Binning method for artifact-free time-tag based correlation function calculations.

Correlation functions are nowadays routinely computed using time-tagged photon information instead of a hardware autocorrelator. The algorithm developed by Laurence et al. [Opt.

Unveiling the Configurational Landscape of Carbamate: Paving the Way for Designing Functional Sequence-Defined Polymers.

Carbamate is an emerging class of a polymer backbone for constructing sequence-defined, abiotic polymers. It is expected that new functional materials can be designed by controlling the primary polycarbamate sequence. While amino acids have been actively studied as building blocks for protein folding and peptide self-assembly, carbamates have not been widely investigated from this perspective.

Toward time resolved dynamic light scattering microscopy: Retrieving particle size distributions at high temporal resolutions.

Dynamic light scattering (DLS) is a widely applied technique in multiple scientific and industrial fields for the size characterization of nanoscale objects in solution. While DLS is typically applied to characterize systems under static conditions, the emerging interest in using DLS on temporally evolving systems stimulates the latent need to improve the time resolution of measurements. Herein, we present a DLS microscopy setup (micro-DLS) that can accurately characterize the size of particles from autocorrelation functions built from sub-100 ms time windows, several orders of magnitude faster than previously reported.

Hazardous chemical elements in cleaning cloths, a potential source of microfibres.

Although potentially hazardous chemical elements (e.g., Cu, Cr, Pb, Sb, Ti, Zn) have been studied in clothing textiles, their presence in cleaning textiles is unknown.

In situ optical spectroscopy of crystallization: One crystal nucleation at a time.

While crystallization is a ubiquitous and an important process, the microscopic picture of crystal nucleation is yet to be established. Recent studies suggest that the nucleation process can be more complex than the view offered by the classical nucleation theory. Here, we implement single crystal nucleation spectroscopy (SCNS) by combining Raman microspectroscopy and optical trapping induced crystallization to spectroscopically investigate one crystal nucleation at a time.

Control of Intermolecular Photoinduced Electron Transfer in Deoxyadenosine-Based Fluorescent Probes.

In this work, we report on the Photoinduced Electron Transfer (PET) reaction between a donor (adenine analogue) and an acceptor (3-methoxychromone dye, 3MC) in the context of designing efficient fluorescent probes as DNA sensors. Firstly, Gibbs energy was investigated in disconnected donor-acceptor systems by Rehm-Weller equation. The oxidation potential of the adenine derivative was responsible for exergonicity of the PET reaction in separated combinations.

Excited-State Proton Transfer in Oxyluciferin and Its Analogues.

One of the most characterized bioluminescent reactions involves the firefly luciferase that catalyzes the oxidation of the luciferin producing oxyluciferin in its first excited state. While relaxing to the ground state, oxyluciferin emits visible light with an emission maximum that can vary from green to red. Oxyluciferin exists under six different chemical forms resulting from a keto/enol tautomerization and the deprotonation of the phenol or enol moieties.

E to Z Photoisomerization of Phytochrome Cph1Δ Exceeds the Born-Oppenheimer Adiabatic Limit.

The Born-Oppenheimer adiabatic limit applies broadly in chemistry because most reactions occur on the ground electronic state. Photochemical reactions involve two or more electronic states and need not be subject to this adiabatic limit. The spectroscopic signatures of nonadiabatic processes are subtle, and therefore, experimental investigations have been limited to the few systems dominated by single photochemical outcomes.

Resolving the Singlet Excited State Manifold of Benzophenone by First-Principles Simulations and Ultrafast Spectroscopy.

Accurate characterization of the high-lying excited state manifolds of organic molecules is of fundamental importance for the interpretation of the rich response detected in time-resolved nonlinear electronic spectroscopies. Here, we have characterized the singlet excited state manifold of benzophenone (BP), a versatile organic photoinitiator and a well-known DNA photosensitizer. Benchmarks of various multiconfigurational/multireference (RASSCF/PT2) and time-dependent density functional theory (TD-DFT) approaches allowed assignments of experimental linear absorption signals of BP in the ultraviolet (UV) region, with unprecedented characterization of ground state absorptions in the far UV.

Electronic Couplings in (Bio-) Chemical Processes.

During the last two decades, 2D optical techniques have been extended to the visible range, targeting electronic transitions. Since the report of the very first 2D electronic measurement (Hybl et al. in J Chem Phys 115:6606-6622, [2001]), two-dimensional electronic spectroscopy (2DES) has allowed fundamentally new insights into the structure and dynamics of condensed-phase systems (Ginsberg et al.

Effect of point mutations on the ultrafast photo-isomerization of Anabaena sensory rhodopsin.

Anabaena sensory rhodopsin (ASR) is a particular microbial retinal protein for which light-adaptation leads to the ability to bind both the all-trans, 15-anti (AT) and the 13-cis, 15-syn (13C) isomers of the protonated Schiff base of retinal (PSBR). In the context of obtaining insight into the mechanisms by which retinal proteins catalyse the PSBR photo-isomerization reaction, ASR is a model system allowing to study, within the same protein, the protein-PSBR interactions for two different PSBR conformers at the same time. A detailed analysis of the vibrational spectra of AT and 13C, and their photo-products in wild-type ASR obtained through femtosecond (pump-) four-wave-mixing is reported for the first time, and compared to bacterio- and channelrhodopsin.

