Shopping malls are crowded areas which makes the evacuation routes unable to meet personnel evacuation needs. Therefore, this paper proposes the idea of using escalators evacuation to increasing ...evacuation routes. In addition, the effects of escalator fire shutters on the use of escalator evacuation paths, and the efficiency of mall personnel evacuation under different conditions were simulated. The results show that the different states of fire shutters have different effects on the emergency evacuation. When the fire shutter is not lowered, it will result in 1 person not being evacuated to complete. However, when the fire shutter is lowered to 1.8 m from the ground or sprinklers are set, escalators can be used for evacuation routes are verified. And compared to the normal descent of the fire shutter (only the staircase evacuation, 2 people not evacuate completed), the evacuation of people is completed and the efficiency of evacuation is improved. This result can improve the new evacuation model for emergency evacuation plans of shopping malls with escalators.
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Near-infrared (NIR) fluorophores absorbing maximally in the region beyond 800 nm, i.e., deep-NIR spectral region, are actively sought for biomedical applications. Ideal dyes are bright, nontoxic, ...photostable, biocompatible, and easily derivatized to introduce functionalities (e.g., for bioconjugation or aqueous solubility). The rational design of such fluorophores remains a major challenge. Silicon-substituted rhodamines have been successful for bioimaging applications in the red spectral region. The longer-wavelength silicon-substituted congeners for the deep-NIR spectral region are unknown to date. We successfully prepared four silicon-substituted bis-benzannulated rhodamine dyes (ESi5a–ESi5d), with an efficient five-step cascade on a gram-scale. Because of the extensive overlapping of their HOMO–LUMO orbitals, ESi5a–ESi5d are highly absorbing (λabs ≈ 865 nm and ε > 105 cm–1 M–1). By restraining both the rotational freedom via annulation and the vibrational freedom via silicon-imparted strain, the fluorochromic scaffold of ESi5 is highly rigid, resulting in an unusually long fluorescence lifetime (τ > 700 ps in CH2Cl2) and a high fluorescence quantum yield (ϕ = 0.14 in CH2Cl2). Their half-lives toward photobleaching are 2 orders of magnitude longer than the current standard (ICG in serum). They are stable in the presence of biorelevant concentration of nucleophiles or reactive oxygen species. They are minimally toxic and readily metabolized. Upon tail vein injection of ESi5a (as an example), the vasculature of a nude mouse was imaged with a high signal-to-background ratio. ESi5 dyes have broad potentials for bioimaging in the deep-NIR spectral region.
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Natural nucleobases and many of their derivatives have ultrashort excited state lifetimes that make them excellent model systems for studying intermolecular energy flow from a hot solute molecule to ...the solvent. UV-pump/broadband-mid-IR-probe transient absorption spectra of canonical purine nucleobases and several xanthine derivatives were acquired in D2O and acetonitrile in the probe frequency range of 1500–1750 cm–1. The spectra reveal that vibrationally hot ground state molecules created by ultrafast internal conversion return to thermal equilibrium in several picoseconds by dissipating their excess energy to solvent molecules. In acetonitrile solution, where hydrogen bonding is minimal, vibrational cooling (VC) occurs with the same time constant of 10 ± 3 ps for paraxanthine, theophylline, and caffeine within experimental uncertainty. In D2O, VC by these molecules occurs more rapidly and at different rates that are correlated with the number of N–D bonds. Hypoxanthine has a VC time constant of 3 ± 1 ps, while similar lifetimes of 2.3 ± 0.8 ps and 3.1 ± 0.3 ps are seen for 5′-adenosine monophosphate and 5′-guanosine monophosphate, respectively. All three molecules have at least two N–D bonds. Slightly slower VC time constants are measured for paraxanthine (4 ± 1 ps) and theophylline (5.1 ± 0.8 ps), dimethylated xanthines that have only one N–D bond. Caffeine, a trimethylated xanthine with no N–D bonds, has a VC time constant of 7.7 ± 0.9 ps, the longest ever observed for any nucleobase in aqueous solution. Hydrogen bond donation by solute molecules is proposed to enable rapid energy disposal to water via direct coupling of high frequency solute–solvent modes.
