Insight into the drastically different triplet lifetimes of BODIPY obtained by optical/magnetic spectroscopy and theoretical computations

The triplet state lifetimes of organic chromophores are crucial for fundamental photochemistry studies as well as applications as photosensitizers in photocatalysis, photovoltaics, photodynamic therapy and photon upconversion. It is noteworthy that the triplet state lifetime of a chromophore can vary significantly for its analogues, while the exact reason was rarely studied. Herein with a few exemplars of typical BODIPY derivatives, which show triplet lifetimes varying up to 110-fold (1.4–160 μs), we found that for these derivatives with short triplet state lifetimes (ca. 1–3 μs), the electron spin polarization (ESP) pattern of the time-resolved electron paramagnetic resonance (TREPR) spectra of the triplet state is inverted at a longer delay time after laser pulse excitation, as a consequence of a strong anisotropy in the decay rates of the zero-field state sublevel of the triplet state. For the derivatives showing longer triplet state lifetimes (>50 μs), no such ESP inversion was observed. The observed fast decay of one sublevel is responsible for the short triplet state lifetime; theoretical computations indicate that it is due to a strong coupling between the T_z sublevel and the ground state mediated by the spin–orbit interaction. Another finding is that the heavy atom effect on the shortening of the triplet state lifetime is more significant for the T₁ states with lower energy. To the best of our knowledge, this is the first systematic study to rationalize the short triplet state lifetime of visible-light-harvesting organic chromophores. Our results are useful for fundamental photochemistry and the design of photosensitizers showing long-lived triplet states.

The electron spin polarization inversion and anisotropic decay of triplet substates explain the short triplet state lifetime of BODIPY derivatives.     

Integrated Conversion of Lignocellulosic Biomass to Bio-Based Amphiphiles using a Functionalization-Defunctionalization Approach

Concerns over the sustainability and end-of-life properties of fossil-derived surfactants have driven interest in bio-based alternatives. Lignocellulosic biomass with its polar functional groups is an obvious feedstock for surfactant production but its use is limited by process complexity and low yield. Here, we present a simple two-step approach to prepare bio-based amphiphiles directly from hemicellulose and lignin at high yields (29 % w/w based on the total raw biomass and >80 % w/w of these two fractions). Acetal functionalization of xylan and lignin with fatty aldehydes during fractionation introduced hydrophobic segments and subsequent defunctionalization by hydrogenolysis of the xylose derivatives or acidic hydrolysis of the lignin derivatives produced amphiphiles. The resulting biodegradable xylose acetals and/or ethers, and lignin-based amphiphilic polymers both largely retained their original natural structures, but exhibited competitive or superior surface activity in water/oil systems compared to common bio-based surfactants.     

Light-Activated Assembly of DNA Origami into Dissipative Fibrils

Hierarchical DNA nanostructures offer programmable functions at scale, but making these structures dynamic, while keeping individual components intact, is challenging. Here we show that the DNA A-motif—protonated, self-complementary poly(adenine) sequences—can propagate DNA origami into one-dimensional, micron-length fibrils. When coupled to a small molecule pH regulator, visible light can activate the hierarchical assembly of our DNA origami into dissipative fibrils. This system is recyclable and does not require DNA modification. By employing a modular and waste-free strategy to assemble and disassemble hierarchical structures built from DNA origami, we offer a facile and accessible route to developing well-defined, dynamic, and large DNA assemblies with temporal control. As a general tool, we envision that coupling the A-motif to cycles of dissipative protonation will allow the transient construction of diverse DNA nanostructures, finding broad applications in dynamic and non-equilibrium nanotechnology.     

A Bayesian approach to seafloor classification using multi-beam echo-sounder backscatter data

Seafloor classification using acoustic remote sensing techniques is an attractive approach due to its high-coverage capabilities and limited costs. The multi-beam echo-sounder (MBES) system provides high-resolution bathymetry and backscatter information with 100% coverage. In this paper, we present a seafloor classification method that employs the MBES backscatter data. The method uses the averaged backscatter data per beam. It, therefore, is independent on the quality of the MBES calibration. Also, its performance is insensitive to seafloor type variation along the MBES swathe and corrections for the angular dependence of the backscatter are not needed. The method accounts for the ping-to-ping variability of the backscatter intensity. It estimates both the number of seafloor types present in the survey area and the probability density function for the backscatter strength at a certain angle for each of the seafloor types. Application of the method to MBES backscatter data acquired in a well-known test area in the North Sea shows very good agreement with available ground truth. The method’s discriminatory performance for this area is demonstrated to be comparable to that of taking samples of the sediment. All seafloor types known to be present in the area are resolved for. Application of the method to the Stanton bank data set shows clearly separable areas that differ in seafloor composition.     

Macroscopic evidence of soliton formation in multiterawatt laser-plasma interaction

A novel physical phenomenon has been observed following the interaction of an intense (10(19) W/cm(2)) laser pulse with an underdense plasma. Long-lived, macroscopic bubblelike structures have been detected through the deflection that the associated electric charge separation causes in a proton probe beam. These structures are interpreted as the remnants of a cloud of relativistic solitons generated in the plasma by the ultraintense laser pulse. This interpretation is supported by an analytical study of the soliton cloud evolution, by particle-in-cell simulations, and by a reconstruction of the proton-beam deflection.     

A class of multidimensional periodic splines

Periodic spline functions are introduced by use of reproducing kernel structure in Hilbert spaces. Minimum properties are described in interpolation and best approximation problems. A numerical method for determining interpolating splines and best approximations is proposed.Dedicated to Prof. Dr. F. Reutter on the occasion of his 70th birthday     

Studies on the Thorpe-Ziegler-reaction. A new synthesis of the pyridine part of thiamine]

Thorpe-Ziegler cyclization of N′-cyano-N-(2-cyanoethyl)-acetamidine ( 5a ) yields 4-amino-2-methyl-1,6-dihydro-5-pyrimidinecarbonitrile ( 8a ). The acetamidine 5a is accessible either from the N-cyanoimidate 1 and β-aminopropionitrile ( 3a ) or the N-cyanoamidine 2 and acrylonitrile ( 4 ). The dihydropyrimidine 8a is easily converted to 4-amino-2-methyl-5-pyrimidine-carbonitrile ( 13 ) by dehydrogenation or to 4-amino-5-aminomethyl-2-methylpyrimidine ( 15 ) by hydrogenation-dehydrogenation. Both products are important intermediates in the synthesis of thiamine.     

Audiogram of a striped dolphin (Stenella coeruleoalba)

The underwater hearing sensitivity of a striped dolphin was measured in a pool using standard psycho-acoustic techniques. The go/no-go response paradigm and up-down staircase psychometric method were used. Auditory sensitivity was measured by using 12 narrow-band frequency-modulated signals having center frequencies between 0.5 and 160 kHz. The 50% detection threshold was determined for each frequency. The resulting audiogram for this animal was U-shaped, with hearing capabilities from 0.5 to 160 kHz (8 1/3 oct). Maximum sensitivity (42 dB re 1 microPa) occurred at 64 kHz. The range of most sensitive hearing (defined as the frequency range with sensitivities within 10 dB of maximum sensitivity) was from 29 to 123 kHz (approximately 2 oct). The animal's hearing became less sensitive below 32 kHz and above 120 kHz. Sensitivity decreased by about 8 dB per octave below 1 kHz and fell sharply at a rate of about 390 dB per octave above 140 kHz.