Physical Chemistry Chemical Physics最新文献

Copolymer-surfactant assemblies are frequently utilized across various fields, from medicine to nanotechnology. Understanding the organization of the mixed assemblies in a saline environment will further expand their application horizons, especially under physiological conditions. Excited-state proton transfer (ESPT) can provide insight into the hydration nature and organization of the non-toxic assembly of a triblock copolymer F127 (poly-(ethylene oxide)₁₀₁ (PEO₁₀₁)-poly(propylene oxide)₅₆ (PPO₅₆)-PEO₁₀₁)) and a zwitterionic sulfobetaine surfactant N-dodecyl-N,N-dimethyl-3-ammoniopropane sulfonate (SB12). Here, we present a comprehensive investigation of the compactness and hydration nature of the F127-SB12 mixed assemblies at different salt concentrations using the ESPT of 8-hydroxy pyrene-1,3,6-trisulfonate (HPTS). In the absence of salts, gradual SB12 addition to a premicellar (0.4 mM) or a post-micellar (4 mM) F127 solution leads to an anomalous modulation of the protonated and deprotonated emission bands. The emission intensity ratio (protonated/deprotonated) first increases to a maximum at a particular SB12 concentration (6 mM and 35 mM for the premicellar and post-micellar F127 assemblies, respectively), and then the ratio decreases with a further increase in the surfactant concentration. Since the intensity ratio is an indicator of the retardation of the ESPT process, the mixed micellar configuration displaying a maximum intensity ratio represents the most compact and least hydrated state. Salt addition to this configuration lowers the intensity ratio, signifying an enhanced ESPT process. Dynamic light scattering (DLS) results indicate that the size of the mixed assembly remains almost unaltered with the addition of salts. Thus, salinity enhances the ESPT process inside the F127-SB12 mixed assemblies without significantly altering the hydrodynamic radius.

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

This study investigates the conformational intricacies of trans-2-pentenal (trans-2PA), a significant biogenic volatile organic compound. To unveil its potential implications in atmospheric chemistry and environmental pollution, we employ advanced infrared resonant vacuum ultraviolet mass-analysed threshold ionisation spectroscopy. Through this method, we identify the major conformers within trans-2PA, encompassing trans-s-trans (tt-) and trans-s-cis (tc-) structures with planar (cis) and non-planar (gauche) configurations introduced by a methyl group. In a pioneering spectroscopic examination, we analyze trans-2PA in both the neutral and cationic states. This approach allows us to gain a comprehensive understanding of its molecular behavior. Our conformer-specific vibrational spectra not only reveal the relative populations of the main conformers, notably tt-cis and tt-gauche conformers, but also shed light on atmospheric oxidation processes and lower tropospheric organic aerosol formation mechanisms. Our findings expand the understanding of the role of trans-2PA in environmental and biological contexts. Additionally, they contribute to a broader understanding of its influence on air quality, climate, and atmospheric dynamics. The collaboration between advanced experimental techniques and computational methods fortifies the scientific underpinning of this study, opening doors to further exploration in the realms of atmospheric chemistry and environmental science.

Recently, nanofluidic osmotic power, a promising technology converting the salinity difference between brine and fresh water into electricity using nanopores, has drawn the attention of researchers. Previous studies in this field were based mainly on nanopores having a smooth inner surface. To enhance the performance of nanofluidic osmotic power, we investigated four types of cylindrical nanopores, each with a unique waveform wall design (square, saw-tooth, triangle, and sine waves). This study focused on elucidating the influence of bulk salt concentration and geometric characteristics at the solid–liquid interface. We demonstrated that the presence of a waveform wall introduces new variables that have a significant impact on the overall performance of a nanofluidic osmotic power system. At the optimal amplitude of the waveform wall, raising waveform frequency can remarkably improve the osmotic current, diffusion potential, maximum power, and maximum efficiency. The present study provides a novel aspect of osmotic power, where the geometric nature of the nanopore reveals profound and intriguing phenomena primarily attributed to the distribution of ions within its interior.

The search for intrinsic half-metallic ferromagnetic (FM) monolayers with a high Curie temperature (T_C), considerable magnetic anisotropy energy (MAE), and multiferroic coupling is key for the development of ultra-compact spintronics. Here, we have identified a new stable FM Janus monolayer, the tetrahedral CrSSe, through first-principles structural search calculations, which not only exhibits very interesting magnetoelectric properties with a high T_C of 790 K, a large MAE of 0.622 meV per Cr, and robust half-metallicity, but also shows obvious ferroelasticity with a modest energy barrier of 0.31 eV per atom. Additionally, there appears to be interesting multiferroic coupling between in-plane magnetization and ferroelasticity. Furthermore, by replacing the Se/S atoms in the CrSSe monolayer with S/Se atoms, we obtained two new half-metallic FM CrS₂ and CrSe₂ monolayers, which also exhibit excellent magnetoelectric properties. Therefore, our findings provide a pathway to design novel multiferroic materials and enrich the understanding of 2D transition metal chalcogenides.

