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1.
Xiao  Yang  He  Chong  Yang  Zi-Fan  Chen  Er-Qiang  Lu  Huan-Jun  Li  Xiao-Hong  Tu  Ying-Feng 《高分子科学》2022,40(6):584-592

We demonstrate here a novel method for the design of liquid crystals (LCs) via the cyclization of mesogens by flexible chains. For two azobenzene-4,4′-dicarboxylate derivatives, the cyclic dimer, cyclic bis(tetraethylene glycol azobenzene-4,4′-dicarboxylate) (CBTAD), shows LC properties with smectic A phase, while its linear counterpart, bis(2-(2′-hydroxyethyloxy)ethyl azobenzene-4,4′-dicarboxylate (BHAD), has no LC phase. The difference is ascribed to the shackling effect from the cyclic topology, which leads to the much smaller entropy change during phase transitions and increases the isotropic temperature greatly for cyclics. In addition, the trans-to-cis isomerization of azobenzene groups under UV-light is also limited in CBTAD. With the reversible isomerization of azobenzene groups, CBTAD showed interesting isothermal phase transition behaviors, where the LC phase disappeared upon photoirradiation of 365 nm UV-light, and recovered when the UV-light was off. Combined with the smectic LC nature, a novel UV-light tuned visible light regulator was designed, by simply placing CBTAD in two glass plates. The scattered phase of smectic LC was utilized as the “OFF” state for light passage, while the UV-light induced isotropic phase was utilized as the “ON” state. The shackling effect outlined here should be applicable for the design of cyclic LC oligomers/polymers with special properties.

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2.
Photocatalytic reduction of CO2 is one important approach to alleviate greenhouse gas emission and energy crisis, which has gained huge attention in the past decades. However, the lack of understanding complex reaction mechanism impedes new catalysts design. It is also very difficult to understand the mechanism by using only experimental approaches. For this concern, theoretical calculations can effectively supplement the experimental deficiency and thus play an important role. Recently theoretical calculations have been performed on adsorption, migration and reduction of CO2 molecule on the photocatalyst surface, leading to useful information that have contributed greatly to this field. This review summarizes recent advances in first-principles calculations about CO2 photoreduction over various semiconductor photocatalysts like metal oxides, sulfides and g-C3N4. The methods, models, adsorption and reaction pathways have been discussed in detail. The perspective about future investigation on the photocatalytic reduction of CO2 using first principles calculations is also presented.  相似文献   
3.
《中国化学快报》2020,31(7):1914-1918
Unremitting efforts have been intensively making for pursuing the goal of the reversible transition of electrowetting owing to its vital importance to many practical applications, but which remains a major challenge for carbon nanotubes due to the irreversible electrochemical damage. Herein, we proposed a subtly method to prevent the CNT array from electrochemical damage by using liquid medium instead of air medium to form a liquid/liquid/solid triphase system. The dimethicone dynamically refills in CNT arrays after removing of voltage that makes the surface back to hydrophobic, which is an elegant way to not only decrease energy dissipation in electrowetting process but also obtain extra energy in reversible dewetting process. Repeated cycles of in situ experiments showed that more than four reversible electrowetting cycles could be achieved in air. It worth mention that the in situ reversible electrowetting voltage of the dimethicone infused CNT array has been lowered to 2 V from 7 V which is the electrowetting voltage for the pure CNT array. The surface of the dimethicone infused CNT array can maintain hydrophobicity with a contact angle of 145.6° after four cycles, compared with 148.1° of the initial state. Moreover, a novel perspective of theoretical simulations through the binding energy has been provided which proved that the charged CNTs preferred binding with water molecules thereby replacing the dimethicone molecules adsorbed on the CNTs, whereas reconnected with dimethicone after removing the charges. Our study provides distinct insight into dynamic reversible electrowetting on the nanostructured surface in air and supplies a way for precise control of wettability in surface chemistry, smart phase-change heat transfer enhancement, liquid lenses, microfluidics, and other chemical engineering applications.  相似文献   
4.
《中国化学快报》2020,31(4):922-930
MXenes have emerged as versatile 2D materials that are already gaining paramount attention in the areas of energy,catalyst,electromagnetic shielding,and sensors.The unique surface chemistry,graphene-like mo rphology,high hydrophilicity,metal-like conductivity with redox capability identifies MXenes,as an ideal material for surface-related applications.This short review summarizes the most recent reports that discuss the potential application of MXenes and their hybrids as a transducer material for advanced sensors.Based on the nature of transducing signals,the discussion is categorized into three sections,which include electrochemical(bio) sensors,gas sensors,and finally,electro-chemiluminescence fluorescent sensors.The review provides a concise summary of all the analytical merits obtained subsequent to the use of MXenes,followed by endeavors that have been made to accentuate the future perspective of MXenes in sensor devices.  相似文献   
5.
《中国化学快报》2020,31(6):1640-1643
The physicochemical properties of surfaces have a great effect on the micro-morphologies of the crystal structures which are in contact with them.Understanding the interaction mechanism between the internal driving forces of the crystal and external inducing forces of the surfaces is the prerequisite of controlling and obtaining the desirable morphologies.In this work,the dynamic density functional theory was applied to construct the free energy functional expression of polyethylene(PE) lattice,and the micro-dynamic evolution processes of PE lattice morphology near the surfaces with different properties were observed to reveal the interaction mechanism at atomic scale.The results showed that the physical and chemical properties of the external surfaces synergistically affect the morphologies in both the defect shapes and the distribution of the defect regions.In the absence of the contact surfaces,driven by the oriented interactions among different CH2 groups,PE lattices gradually grow and form a defect-free structure.Conversely,the presence of contact surfaces leads to lattice defects in the interfacial regions,and PE lattice shows different self-healing abilities around different surfaces.  相似文献   
6.
Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3′H-[1,1′-biisobenzofuranylidene]-3,3′-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3′H-[1,1′-bibenzo[c] thiophenylidene]-3,3′-dione, are found to fluoresce in their neat solid phases, from upper (S2) and lowest (S1) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S2 and S1 states (T2 and T1 states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S2 excited states (phosphorescence from T2 excited states). These results, including unprecedented fluorescence quantum yields (2.3–9.6 %) from the S2 states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by “suppressing” Kasha's rule.  相似文献   
7.
We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols. Four poly(dithioacetal)s(P1-P4) were prepared via the base-catalyzed thiol-yne "click" polyaddition of two dithiols(1,4-butanedithiol(4 S) and 1,5-pentanedithiol(5 S)) and two alkynones(3-butyn-2-one(Y1) and 1-phenyl-2-propyn-1-one(Y2)) at high concentrations. We systematically investigated the base-catalyzed polymerization of 4 S and Y1(for polymer P1) under different conditions, and found that this polymerization was a highly concentration-dependent dynamic system: polymer P1 was formed at high concentration, while seven-membered dithioacetal, 1-(1,3-dithiepan-2-yl) propan-2-one(C1), was obtained at low concentration. The polymerization of 4 S and Y2(for polymer P4)displayed similar polymerization behavior, generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4) at low concentration. On the contrary,polymer P2(from Y1 and 5 S) was exclusively obtained with no formation of eight-membered dithioacetal. The polymerizations of Y1 with 1,2-ethanedithiol(2 S) and 1,3-dimercaptopropane(3 S) only afforded corresponding five-and six-membered dithioacetals, 1-(1,3-dithiolan-2-yl)propan-2-one(C2) and 1-(1,3-dithian-2-yl) propan-2-one(C3). This dynamic behavior of P1 and P4 was attributed to the concentrationdependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases.Furthermore, polymers P1 and P4 could be depolymerized into C1 and C4 in yields of 58% and 95%, respectively. The ring-opening polymerization of C1 at high concentration could successfully regenerate polymer P1. Thus, a new type of closed-loop recyclable poly(dithioacetal)s was developed.  相似文献   
8.
The remarkable properties of acoustic metamaterials have attracted massive researches and applications, especially on low-frequency sound absorptions. Currently, most of the acoustic metamaterial absorbers employ resonances in plastic cavities, and their structural strengths are important in many circumstances, especially in harsh environment. However, studies of metamaterials including this point are very scarce. Here, we propose an acoustic metamaterial for low-frequency (<500 Hz) absorptions, composed of three nested square split tubes with inverted opening directions. The efficiency of the absorber is investigated both numerically and experimentally, and absorptions at the peeks are found to exceed 90% and the frequency can be effectively adjusted by tuning its geometric parameters. We further test its yield strength under compression and confirm its buckling behavior happens from the outmost layer. This tunable acoustic metamaterial with a fairly good mechanical strength may lead to broad applications in noise reduction.  相似文献   
9.
Precise synthesis of nanobuilding blocks with accurately positioned functional groups presents a daunting challenge. Herein, a practical synthesis and thorough characterization of a series of T8‐polyhedral oligomeric silsesquioxane (POSS) di‐ and triadducts is reported. Upon addition of triflic acid across the double bonds in octavinylPOSS (V8T8) followed by hydrolysis, the cubic symmetry of the T8‐POSS cage (Oh) is broken into C2v (ortho‐), C2v (meta‐), and D3d (para‐) for diadducts and further to Cs (oom‐), Cs (omp‐), and C3v (mmm‐) for triadducts in a stochastic fashion. Their structures and regioconfigurations have been unambiguously demonstrated by 1H, 13C, and 29Si NMR spectroscopy, as well as MALDI‐TOF mass spectrometry. The assignment of the diadducts was further corroborated by converting each individual diadduct into triadduct(s), the structure of which is controlled by the symmetry of the precursor. Except for the C3v triadduct, they can all be prepared in synthetically useful quantities. The presence of two types of highly reactive and mutually orthogonal functional groups facilitates further modification into complex nanostructures and composite materials. These unique regioisomers provide a versatile platform for constructing giant molecules and Janus silsesquioxanes.  相似文献   
10.
Catalysts that catalyze the generation of products in the gas phase, especially those involved in the hydrogen evolution reaction (HER), hold great promise for ecofriendly and sustainable energy development. In general, gas chromatography is widely used to measure catalytic activity. Unfortunately, it gives an averaged output that washes out the heterogeneities among individuals. To assess the unique catalytic properties at the single nanoparticle level, various methods based on single particle catalysis have been proposed. Over the past fifteen years, tremendous breakthroughs have been achieved, which uncovered hidden spatial and temporal heterogeneities. Although powerful, effectively quantifying the activities of single HER nanocatalysts remains challenging because of the fast diffusion of hydrogen (H2). In 2017, a novel approach based on a nanobubble indicator was proposed to correlate the kinetics of gas bubble evolution with the catalytic activities of individual nanoentities during the HER process. Since then, a plethora of optical microscopy techniques have been utilized to monitor dynamically evolved nanobubbles and to measure the catalytic activities of single HER catalysts. In this minireview, we summarized state-of-the-art optical microscopy for in operando imaging of dynamic nanobubbles involved in gas-generating reactions while highlighting some important discoveries, including the blinking photocatalytic activity and heterogeneous distribution of active sites. Finally, challenges and future perspectives in this promising field were identified.  相似文献   
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