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Excited state lifetimes of hypoxanthine and four methylxanthine compounds (paraxanthine, theophylline, theobromine, and caffeine) were studied by femtosecond transient absorption spectroscopy in ...aqueous and acetonitrile solution. Transient absorption signals recorded at visible and UV probe wavelengths reveal that internal conversion from the photoexcited state to the electronic ground state takes place in water on the hundreds of femtoseconds time scale. Excited-state relaxation occurs approximately threefold more slowly in acetonitrile solution than in water. Structural considerations suggest that the deactivating conical intersection for the methylxanthines differs from that responsible for nonradiative decay by hypoxanthine, adenine, and guanine. All compounds studied have ultrashort excited state lifetimes similar to those of adenine and guanine, suggesting that these xanthine derivatives could have been photostable building blocks in prebiotic environments exposed to intense UV radiation.
Femtosecond transient absorption spectroscopy reveals that hypoxanthine, caffeine, and several dimethylxanthines have subpicosecond excited-state lifetimes.
The spray system mechanism during a gas explosion in an underground square pipeline is complex. In this paper, the underground square of Fuxin City is selected as the research object. FLACS numerical ...simulation software is used to analyze the spatial and temporal distribution characteristics of a gas explosion in an underground square pipeline with an unopened spray system using combustion and combustion rate models. Different spray pressures were compared and analyzed to determine the optimal spray control pressure, and the spray system mechanism was clarified. The results revealed that the gas explosion overpressure is divided into the overpressure gentle, overpressure rising, and overpressure decay stages, corresponding to a trend of rapid growth and slow decline. The influence of spray pressure on the gas explosion exhibits a promotion-inhibition-promotion trend, corresponding to 0-0.2 MPa, 0.2-0.6 MPa, and 0.6-1.6 Mpa, respectively. The peak overpressure and overpressure propagation rates are the lowest at 0.6 MPa, and the explosion suppression effect is the most pronounced. The spray system mechanism varies with the explosion overpressure stages. Generally, the time to peak value, that is, the peak time, the overall duration of the explosion, and the duration of the explosion stage decrease, whereas the peak explosion overpressure decreases.
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Methylated cytosine is proved to have an important role as an epigenetic signal in gene regulation and is often referred to “the fifth base of DNA”. A comprehensive understanding of the electronic ...excited state relaxation in cytosine and its methylated derivatives is crucial for revealing UV-induced photodamage to the biological genome. Because of the existence of multiple closely lying “bright” and “dark” excited states, the decay pathways in these DNA nucleosides are the most complex and the least understood so far. In this study, femtosecond transient absorption with different excitation wavelengths (240–296 nm) was used to study the relaxation of excited electronic states of 5-methylcytosine (5mC) and 2′-deoxy-5-methylcytidine (5mdCyd) in phosphate buffered aqueous solution and in acetonitrile solution. Two distinct nonradiative decay channels were directly observed. The first one is a several picosecond internal conversion channel that involves two bright ππ* states (ππ*2 and ππ*1) when ππ*2 state is initially populated. The second channel contains the lower energy ππ*1 state and a so far experimental unidentified long-lived state which exhibits a several nanosecond lifetime. The long-lived state can only be accessed by the initially excited ππ*1 state. Inspired by this new discovery in 5mC and 5mdCyd, we revisited the decay of excited state of 2′-deoxycytidine (dCyd), revealing very similar decay pathways. Additionally, a well-known dark nOπ* state (carbonyl lone pair) with ∼30 ps lifetime is present in both decay channels in dCyd. With our detailed experimental results, we successfully reconcile the long history debate of cytosine excited state relaxation mechanism by pointing out that the reason for the complex dynamics under traditional 266 nm excitation is mixed signals from the above-mentioned two distinct decay pathways. Our findings lead to a dramatically different and new picture of electronic energy relaxation in 5mdCyd/dCyd and could help to understand photostability as well as UV-induced photodamage of these nucleotides and related DNAs.
