Symmetrically substituted poly(diphenylacetylene) (PDPA) bearing carboxy pendants was found to fold into a one-handed helix upon thermal annealing with nonracemic amines in water accompanied by chiral amplification of the helicity. The induced right- or left-handed helical PDPA was retained (memorized) after complete removal of the chiral amines, thus producing a one-handed helical circularly polarized luminescent PDPA in a helix-sense-selective manner. The helical PDPA with static helicity memory is tolerant toward modification of carboxy pendants, providing functional PDPAs with an optical activity solely due to macromolecular helicity. The PDPA and its derivatives before and after the one-handed helicity induction and its subsequent memory of the helicity exhibited well-resolved very simple 1H and 13C NMR and Raman spectra whose spectral patterns are virtually identical independent of the helical sense bias. On the basis of the 1H and 13C NMR, IR, Raman, and vibrational and electronic circular dichroism spectral measurement results combined with theoretical calculations, the key structural features (cis or trans and cisoid or transoid) of the PDPA as well as its helix inversion barrier and absolute handedness (right- or left-handed helix) and helix-sense excess of the one-handed helical PDPA and its derivatives with static helicity memory were determined. As a result, almost complete right- and left-handed helical cis-transoidal PDPAs with 98% helix-sense excess were successfully obtained using noncovalent helicity induction and memory strategy.Exploring new energetic derivatives of 1,1-diamino-2,2-dinitroethylene (FOX-7) is still a key aspect in the field of energetic materials. However, so far most of the attention has been focused on modification of FOX-7 via different reaction strategies. Now we report the design of three new FOX-7-like compounds (3-5) where one nitro group in FOX-7 is replaced by a nitrogen-rich heterocyclic ring. Each of them is characterized by single-crystal X-ray crystallography. Electronic structures are studied through computational methods in comparison with FOX-7. In addition, the chemical reactivity of 3 was also investigated. Its hydroxylammonium (7), hydrazinium (8), and ammonium (9) salts were prepared, and the nitrate product (10) was also isolated. Compound 10 has a C-N bond length of 1.577 Å that is one of the longest values found for the C-NO2 bond. It was found that the incorporation of a tetrazole or triazole ring into the backbone of a conjugated nitroenamine does lead to a planar structure, which not only enhances the thermal stability but also improves the sensitivity of the product.An extraordinary prolonged freezing delay was detected for the first time for deeply undercooled sessile droplets of aqueous solutions of alkali metal chlorides deposited onto a superhydrophobic surface. Accounting for the variation in the hydration energy of ions, their distribution in the vicinity of charged interfaces of solution/air and solution/superhydrophobic surface allows qualitative description of the observed ice nucleation kinetics and ionic specificity in freezing phenomena.Understanding the conformational ensemble of an intrinsically disordered protein (IDP) is of great interest due to its relevance to critical intracellular functions and diseases. It is now well established that the polymer scaling behavior can provide a great deal of information about the conformational properties as well as liquid-liquid phase separation of an IDP. It is, therefore, extremely desirable to be able to predict an IDP’s scaling behavior from the protein sequence itself. The work in this direction so far has focused on highly charged proteins and how charge patterning can perturb their structural properties. As naturally occurring IDPs are composed of a significant fraction of uncharged amino acids, the rules based on charge content and patterning are only partially helpful in solving the problem. Here, we propose a new order parameter, sequence hydropathy decoration, which can provide a near-quantitative understanding of scaling and structural properties of IDPs devoid of charged residues. We combine this with a charge patterning parameter, sequence charge decoration, to obtain a general equation, parametrized from extensive coarse-grained simulation data, for predicting protein dimensions from the sequence. We finally test this equation against available experimental data and find a semiquantitative match in predicting the scaling behavior. We also provide guidance on how to extend this approach to experimental data, which should be feasible in the near future.Quasi-classical mapping Hamiltonian methods have recently emerged as a promising approach for simulating electronically nonadiabatic molecular dynamics. The classical-like dynamics of the overall system within these methods makes them computationally feasible, and they can be derived based on well-defined semiclassical approximations. However, the existence of a variety of different quasi-classical mapping Hamiltonian methods necessitates a systematic comparison of their respective advantages and limitations. Such a benchmark comparison is presented in this paper. The approaches compared include the Ehrenfest method, the symmetrical quasi-classical (SQC) method, and five variations of the linearized semiclassical (LSC) method, three of which employ a modified identity operator. The comparison is based on a number of popular nonadiabatic model systems; the spin-boson model, a Frenkel biexciton model, and Tully’s scattering models 1 and 2. The relative accuracy of the different methods is tested by comparing with quantum-mechanically exact results for the dynamics of the electronic populations and coherences. We find that LSC with the modified identity operator typically performs better than the Ehrenfest and standard LSC approaches. Nintedanib In comparison to SQC, these modified methods appear to be slightly more accurate for condensed phase problems, but for scattering models there is little distinction between them.In this note, we present a series of N-(8-fluoronaphthalen-1-yl)benzamide derivatives designed to maximize amide-NH···F hydrogen bond interactions therein. A combination of IR and NMR spectroscopy indicates a linear correlation between the high energy shift in NH stretching frequency and the electron withdrawing nature of the substituent, consistent with the trend predicted by DFT calculations. Additionally, a limiting case of hydrogen bonding is observed when the benzamide derivatives are replaced with trifluoroacetamide, causing an additional red shift of 44 cm-1 in the NH stretching frequency. Most importantly, 1H-19F coupling constants in this series are among the largest measured for amide-NH···F interactions. X-ray crystallography reveals face-to-face alignment of naphthalene rings in these derivatives resulting in part from the NH···F hydrogen bonds. This motif also dictates the formation of sheets composed of stacked naphthalene rings in the crystal structure as opposed to unfluorinated analogues wherein NH···OC hydrogen-bonding interactions force benzamide and naphthalene rings to engage in T-shaped π-π interactions instead.