Ultrafast delocalization of excitation in synthetic light-harvesting nanorings

Rings of chlorophyll molecules harvest sunlight remarkably efficiently during photosynthesis in purple bacteria. The key to their efficiency lies in their highly delocalized excited states that allow for ultrafast energy migration. Here we show that a family of synthetic nanorings mimic the ultrafast energy transfer and delocalization observed in nature. π-Conjugated nanorings with diameters of up to 10 nm, consisting of up to 24 porphyrin units, are found to exhibit excitation delocalization within the first 200 fs of light absorption. Transitions from the first singlet excited state of the circular nanorings are dipole-forbidden as a result of symmetry constraints, but these selection rules can be lifted through static and dynamic distortions of the rings. The increase in the radiative emission rate in the larger nanorings correlates with an increase in static disorder expected from Monte Carlo simulations. For highly symmetric rings, the radiative rate is found to increase with increasing temperature. Although this type of thermally activated superradiance has been theoretically predicted in circular chromophore arrays, it has not previously been observed in any natural or synthetic systems. As expected, the activation energy for emission increases when a nanoring is fixed in a circular conformation by coordination to a radial template. These nanorings offer extended chromophores with high excitation delocalization that is remarkably stable against thermally induced disorder. Such findings open new opportunities for exploring coherence effects in nanometer molecular rings and for implementing these biomimetic light-harvesters in man-made devices.     

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O2-tolerant NAD+-reducing [NiFe] hydrogenase

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD⁺-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H₂ conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by ⁵⁷Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD⁺-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective ¹³C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.     

Ultrafast intermolecular dynamics of liquid water: a theoretical study on two-dimensional infrared spectroscopy

Physical and chemical properties of liquid water are dominated by hydrogen bond structure and dynamics. Recent studies on nonlinear vibrational spectroscopy of intramolecular motion provided new insight into ultrafast hydrogen bond dynamics. However, our understanding of intermolecular dynamics of water is still limited. We theoretically investigated the intermolecular dynamics of liquid water in terms of two-dimensional infrared (2D IR) spectroscopy. The 2D IR spectrum of intermolecular frequency region (<1000 cm(-1)) is calculated by using the equilibrium and nonequilibrium hybrid molecular dynamics method. We find the ultrafast loss of the correlation of the libration motion with the time scale of approximately 110 fs. It is also found that the energy relaxation from the libration motion to the low frequency motion takes place with the time scale of about 180 fs. We analyze the effect of the hindered translation motion on these ultrafast dynamics. It is shown that both the frequency modulation of libration motion and the energy relaxation from the libration to the low frequency motion significantly slow down in the absence of the hindered translation motion. The present result reveals that the anharmonic coupling between the hindered translation and libration motions is essential for the ultrafast relaxation dynamics in liquid water.     

Ultrafast infrared spectroscopy of riboflavin: dynamics, electronic structure, and vibrational mode analysis

Femtosecond time-resolved infrared spectroscopy was used to study the vibrational response of riboflavin in DMSO to photoexcitation at 387 nm. Vibrational cooling in the excited electronic state is observed and characterized by a time constant of 4.0 +/- 0.1 ps. Its characteristic pattern of negative and positive IR difference signals allows the identification and determination of excited-state vibrational frequencies of riboflavin in the spectral region between 1100 and 1740 cm (-1). Density functional theory (B3LYP), Hartree-Fock (HF) and configuration interaction singles (CIS) methods were employed to calculate the vibrational spectra of the electronic ground state and the first singlet excited pipi* state as well as respective electronic energies, structural parameters, electronic dipole moments and intrinsic force constants. The harmonic frequencies of the S 1 excited state calculated by the CIS method are in satisfactory agreement with the observed band positions. There is a clear correspondence between computed ground- and excited-state vibrations. Major changes upon photoexcitation include the loss of the double bond between the C4a and N5 atoms, reflected in a downshift of related vibrations in the spectral region from 1450 to 1720 cm (-1). Furthermore, the vibrational analysis reveals intra- and intermolecular hydrogen bonding of the riboflavin chromophore.     