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Microbial methods are promising and environmentally friendly methods for remediating heavy metal contamination. In this study, a Cr(VI)-resistant bacterial strain, DC-B3, which was identified as
...Pseudomonas
sp. by 16S rDNA gene sequencing, was isolated from heavy metal-contaminated mine soil, and its performance in Cr(VI) removal from wastewater in terms of Cr(VI) reduction and total Cr adsorption was assessed. This strain exhibited a high capability to reduce Cr(VI) to less toxic Cr(III) without the addition of an external electron donor at low pH (2.0). The Cr(VI) reduction capacity and rate both increased linearly with increasing Cr(VI) concentration, with a reduction capacity of 32.0 mg Cr(VI)·g
−1
achieved at an initial concentration of 135.0 mg L
−1
over 75 h. In addition, 41.0% of the total Cr was removed from the solution by biosorption, and equilibrium was reached within approximately 5 h. The total Cr sorption process was well described by the pseudo-second-order kinetic and Langmuir isotherm models. Desorption assays indicated that NaOH was the most efficient agent for total Cr desorption, and Cr(VI) and generated Cr(III) were both loaded on the DC-B3 biomass. The bacterial cells after Cr treatment were characterized by scanning electron microscopy-energy dispersive X-ray spectrometer and Fourier transform infrared spectroscopy analyses. Strain DC-B3 showed high potential for possible application in the remediation of Cr(VI) contamination in mine areas.
CdSe/CdS core/crown nanoplatelet type I heterostructures are a class of two-dimensional materials with atomically precise thickness and many potential optoelectronic applications. It remains unclear ...how the precise thickness and lack of energy disorder affect the properties of exciton transport in these materials. By steady-state photoluminescence excitation spectroscopy and ultrafast transient absorption spectroscopy, we show that in five CdSe/CdS core/crown structures with the same core and increasing crown size (with thickness of ∼1.8 nm, width of ∼11 nm, and length from 20 to 40 nm), the crown-to-core exciton localization efficiency is independent of crown size and increases with photon energy above the band edge (from 70% at 400 nm to ∼100% at 370 nm), while the localization time increases with the crown size. These observations can be understood by a model that accounts for the competition of in-plane exciton diffusion and selective hole trapping at the core/crown interface. Our findings suggest that the exciton localization efficiency can be further improved by reducing interfacial defects.
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Ultrafast laser experiments on carefully selected DNA model compounds probe the effects of base stacking, base pairing, and structural disorder on excited electronic states formed by UV absorption in ...single and double DNA strands. Direct π-orbital overlap between two stacked bases in a dinucleotide or in a longer single strand creates new excited states that decay orders of magnitude more slowly than the generally subpicosecond excited states of monomeric bases. Half or more of all excited states in single strands decay in this manner. Ultrafast mid-IR transient absorption experiments reveal that the long-lived excited states in a number of model compounds are charge transfer states formed by interbase electron transfer, which subsequently decay by charge recombination. The lifetimes of the charge transfer states are surprisingly independent of how the stacked bases are oriented, but disruption of π-stacking, either by elevating temperature or by adding a denaturing co-solvent, completely eliminates this decay channel. Time-resolved emission measurements support the conclusion that these states are populated very rapidly from initial excitons. These experiments also reveal the existence of populations of emissive excited states that decay on the nanosecond time scale. The quantum yield of these states is very small for UVB/UVC excitation, but increases at UVA wavelengths. In double strands, hydrogen bonding between bases perturbs, but does not quench, the long-lived excited states. Kinetic isotope effects on the excited-state dynamics suggest that intrastrand electron transfer may couple to interstrand proton transfer. By revealing how structure and non-covalent interactions affect excited-state dynamics, on-going experimental and theoretical studies of excited states in DNA strands can advance understanding of fundamental photophysics in other nanoscale systems.
The fluorescence–phosphorescence dual solvoluminescence (SL) of water-soluble metal nanoclusters (NCs) at room temperature was successfully achieved by a simple solvent-stimulated strategy. The ...strong interaction between carboxylate ligands and the metal core at the nanoscale interface not only induces rigid conformations of carbonyl groups but also affords a perfect carbonyl cluster that acts as an exact chromophore of metal NCs for aggregation-induced emission (AIE) mechanics. The clustering of carbonyl groups bearing on the polymer backbone chain is promoted by newly discovered n → π* noncovalent interactions. The efficient delocalization of electrons in overlapped CO double bonds between neighboring carbonyl groups triggered by strong n → π* interactions in the polymer cluster accounts for its unique SL properties, especially the abnormal phosphorescence. This was further confirmed by controlled experiments for the presence of intersystem crossing (ISC) transitions. The results provide novel insights for understanding the complex SL process and open up a new way to study the inherent mechanism of SL by broadening the application of metal NCs.
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