Guest-assisted assembly strategy: boosting solvent-processed organic solar cells toward commercialization

Science China Chemistry -     

Topical application of zein-silk sericin nanoparticles loaded with curcumin for improved therapy of dermatitis

Atopic dermatitis is characterized by leukocyte migration into the skin dermis and typically driven by excessive chemokine production at the site of inflammation. Conventional topical formulations such as gels, creams, and ointments are insufficient for this treatment because of low penetration of drug molecules into the targeted skin tissues. Herein, using a simple, green, sustainable strategy, we have developed novel primary zein nanoparticles embedded in curcumin (Cur) and coated with silk sericin (ZHSCs) for the topical delivery of Cur to penetrate into the dermis and exercise anti-dermatitis effects on the lesion with minimal side-effects. Transdermal delivery experiments and porcine skin fluorescence imaging indicated that ZHSCs facilitate the penetration of Cur across the epidermis layer of skin to reach deep-seated sites. Notably, ZHSCs = 1:0.25 (zein-to-silk sericin mass ratios of 1:0.25) markedly elevated the skin permeability and cumulative turnover of Cur transferred, which were provided a greater than a 3.8-fold increase relative to free Cur. The special nanoparticles of ZHS = 1:0.25 possessed the deepest localization depth and experience a transition of the particle structure and core-shell separation after penetrating into the dermis of skin. In a cell model of dermatitis induced by tumor necrosis factor α/interferon γ co-stimulation, compared with free Cur, Cur-loaded ZHS nanoparticles down-regulated the generation of inflammatory cytokines and chemokines in keratinocytes through suppression of the nuclear translocation of NF-κBp65 and hence exerted an anti-dermatitis effect. This strategy may provide new avenues and direction for the demanding issues of valid topical delivery systems.     

The behavior of capillary suspensions at diverse length scales: From single capillary bridges to bulk

Liquid-liquid-solid systems are becoming increasingly common in everyday life with many possible applications. Here, we focus on a special case of such liquid-liquid-solid systems, namely, capillary suspensions. These capillary suspensions originate from particles that form a network based on capillary forces and are typically composed of solids in a bulk liquid with an added secondary liquid. The structure of particle networks based on capillary bridges possesses unique properties compared with networks formed via other attractive interactions where these differences are inherently related to the properties of the capillary bridges, such as bridge breaking and coalescence between adjacent bridges. Thus, to tailor the mechanical properties of capillary suspensions to specific requirements, it is important to understand the influences on different length scales ranging from the dynamics of the bridges with varying external stimuli to the often heterogeneous network structure.     

Enhanced thermoelectric performance of PEDOT:PSS films via ionic liquid post-treatment

Thermoelectric(TE)energy harvesting can effectively convert waste heat into electricity,which is a crucial technology to solve energy concerns.As a promising candidate for energy conversion,poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)has gained significant attention owing to its easy doping,high transparency,and solution processability.However,the TE performance of PEDOT:PSS still needs to be further enhanced.Herein,different approaches have been applied for tuning the TE properties:(i)direct dipping PEDOT:PSS thin films in ionic liquid;(ii)post-treatment of the films with concentrated sulfuric acid(H₂SO₄),and then dipping in ionic liquid.Besides,the same bis(trifluoromethanesulfonyl)amide(TFSI)anion and different cation salts,including 1-ethyl-3-methylimidazolium(EMIM+)and lithium(Li+),are selected to study the influence of varying cation types on the TE properties of PEDOT:PSS.The Seebeck coefficient and electrical conductivity of the PEDOT:PSS film treated with H2SO4EMIM:TFSI increase simultaneously,and the resulting maximum power factor is 46.7μW·m^-1·K^-2,which may be attributed to the ionic liquid facilitating the rearrangement of the molecular chain of PEDOT.The work provides a reference for the development of organic films with high TE properties.     

Moderate Deviations for Extreme Eigenvalues of Real-Valued Sample Covariance Matrices

Journal of Theoretical Probability - Consider the sample covariance matrices of form $$W=n^{-1}C C^{\top }$$ , where C is a $$k\times n$$ matrix with real-valued, independent and identically...     

The Green polynomials via vertex operators

An iterative formula for the Green polynomial is given using the vertex operator realization of the Hall-Littlewood function. Based on this, (1) a general combinatorial formula of the Green polynomial is given; (2) several compact formulas are given for Green's polynomials associated with upper partitions of length ≤3 and the diagonal lengths ≤3; (3) a Murnaghan-Nakayama type formula for the Green polynomial is obtained; and (4) an iterative formula is derived for the bitrace of the finite general linear group G and the Iwahori-Hecke algebra of type A on the permutation module of G by its Borel subgroup.     