Functional modulation and directed assembly of an enzyme through designed non-natural post-translation modification

Post-translational modification (PTM) modulates and supplements protein functionality. In nature this high precision event requires specific motifs and/or associated modification machinery. To overcome the inherent complexity that hinders PTM''s wider use, we have utilized a non-native biocompatible Click chemistry approach to site-specifically modify TEM β-lactamase that adds new functionality. In silico modelling was used to design TEM β-lactamase variants with the non-natural amino acid p-azido-l-phenylalanine (azF) placed at functionally strategic positions permitting residue-specific modification with alkyne adducts by exploiting strain-promoted azide–alkyne cycloaddition. Three designs were implemented so that the modification would: (i) inhibit TEM activity (Y105azF); (ii) restore activity compromised by the initial mutation (P174azF); (iii) facilitate assembly on pristine graphene (W165azF). A dibenzylcyclooctyne (DBCO) with amine functionality was enough to modulate enzymatic activity. Modification of TEM^W165azF with a DBCO–pyrene adduct had little effect on activity despite the modification site being close to a key catalytic residue but allowed directed assembly of the enzyme on graphene, potentially facilitating the construction of protein-gated carbon transistor systems.     

Ultrafast dynamics of the carbonyl stretching vibration in acetic acid in aqueous solution studied by sub-picosecond infrared spectroscopy

Vibrational energy relaxation of the carbonyl CO stretching modes of CH3COOD and CD3COOD in D2O is studied by frequency-resolved infrared pump-probe spectroscopy. The spectral change caused by the vibrational excitation includes two dynamical components with the time constants of 450 and 980 fs for CH3COOD and 390 and 930 fs for CD3COOD. The two dynamical components exhibit different spectral properties. There are two species of acetic acid forming different complexes with solvent water molecules. The time constants are almost the same for CH3COOD and CD3COOD, suggesting that the vibrational energy deposited to the carbonyl group is first distributed among vibrational modes not related to the methyl group.     

In vivo visible light-triggered drug release from an implanted depot

Controlling chemistry in space and time has offered scientists and engineers powerful tools for research and technology. For example, on-demand photo-triggered activation of neurotransmitters has revolutionized neuroscience. Non-invasive control of the availability of bioactive molecules in living organisms will undoubtedly lead to major advances; however, this requires the development of photosystems that efficiently respond to regions of the electromagnetic spectrum that innocuously penetrate tissue. To this end, we have developed a polymer that photochemically degrades upon absorption of one photon of visible light and demonstrated its potential for medical applications. Particles formulated from this polymer release molecular cargo in vitro and in vivo upon irradiation with blue visible light through a photoexpansile swelling mechanism.     

Ultrafast coherent photoexcited dynamics in a trimeric dendrimer probed by X-ray stimulated-Raman signals

The photoinduced ultrafast coherent inter-chromophore energy redistribution in a triarylamine trimer is explored using nonadiabatic excited state molecular dynamics followed by simulations of X-ray Raman signals. The nitrogencentered system ensures strong interchromophore interactions and, thus, the presence of coherences. Nevertheless, the multitude of non-deterministic photoinduced pathways during the ultrafast inter-branch migration of the excitation results in random confinement on some branches and, therefore, spatial exciton scrambling and loss of phase information at long times. We show that the vibronic coherence dynamics evolving into the incoherent scrambling mechanism on ultrafast 50 fs timescale, is accurately probed by the TRUECARS X-ray stimulated Raman signal. In combination with previous results, where the technique has revealed long-lived coherences in a rigid heterodimer, the signal is most valuable for detecting ultrafast molecular coherences or their absence. We demonstrate that X-ray Raman spectroscopy is a useful tool in the chemical design of functional molecular building blocks.