The effect of solvent relaxation in the ultrafast time-resolved spectroscopy of solvated benzophenone.

Benzophenone (BP) despite its relatively simple molecular structure is a paradigmatic sensitizer, featuring both photocatalytic and photobiological effects due to its rather complex photophysical properties. In this contribution we report an original theoretical approach to model realistic, ultra-fast spectroscopy data, which requires describing intra- and intermolecular energy and structural relaxation. In particular we explicitly simulate time-resolved pump-probe spectra using a combination of state-of-the art hybrid quantum mechanics/molecular mechanics dynamics to treat relaxation and vibrational effects.

Conformational Homogeneity in the P Isomer of Phytochrome Cph1.

Numerous time-resolved studies of the P to P photoisomerization in phytochrome Cph1 have revealed multiphasic excited-state decay kinetics. It remains unclear whether these kinetics arise from multiple ground-state conformational subpopulations or from a single ground-state conformation that undergoes an excited-state photoisomerization process-either branching on the excited state or relaxing through multiple sequential intermediates. Many studies have attempted to resolve this debate by fitting the measured dynamics to proposed kinetic models, arriving at different conclusions.

High-Energy Long-Lived Mixed Frenkel-Charge-Transfer Excitons: From Double Stranded (AT)n to Natural DNA.

The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV-induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine-thymine double-stranded structures (AT)n . Fluorescence measurements on (AT)n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale.

Experimental Detection of Branching at a Conical Intersection in a Highly Fluorescent Molecule.

Conical intersections are molecular configurations at which adiabatic potential-energy surfaces touch. They are predicted to be ubiquitous, yet condensed-phase experiments have focused on the few systems with clear spectroscopic signatures of negligible fluorescence, high photoactivity, or femtosecond electronic kinetics. Although rare, these signatures have become diagnostic for conical intersections.

Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy.

Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy.

Stabilization of Mixed Frenkel-Charge Transfer Excitons Extended Across Both Strands of Guanine-Cytosine DNA Duplexes.

The photoreactive pathways that may lead to DNA damage depend crucially upon the nature of the excited electronic states. The study of alternating guanine-cytosine duplexes by fluorescence spectroscopy and quantum mechanical calculations identifies a novel type of excited states that can be populated following UVB excitation. These states, denoted High-energy Emitting Long-lived Mixed (HELM) states, extend across both strands and arise from mixing between cytosine Frenkel excitons and guanine-to-cytosine charge transfer states.

Accurate convergence of transient-absorption spectra using pulsed lasers.

Transient-absorption spectroscopy is a common and well-developed technique for measuring time-dependent optical phenomena. One important aspect, especially for measurements using pulsed lasers, is how to average multiple data acquisition events. Here, we use a mathematical analysis method based on covariance to evaluate various averaging schemes.

Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy.

Guanine-cytosine hairpins, containing a hexaethylene glycol bridge, are studied by steady-state fluorescence spectroscopy and time-correlated single photon counting; their properties are compared to those of duplexes with the same sequence. It is shown that, both in hairpins and in duplexes, base pairing induces quenching of the ππ* fluorescence, the quantum yield decreasing by at least two orders of magnitude. When the size of the systems increases from two to ten base pairs, a fluorescent component decaying on the nanosecond time-scale appears at energy higher than that stemming from the bright states of non-interacting mono-nucleotides (ca.

Electronically excited states of DNA oligonucleotides with disordered base sequences studied by fluorescence spectroscopy.

DNA double-stranded oligomers are studied by steady-state and time-resolved fluorescence spectroscopy from the femtosecond to the nanosecond time-scale, following excitation at 267 nm. It is shown that emission arises from three types of excited states. (i) Bright ππ* states emitting around 330 nm and decaying on the sub-picosecond time-scale with an average lifetime of ca.

Conformation and energy transfer in single conjugated polymers.

In contrast to the detailed understanding of inorganic materials, researchers lack a comprehensive view of how the properties of bulk organic materials arise from their individual components. For conjugated polymers to eventually serve as low cost semiconductor layers in electronic devices, researchers need to better understand their functionality. For organics, traditional materials science measurements tend to destroy the species of interest, especially at low concentrations.

Mimicking conjugated polymer thin-film photophysics with a well-defined triblock copolymer in solution.

Conjugated polymers (CPs) are promising materials for use in electronic applications, such as low-cost, easily processed organic photovoltaic (OPV) devices. Improving OPV efficiencies is hindered by a lack of a fundamental understanding of the photophysics in CP-based thin films that is complicated by their heterogeneous nanoscale morphologies. Here, we report on a poly(3-hexylthiophene)-block-poly(tert-butyl acrylate)-block-poly(3-hexylthiophene) rod-coil-rod triblock copolymer.

Self-assembly of highly ordered conjugated polymer aggregates with long-range energy transfer.

Applications of conjugated polymers (CP) in organic electronic devices such as light-emitting diodes and solar cells depend critically on the nature of electronic energy transport in these materials. Single-molecule spectroscopy has revealed their fundamental properties with molecular detail, and recent reports suggest that energy transport in single CP chains can extend over extraordinarily long distances of up to 75 nm. An important question arises as to whether these characteristics are sustained when CP chains agglomerate into a neat solid.