A bacteriochlorophyll a (Bchla) dimer is a basic functional unit in the LH1 and LH2 photosynthetic pigment–protein antenna complexes of purple bacteria, where an ordered, close arrangement of Bchla pigments—secured by noncovalent bonding to a protein template—enables exciton delocalization at room temperature. Stable and tunable synthetic analogs of this key photosynthetic subunit could lead to facile engineering of exciton-based systems such as in artificial photosynthesis, organic optoelectronics, and molecular quantum computing. Here, using a combination of synthesis and theory, we demonstrate that exciton delocalization can be achieved in a dimer of a synthetic bacteriochlorin (BC) featuring stability, high structural modularity, and spectral properties advantageous for exciton-based devices. The BC dimer was covalently templated by DNA, a stable and highly programmable scaffold. To achieve exciton delocalization in the absence of pigment–protein interactions critical for the Bchla dimer, we relied on the strong transition dipole moment in BC enabled by two auxochromes along the Q_y transition, and omitting the central metal and isocyclic ring. The spectral properties of the synthetic “free” BC closely resembled those of Bchla in an organic solvent. Applying spectroscopic modeling, the exciton delocalization in the DNA-templated BC dimer was evaluated by extracting the excitonic hopping parameter, J to be 214 cm⁻¹ (26.6 meV). For comparison, the same method applied to the natural protein-templated Bchla dimer yielded J of 286 cm⁻¹ (35.5 meV). The smaller value of J in the BC dimer likely arose from the partial bacteriochlorin intercalation and the difference in medium effect between DNA and protein.

With the advent of graphene, two-dimensional (2D) materials have emerged as promising candidates for next-generation electronic and optoelectronic applications. The most anticipated 2D materials have been synthesized and exploited for novel applications. Multilayered zinc chalcogenides (ZnX) are the best precursors for obtaining atomic layer two-dimensional materials by exfoliation. Therefore, we carry out a detailed density functional theory-based study to achieve an exfoliation process of ZnX non-van der Waals sheets by straining and provide a microscopic understanding of the ferroelectric, optic, and spin behaviors of ZnX systems and the corresponding self-healable two-dimensional ZnX devices. The results revealed that 2D ZnX sheets can be obtained when strain is 14% for ZnS and ZnSe, and the peak values of exfoliation energy have a similar order of magnitude to those of traditional 2D materials, indicating the possibility of obtaining 2D ZnX monolayers. For intrinsic 2D ferroelectric materials with in-plane electric polarization, the direction of ZnX sheets can be reversed using an electric field with an energy barrier of ∼0.175 eV per atom for ZnSe, offering a promising functional basis for their application in ferroelectric nanodevices. The first absorption of photons for polarization perpendicular to the monolayer plane occurs in a high energy range of photons, facilitating their application in LEDs. The spin splitting in non-centrosymmetric ZnX crystals exhibits a Rashba spin-texture according to first-principles calculations. The self-healable two-dimensional nanodevices have a smooth curve from −0.5 to 0.5 eV. This work indicates the potential value of non-van der Waals ZnX 2D materials for their application in photoelectric and spintronic nanodevices.

Understanding the motion of surface-rolling nanomachines has attracted lots of attention in recent studies, due to their ability in carrying molecular payloads and nanomaterials on the surface. Controlling the surface motion of these nanovehicles is beneficial in the fabrication of nano-transportation systems. In the present study, molecular dynamics (MD) simulations alongside the potential energy analysis have been utilized to investigate the motion of C₆₀ and C₆₀-based nanovehicles on the silicene monolayer. Nano-machine simulations are performed using molecular mechanic forcefield. Compared with graphene and hexagonal boron-nitride, the molecules experience a higher energy barrier on the silicene, which leads to a lower diffusion coefficient and higher activation energy of C₆₀ and nanomachines. Overcoming the maximum energy barrier against sliding motion is more probable at higher temperatures where the nanomachines receive higher thermal energy. After evaluating the motion of molecules around local vacancies, we introduce a nanoroad structure that can restrict surface motion. The motion of C₆₀ and nanovehicles over the surface is limited to the width of nanorods up to a certain temperature. To increase the controllability of the motion, a thermal gradient has been applied to the surface and the molecules move toward the lower temperature regions, where they find lower energy levels. Comparing the results of this study with other investigations regarding the surface motion of molecules on boron-nitride and graphene surfaces brings forth the idea of controlling the motion by silicene-based hybrid substrates, which can be further investigated.

Two triplet excitons are generated through an ultrafast photophysical process, namely singlet fission (SF), providing a solution for efficient solar energy usage. In this work, we provide an effective guideline for designing SF materials by adjusting the planarity in cyclopentadithiophene (CPDT) derivatives. A practical strategy is proposed for tuning the quinoidal-biradical resonance structures by varying the electron push–pull groups of CPDTs for SF. The localized, delocalized, and intermediate charge-transfer excited configurations are predicted in the singlet excited state via computational simulations, which is further confirmed by ultrafast spectroscopy. Deduced from the potential energy surfaces in the low-lying excited states and transient absorption, the delocalized excited state is formed in 2.1 ps via postulated intramolecular SF in a polar solvent, followed by the ultrafast formation of the free triplet state with a lifetime of 6.8 ps. In comparison with different cross-conjugated chromophores, it is found that the increase in the charge separation could enhance the triplet-pair generation for iSF. We expect that by introducing symmetry-breaking modifications in the electronic configurations and adjusting the separation between the push–pull groups of CPDTs, it should be possible to prolong the duration of the free triplet state by preventing recombination within the triplet-pair excited configuration.

Fluorescent probes capable of sensing the biological medium are of utmost importance in medical diagnostics. However, the optical spectrum of such probes needs to be tuned with care for compatibility with living tissues. More specifically, fluorescent bioprobes must be adjusted so as to avoid light interference with pigments (e.g. hemoglobin), tissue photodamage, scattering of the emitted light, and autofluorescence. This leads to two important conditions on the optical spectrum of the probes. On the one hand, the emission wavelength must be in an optical window of 650 to 950 nm. On the other hand, the Stokes shift must be large, ideally greater than 150 nm. In this paper, we showcase the in-silico design of potential fluorescent biomarkers fulfilling these two conditions by means of heteroatomic substitution and conjugation on a 1,2,4-triazole core initially far away from biological standards.