The photoinduced ultrafast coherent inter-chromophore energy redistribution in a triarylamine trimer is explored using nonadiabatic excited state molecular dynamics followed by simulations of X-ray Raman signals.     

Ultrafast carrier dynamics in single-walled carbon nanotubes probed by femtosecond spectroscopy

Ultrafast carrier dynamics in individual semiconducting single-walled carbon nanotubes was studied by femtosecond transient absorption and fluorescence measurements. After photoexcitation of the second van Hove singularity of a specific tube structure, the relaxation of electrons and holes to the fundamental band edge occurs to within 100 fs. The fluorescence decay from this band is dependent on the excitation density and can be rationalized by exciton annihilation theory. In contrast to fluorescence, the transient absorption has a distinctly different time and intensity dependence for different tube structures, suggesting a branching to emissive and trap states following photoexcitation.     

17O NMR spectroscopy of crystalline microporous materials

Microporous materials, containing pores and channels of similar dimensions to small molecules have a range of applications in catalysis, gas storage and separation and in drug delivery. Their complex structure, often containing different types and levels of positional, compositional and temporal disorder, makes structural characterisation challenging, with information on both long-range order and the local environment required to understand the structure–property relationships and improve the future design of functional materials. In principle, ¹⁷O NMR spectroscopy should offer an ideal tool, with oxygen atoms lining the pores of many zeolites and phosphate frameworks, playing a vital role in host–guest chemistry and reactivity, and linking the organic and inorganic components of metal–organic frameworks (MOFs). However, routine study is challenging, primarily as a result of the low natural abundance of this isotope (0.037%), exacerbated by the presence of the quadrupolar interaction that broadens the spectral lines and hinders the extraction of information. In this Perspective, we will highlight the current state-of-the-art for ¹⁷O NMR of microporous materials, focusing in particular on cost-effective and atom-efficient approaches to enrichment, the use of enrichment to explore chemical reactivity, the challenge of spectral interpretation and the approaches used to help this and the information that can be obtained from NMR spectra. Finally, we will turn to the remaining challenges, including further improving sensitivity, the high-throughput generation of multiple structural models for computational study and the possibility of in situ and in operando measurements, and give a personal perspective on how these required improvements can be used to help solve important problems in microporous materials chemistry.

Cost-effective and atom-efficient isotopic enrichment enables ¹⁷O NMR spectroscopy of microporous materials to be used to probe local structure and disorder and to explore chemical reactivity.     

Ultrafast dynamics and coherent oscillations in ethylene and ethylene-d4 excited at 162 nm

The fifth harmonic (162 nm, 11 fs), generated in a short argon cell from 12 fs Ti-sapphire laser pulses, was used to excite C2H4 and C2D4 in the maximum of the first pi pi* transition. Around 10% of the molecules were excited to the pi3s Rydberg state instead. The subsequent motion of the wave packet, moving over the potentials from the Franck-Condon region down to the ground state, was monitored by nonresonant ionization at 810 nm with mass-selective detection of the ion yield. Five time constants (from approximately 20 fs in excited states to 0.6-11 ps in the hot ground state) and four coherent oscillations (CC stretch and torsion vibrations or hindered free rotation) were determined for each isotopomer. The initial relaxation follows a superposition of CC twist and stretch coordinates; this explains a surprisingly small deuterium isotope effect of the initial time constant (21 versus 24 fs). Also the vibrations in the Franck-Condon region have such a mixed character and a correspondingly small isotope shift. From the perpendicular minimum the wave packet reaches (within 17 or 21 fs for the two isotopomers) a conical intersection via a direction that also involves partial hydrogen migration. This is concluded from the detection of ethylidene (CH3CH), formed simultaneously with ground-state ethylene. This carbene isomerizes in the ground state within 0.6 ps (1.6 ps for CD3CD) to ethylene. Two time constants for dissociation (4.5 and 11 ps) in the hot ground state were also identified. The small yields of bimolecular reactions (photodimerization, addition reactions involving a "suddenly polarized" excited state, carbene reactions) are interpreted in terms of the short lifetimes. It is pointed out that the relaxation path starting from the Rydberg state merges into that from the pi pi* state; nevertheless, there is a wavelength dependence in the photochemistry of olefins, because due to a momentum effect the wave packet remembers from which state it came.     

