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Long-lived phosphorescence has been observed at room temperature in two gold(i) complexes of a fluorenyl-substituted N-heterocyclic carbene.

Four new laterally asymmetric dinuclear gold(I) complexes made from a new chromophoric ligand (Au-DiBTF0–3) have been characterized. Changing the organic ancillary ligand from a phosphine ((Au-DiBT...

The syntheses and photophysical characterization of five new gold(I) complexes bearing diphenylamine-substituted fluorenyl moieties are reported; four are characterized by X-ray diffraction crystallography. Ancillary ligation on gold(I) is provided by organophosphine and N-heterocyclic carbene ligands. Two complexes

DNA strands are polymeric ligands that both protect and tune molecular-sized silver cluster chromophores. We studied single-stranded DNA C4AC4TC3XT4 with X = guanosine and inosine that form a green fluorescent Ag106+ cluster, but these two hosts are distinguished by their binding sites and the brightness of their Ag106+ adducts. The nucleobase subunits in these oligomers collectively coordinate this cluster, and fs time-resolved infrared spectra previously identified one point of contact between the C2–NH2 of the X = guanosine, an interaction that is precluded for inosine. Furthermore, this single nucleobase controls the cluster fluorescence as the X = guanosine complex is ∼2.5× dimmer. We discuss the electronic relaxation in these two complexes using transient absorption spectroscopy in the time window 200 fs–400 µs. Three prominent features emerged: a ground state bleach, an excited state absorption, and a stimulated emission. Stimulated emission at the earliest delay time (200 fs) suggests that the emissive state is populated promptly following photoexcitation. Concurrently, the excited state decays and the ground state recovers, and these changes are ∼2× faster for the X = guanosine compared to the X = inosine cluster, paralleling their brightness difference. In contrast to similar radiative decay rates, the nonradiative decay rate is 7× higher with the X = guanosine vs inosine strand. A minor decay channel via a dark state is discussed. The possible correlation between the nonradiative decay and selective coordination with the X = guanosine/inosine suggests that specific nucleobase subunits within a DNA strand can modulate cluster–ligand interactions and, in turn, cluster brightness.

Discovery of planets outside our solar system, known as extra-solar planets or exoplanets for short, has been at the forefront of astronomical research for over 25 years. Reports of new discoveries have almost become routine; however, the excitement surrounding them has not. Amazingly, as groundbreaking as exoplanet science is, the basic physics is quite accessible to first-year physics students, as discussed in previous TPT articles. To further illustrate this point, we developed an iOS application that generates synthetic exoplanet data to provide students and teachers with interactive learning activities. Using introductory physics concepts, we demonstrate how to estimate exoplanet mass, radius, and density from the app output. These calculations form the basis for a diverse range of classroom activities. We conclude with a summary of exoplanet science resources for teachers.

Changing the solvent from H2O to D2O dramatically affects the branching of the initial excited electronic states in an alternating G·C DNA duplex into two distinct decay channels. The slower, multisite PCET channel that deactivates more than half of all excited states in D2O becomes six times weaker in H2O.

The excited-state dynamics of three distinct forms of the d(GC)9·d(GC)9 DNA duplex were studied by combined time-resolved infrared experiments and quantum mechanical calculations. In the B- and Z-forms, bases on opposite strands form Watson-Crick (WC) base pairs but stack differently because of salt-induced changes in backbone conformation. At low pH, the two strands associate by Hoogsteen (HG) base pairing. Ultraviolet-induced intrastrand electron transfer (ET) triggers interstrand proton transfer (PT) in the B- and Z-forms, but the PT pathway is blocked in the HG duplex. Despite the different decay mechanisms, a common excited-state lifetime of ∼ 30 ps is observed in all three duplex forms. The ET-PT pathway in the WC duplexes and the solely intrastrand ET pathway in the HG duplex yield the same pair of π-stacked radicals on one strand. Back ET between these radicals is proposed to be the rate-limiting step behind excited-state deactivation in all three duplexes.

The IR spectrum of a charge transfer (CT) excited electronic state in DNA has been computed for the first time, enabling assignment of the long-lived component of the transient IR spectrum of a d(AT)9 single strand to an A → T CT state. Experimentally, the CT state lifetime is much shorter than in the double strand, and our calculations explain this result using Marcus Theory.

Förster resonance energy transfer (FRET) is the basis for many techniques used in biomedical research. Due to its wide use in molecular sensing, FRET is commonly introduced in many biology, chemistry, and physics courses. While FRET is of great importance in the biophysical sciences, the complexity and difficulty of constructing FRET experiments has resulted in limited usage in undergraduate laboratory settings. Here, we present a practical undergraduate laboratory experiment for teaching FRET using a diverse set of green-emitting fluorescent proteins (FPs) as donors for a cross-linked Yukon orange FP. This laboratory experiment enables students to make the connection of basic lab procedures to real world applications and can be applied to molecular biology, biochemistry, physical chemistry, and biophysical laboratory courses. Published 2018. This article is a U.S. Government work and is in the public domain in the USA., 46(5):516-522, 2018.

To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump–probe measurements were performed on a d(AT)9·d(AT)9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps...

UV radiation creates excited states in DNA that lead to mutagenic photoproducts. Photoexcitation of single-stranded DNA can transfer an electron between stacked bases, but the fate of excited states in the double helix has been intensely debated. Here, photoinduced interstrand proton transfer (PT) triggered by intrastrand electron transfer (ET) is detected for the first time by time-resolved vibrational spectroscopy and quantum mechanical calculations. Long-lived excited states are shown to be oppositely charged base pair radical ions. In two of the duplexes, the base pair radical anions are present as tautomers formed by interstrand PT. Charge recombination occurs on the picosecond time scale preventing the accumulation of damaging radicals or mutagenic tautomers.

Excited electronic states with lifetimes longer than those of mononucleotides have been observed in a variety of DNA and RNA base multimers. Most studies reported to date were performed on repetiti...

Excited electronic states in a genomic DNA sequence containing all four DNA bases were studied using femtosecond transient absorption spectroscopy. Long-lived excited states observed in each single strand separately are conserved in the duplex DNA.

Isotope effects on the excited-state dynamics of single- and double-stranded GC-containing DNAs were studied by femtosecond transient absorption spectroscopy. A pronounced deuterium isotope effect was observed in alternating d(GC)(9).d(GC)(9), but none was seen in the nonalternating or single-stranded variations investigated. These findings demonstrate that an interstrand process involving proton-coupled electron transfer contributes to the excited-state dynamics in DNAs having an appropriate base sequence.

DNA photophysics: Femtosecond transient absorption experiments reveal that excited states produced by UV light in a duplex DNA oligonucleotide decay at essentially the same rate in B and Z helix conformers (see figure).