionization delay measurements, we find that the S1(1ππ*) state vibrationless lifetime of gas-phase keto-amino cytosine (Cyt) is τ = 730 ps or ∼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(1nOπ*) and S1(1ππ*) states decreases along the series of N1-derivatives, thereby influencing the S1 state lifetime

The excited-state structure, vibrations, lifetimes, and nonradiative dynamics of jet-cooled 1-methylcytosine

We have investigated the S0 → 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 timeresolved 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 ν′1 (butterfly) vibrations are strongly coupled, in the S1 state. The S0 → S1 vibronic spectrum breaks off at a vibrational excess energy Eexc ∼ 500 cm−1, indicating that a barrier in front of the ethylene-type S1 S0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm−1. The S1 S0 internal conversion rate constant increases from kIC = 2 · 109 s−1 near the S1(v = 0) level to 1 · 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 · 108 s−1 near S1(v = 0) to kISC = 2 · 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 S1 T2 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 → 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 mechanismsThis research has been supported by the Schweiz. Nationalfonds (Grant Nos. 121993 and 132540), the Agència de Gestió d’Ajuts Universitaris i de Recerca (AGAUR) from Catalonia (Spain) (Grant No. 2014SGR1202), the Ministerio de Economía y Competividad (MINECO) from Spain (Grant No. CTQ2015-69363-P), and the National Natural Science Foundation of China (Grant No. 21303007

The excited-state structure, vibrations, lifetimes, and nonradiative dynamics of jet-cooled 1-methylcytosine

We have investigated the S0 → 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 timeresolved 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 ν′1 (butterfly) vibrations are strongly coupled, in the S1 state. The S0 → S1 vibronic spectrum breaks off at a vibrational excess energy Eexc ∼ 500 cm−1, indicating that a barrier in front of the ethylene-type S1 S0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm−1. The S1 S0 internal conversion rate constant increases from kIC = 2 · 109 s−1 near the S1(v = 0) level to 1 · 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 · 108 s−1 near S1(v = 0) to kISC = 2 · 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 S1 T2 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 → 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 mechanismsThis research has been supported by the Schweiz. Nationalfonds (Grant Nos. 121993 and 132540), the Agència de Gestió d’Ajuts Universitaris i de Recerca (AGAUR) from Catalonia (Spain) (Grant No. 2014SGR1202), the Ministerio de Economía y Competividad (MINECO) from Spain (Grant No. CTQ2015-69363-P), and the National Natural Science Foundation of China (Grant No. 21303007

Adsorption of Proteins on Colloidal Lignin Particles for Advanced Biomaterials

| openaire: EC/H2020/720303/EU//ZELCORCoating of colloidal lignin particles (CLPs), or lignin nanoparticles (LNPs), with proteins was evaluated in order to establish a safe, self-assembly mediated modification technique to tune their surface chemistry. Gelatin and poly- l-lysine formed the most pronounced protein corona on the CLP surface, as determined by dynamic light scattering (DLS) and zeta potential measurements. Spherical morphology of individual protein coated CLPs was confirmed by transmission electron (TEM) and atomic force (AFM) microscopy. A mechanistic adsorption study with several random coiled and globular model proteins was carried out using quartz crystal microbalance with dissipation monitoring (QCM-D). The three-dimensional (3D) protein fold structure and certain amino acid interactions were decisive for the protein adsorption on the lignin surface. The main driving forces for protein adsorption were electrostatic, hydrophobic, and van der Waals interactions, and hydrogen bonding. The relative contributions of these interactions were highly dependent on the ionic strength of the surrounding medium. Capillary electrophoresis (CE) and Fourier transform infrared spectroscopy (FTIR) provided further evidence of the adsorption-enhancing role of specific amino acid residues such as serine and proline. These results have high impact on the utilization of lignin as colloidal particles in biomedicine and biodegradable materials, as the protein corona enables tailoring of the CLP surface chemistry for intended applications.Peer reviewe

Gas-Phase Cytosine and Cytosine‑N₁‑Derivatives Have 0.1–1 ns Lifetimes Near the S₁ State Minimum

Ultraviolet radiative damage to DNA is inefficient because of the ultrafast S₁ ⇝ S₀ internal conversion of its nucleobases. Using picosecond pump–ionization delay measurements, we find that the S₁(¹<i>ππ</i>*) state vibrationless lifetime of gas-phase keto-amino cytosine (Cyt) is τ = 730 ps or ∼700 times longer than that measured by femtosecond pump–probe ionization at higher vibrational excess energy, <i>E</i>_exc. 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 <i>E</i>_exc = 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<i>n</i>_Oπ*) and S₁(¹<i>ππ</i>*) states decreases along the series of N₁-derivatives, thereby influencing the S₁ state lifetime