Ultrafast excited-state dynamics in photochromic N-salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy

Ultrafast processes in photoexcited N-salicylideneaniline have been investigated with femtosecond time-resolved resonance-enhanced multiphoton ionization spectroscopy. The ion signals via the S(1)(n,pi( *)) state of the enol form as well as the proton-transferred cis-keto form emerge within a few hundred femtoseconds after photoexcitation to the first S(1)(pi,pi( *)) state of the enol form. This reveals that two ultrafast processes, excited-state intramolecular proton transfer (ESIPT) reaction and an internal conversion (IC) to the S(1)(n,pi( *)) state, occur on a time scale less than a few hundred femtoseconds from the S(1)(pi,pi( *)) state of the enol form. The rise time of the transient corresponding to the production of the proton-transferred cis-keto form is within 750 fs when near the red edge of the absorption is excited, indicating that the ESIPT reaction occurs within 750 fs. The decay time of the S(1)(pi,pi( *)) state of the cis-keto form is 8.9 ps by exciting the enol form at 370 nm, but it dramatically decreases to be 1.5-1.6 ps for the excitation at 365-320 nm. The decrease in the decay time has been attributed to the opening of an efficient nonradiative channel; an IC from S(1)(pi,pi( *)) to S(1)(n,pi( *)) of the cis-keto form promotes the production of the trans-keto form as the final photochromic products. The two IC processes may provide opposite effect on the quantum yield of photochromic products: IC in the enol form may substantially reduce the quantum yield, but IC in the cis-keto form increase it.     

Efficient red light photo-uncaging of active molecules in water upon assembly into nanoparticles

We introduce a means of efficiently photo-uncaging active compounds from amino-1,4-benzoquinone in aqueous environments. Aqueous photochemistry of this photocage with one-photon red light is typically not efficient unless the photocaged molecules are allowed to assemble into nanoparticles. A variety of biologically active molecules were functionalized with the photocage and subsequently formulated into water-dispersible nanoparticles. Red light irradiation through various mammalian tissues achieved efficient photo-uncaging. Co-encapsulation of NIR fluorescent dyes and subsequent photomodulation provides a NIR fluorescent tool to assess both particle location and successful photorelease.     

Efficient chemoenzymatic synthesis of an N-glycan isomer library

Quantification, characterization and biofunctional studies of N-glycans on proteins remain challenging tasks due to the complexity, diversity and low abundance of these glycans. The availability of structurally defined N-glycan (especially isomer) libraries is essential to help solve these tasks. We report herein an efficient chemoenzymatic strategy, namely Core Synthesis/Enzymatic Extension (CSEE), for rapid production of diverse N-glycans. Starting with 5 chemically prepared building blocks, 8 N-glycan core structures containing one or two terminal N-acetyl-d-glucosamine (GlcNAc) residue(s) were chemically synthesized via consistent use of oligosaccharyl thioethers as glycosylation donors in a convergent fragment coupling strategy. Each of these core structures was then extended to 5 to 15 N-glycan sequences by enzymatic reactions catalyzed by 4 robust glycosyltransferases. Success in synthesizing N-glycans with Neu5Gc and core-fucosylation further expanded the ability of the enzymatic extension. Meanwhile, high performance liquid chromatography with an amide column enabled rapid and efficient purification (>98% purity) of N-glycans in milligram scales. A total of 73 N-glycans (63 isomers) were successfully prepared and characterized by MS² and NMR. In summary, the CSEE strategy provides a practical approach for “mass production” of structurally defined N-glycans, which are important standards and probes for glycoscience.     