In situ confinement of iron-based active sites within high porosity carbon frameworks with enhanced activity for rechargeable Zn–air battery

Non-noble bifunctional electrocatalysts with robust activity and stability toward oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are greatly significant but challenging for Zn-air batteries. Here, in situ confinement of FeN_x active sites in high porosity carbon framework (FeN_x/CMCC) derived from chelate of carboxymethylcellulose (CMC) and iron ions were synthesized. Particularly, construction of FeN_x within porous carbon framework accelerates the electron transfer and the sufficient utilization of active centers, and then expedites the reaction kinetics of ORR and OER. As expected, the optimized FeN_x/CMCC exhibits superior ORR activity with a larger half-wave potential of 0.869 V. The rechargeable Zn-air battery delivers a higher power density of 99.6 mW/cm² and a special capacity of 781.9 mA h/g_Zn at 10 mA/cm², together with excellent durability of over 335 h. Remarkably, the as-assembled solid-state battery exhibits a higher open circuit voltage (OCV) of 1.5 V, a special capacity of 709.7 mA h/g_Zn, as well as prolonged cycling stability (90 h). Moreover, the flexible solid-state battery displays negligible loss of electrochemical performance under various bending angles, illustrating its potential application in flexible electronic devices.     

Enhanced deep-red emission in donor-acceptor molecular architecture:The role of ancillary acceptor of cyanophenyl

Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A) type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL) quantum yield(η_(PL)) due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9 H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D) type 2,7-bis(4-(diphenylamino)phenyl)-9 Hfluoren-9-one(DTPA-FO) with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO) itself to 4-(9-oxo-9 H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the high η_(PL) of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of0.13 cd/A and a maximum external quantum efficiency(EQE) of 0.22% with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.     

高压下L-丝氨酸的拉曼光谱研究

压力可以引起蛋白折叠与变性。作为蛋白质的基本构成单位，氨基酸在高压下的变化近来年备受关注。在常见的20种氨基酸中，学者们利用高压拉曼技术已研究了多种氨基酸在高压下的变化，研究的最高压力达到30 GPa。为了探究L-丝氨酸(C₃H₇NO₃)在极高压力下的结构变化情况，采用原位高压拉曼技术在常温下对L-丝氨酸晶体进行研究，最高压力达到22.6 GPa。研究发现，当压力达到2.7 GPa时，在102 cm-1处出现新峰，在1 123 cm-1(NH₃反对称摇摆振动)处的特征峰出现劈裂；当压力达到5.4 GPa时，L-丝氨酸晶体在574 cm-1处出现新峰，同时原来164 cm-1处峰消失；当压力达到6.0 GPa时，位于226，456，770和2 968 cm-1(CH₂伸缩振动)等处出现新峰，877 cm-1处的CC伸缩振动峰发生劈裂，产生894 cm-1新峰；当压力达到7.9 GPa时，在145，151和2 946 cm-1等出现新峰，同时原在CO₂摇摆振动峰的肩峰531 cm-1消失；当压力达到11.0 GPa时，位于249 cm-1处的振动峰开始劈叉，在241 cm-1处形成新峰，位于2 956 cm-1(CH₂伸缩振动)同时原位于391和431 cm-1处的峰消失；当压力达到17.5 GPa时，在200 cm-1处出现新峰。通过进一步分析L-丝氨酸的拉曼波数随压力的变化，发现很多拉曼峰在1.37，2.2，5.3，7.46和11.0 GPa以及15.5 GPa等压力点处都出现了拐点。其结果表明：L-丝氨酸在0.1～22.6 GPa之间共发生7处结构相变，分别位于压力区间0.1~1.37，2.2~2.7，5.3，6.0，7.46~7.9，10.1~11.0和15.5~17.5 GPa之间。而且，在6.0 GPa新的相变点在之前文献中未论述过。由于L-丝氨酸晶体在6.0 GPa时CC伸缩振动峰发生劈裂，这现象可能是由于压力引起L-丝氨酸晶体分子发生重排导致的，同时L-丝氨酸晶体分子重排导致氢键发生重排，使得L-丝氨酸晶体出现新的CH₂伸缩振动峰。L-丝氨酸晶体在10.1~11.0 GPa之间的拉曼光谱变化主要集中在低波数段，该波数段的拉曼振动模式主要与晶体晶格振动等低能量振动有关。同时在高波数段出现新的CH₂峰，由此可推测在10.1~11.0 GPa之间，L-丝氨酸晶体的晶格振动发生变化，产生了新的氢键，从而导致了L-丝氨酸晶体结构的改变。L-丝氨酸晶体在15.5~17.5 GPa之间，由于没有发现直接证据证明其发生结构相变，只是在拉曼波数随压力变化中，发现其在17.5 GPa时出现拐点，因此推测L-丝氨酸晶体在15.5~17.5 GPa之间可能发生结构相变。