Ultrafast vibrational dynamics of SCN(-) and N3(-) in polar solvents studied by nonlinear infrared spectroscopy

In this paper, we report on our investigation into the vibrational dynamics of the antisymmetric stretching modes of SCN(-) and N(3)(-) in several polar solvents. We used an infrared (IR) pump-probe method to study orientational relaxation processes. In two aprotic solvents (N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)), the anisotropy decay shows a bimodal feature, whereas in other solvents the anisotropy decay can be fitted well by a single exponential function. We consider that the relative contribution of fast-decaying components is smaller in the other solvents than in DMF and DMSO. We discuss the possible origins of the different anisotropy decay behavior in different solvents. From the three-pulse IR photon echo measurements for SCN(-) and N(3)(-), we found that the time-correlation functions (TCFs) of vibrational frequency fluctuations decay on two different time scales, one of which is less than 100 fs and the other is approximately 3-6 ps. In aprotic solvents, the fast-decaying components of the TCFs on a <100 fs time scale play an important role in the vibrational frequency fluctuation, although the contribution of collective solvent reorganization in aprotic solvents was clearly observed to have small amplitudes. On the other hand, we found that the amplitude of components that decay in a few picoseconds and/or the constant offset of the TCF in protic solvents is relatively large compared with that in aprotic solvents. With the formation and dissociation of hydrogen bonds between ion solute and solvent molecules, the spectra of different solvated species are exchanged with each other and merged into one band. We considered that this exchange may be an origin of slow-decaying components of the TCFs and that the decay of the TCFs corresponds to the time scales of the exchange for protic solvents such as formamide. The mechanism of vibrational frequency fluctuations for the antisymmetric stretching modes of SCN(-) and N(3)(-) is discussed in terms of the difference between protic and aprotic solvents.     

Vibrational population distributions in infrared multiple-photon excitation probed by coherent anti-stokes Raman spectroscopy

Coherent anti-stokes Raman spectroscopy has been used as a probe for molecules pumped by high-intensity CO₂ laser radiation. Ozone, sulfur hexafluoride, and chloroethane have been investigated. The intensity of the ground-state CARS signal is decreased by IR multiphoton excitation, but signals at new vibrational origins do not appear. The observations on chloroethane are interpreted in terms of a rate-equation model for IRMPE, modified to take vibrational redistribution into account.     

Ultrafast dynamics in thiophene investigated by femtosecond pump probe photoelectron spectroscopy and theory

A hybrid of a time-of-flight mass spectrometer and a time-of-flight "magnetic-bottle type" photoelectron (PE) spectrometer is used for fs pump-probe investigations of the excited state dynamics of thiophene. A resonant two-photon ionization spectrum of the onset of the excited states has been recorded with a tunable UV laser of 190 fs pulse width. With the pump laser set to the first intense transition we find by UV probe ionization first a small time shift of the maxima in the PE spectrum and then a fast decay to a low constant intensity level. The fitted time constants are 80+/-10 fs, and 25+/-10 fs, respectively. Theoretical calculations show that upon geometry relaxation the electronic state order changes and conical intersections between excited states exist. We use the vertical state order S1, S2, S3 to define the terms S1, S2, and S3 for the characterization of the electron configuration of these states. On the basis of our theoretical result we discuss the electronic state order in the UV spectra and identify in the photoelectron spectrum the origin of the first cation excited state D1. The fast excited state dynamics agrees best with a vibrational dynamics in the photo-excited S1 (80+/-10 fs) and an ultrafast decay via a conical intersection, presumably a ring opening to the S3 state (25+/-10 fs). The subsequently observed weak constant signal is taken as an indication, that in the gas phase the ring-closure to S0 is slower than 50 ps. An ultrafast equilibrium between S1 and S2 before ring opening is not supported by our data.