Scalable Preparation of Photochromic Composite Foils with Excellent Reversibility for Light Printing

Photochromic inks for repeatable light‐printed media have attracted increasing attention owing to the fact that they may be widely applied to reduce the consumption of papers and plastics and conserve the environment. Therefore, it is of practical significance to develop convenient photochromic inks with a low cost and on a large scale. In this study, a simple one‐step hydrothermal route was used to prepare tungsten trioxide (WO₃) nanoparticles, which were further used to make photochromic inks and transparent photochromic films. The obtained transparent photochromic film could rapidly respond to UV light within tens of seconds, then return to its initial state, with different recovery times at different temperatures, and also exhibit good reversible coloration–bleaching effect. A typical polyethylene terephthalate (PET) foil coated with the photochromic ink could also be repeatedly printed with various patterns and displayed excellent rewritable performance over tens of cycles. This study proposes a simple method for widespread applications of WO₃‐based photochromic inks.     

Mechanistic Insights into the Ni‐Catalyzed Reductive Carboxylation of C−O Bonds in Aromatic Esters with CO2: Understanding Remarkable Ligand and Traceless‐Directing‐Group Effects

The mechanism of the Ni⁰‐catalyzed reductive carboxylation reaction of C(sp²)?O and C(sp³)?O bonds in aromatic esters with CO₂ to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C?O bond cleavage, reductive elimination, and/or CO₂ insertion. Of these steps, C?O bond cleavage was found to be rate‐determining, and it occurred through either oxidative addition to form a Ni^II intermediate, or a radical pathway that involved a bimetallic species to generate two Ni^I species through homolytic dissociation of the C?O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp²)?O and C(sp³)?O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni⁰ catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two Ni^I species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C?O bonds were also employed to investigate several experimentally observed phenomena, including ligand‐dependent reactivity and site‐selectivity.     

Eosin Y as a Direct Hydrogen‐Atom Transfer Photocatalyst for the Functionalization of C−H Bonds

Eosin Y, a well‐known economical alternative to metal catalysts in visible‐light‐driven single‐electron transfer‐based organic transformations, can behave as an effective direct hydrogen‐atom transfer catalyst for C?H activation. Using the alkylation of C?H bonds with electron‐deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y‐based photocatalytic hydrogen‐atom transfer strategy is promising for diverse functionalization of a wide range of native C?H bonds in a green and sustainable manner.     

Monochalcoplatin: An Actively Transported,Quickly Reducible,and Highly Potent PtIV Anticancer Prodrug

Recently, Pt^IV prodrugs have attracted much attention as the next generation of platinum‐based antineoplastic drug candidates. Here we report the discovery and evaluation of monochalcoplatin, a monocarboxylated Pt^IV prodrug that is among the most cytotoxic Pt^IV prodrugs to date. Compared with its dicarboxylated counterpart chalcoplatin, monochalcoplatin accumulates astonishingly effectively and rapidly in cancer cells, which is not ascribed to its lipophilicity. The prodrug is quickly reduced, causes DNA damage, and induces apoptosis, resulting in superior cytotoxicity with IC₅₀ values in the nanomolar range in both cisplatin‐sensitive and ‐resistant cells; these IC₅₀ values are up to 422‐fold higher than that of cisplatin. A detailed mechanistic study reveals that monochalcoplatin actively enters cells through a transporter‐mediated process. Moreover, monochalcoplatin shows significant antitumor activity in an in vivo colorectal tumor model. Our study implies a practical strategy for the design of more effective Pt^IV prodrugs to conquer drug resistance by tuning both cellular uptake pathways and activation processes.     

One-pot access to indolylchromeno[2,3-b]indoles via iodine-mediated Friedel-Crafts alkylation/oxidative coupling reaction of indoles and salicylaldehydes

An I₂-mediated Friedel-Crafts alkylation/oxidative coupling reaction of indoles and salicylaldehydes was developed. With the developed protocol, a series of indolylchromeno[2,3-b]indoles were obtained in good yields (up to 88%) under mild reaction conditions. Two possible reaction mechanisms were tentatively brought forward to account for the formation of the products in light of some control experiments.     

基于RSM和RA-BPNN的锌窑渣中铜浮选试验优化

云南某地锌窑渣矿样,原矿为高碱性矿石,矿石含铜1.38;,氧化率为30.12;.以磨矿细度、戊基黄药用量、碳酸钠用量、硫酸铜用量和硫化钠用量作自变量,以浮选回收率为因变量,分别建立了CCD响应曲面设计模型(RSM)和基于回归分析-BP神经网络(RA-BPNN)的浮选预测优化模型.根据两种模型的优化能力、优化精度进行分析和对比,结果表明,基于RA-BPNN模型进行预测及试验验证,铜回收率达到了64.06;,误差为0.74;,浮选回收率较RSM模型提高了1.54个百分点,且误差明显小于RSM模型,这表明RA-BPNN模型的优化能力高于RSM.根据试验结果,确定了锌窑渣浮选回收铜的最佳浮选条件为:磨矿细度90;、戊基黄药用量370 g/t、碳酸钠用量720 g/t、硫酸铜用量1080 g/t、硫化钠用量870 g/t.通过"一次粗选、三次精选、两次扫选、中矿顺序返回"的闭路浮选工艺流程,获得了品位为6.58;,回收率为55.98;的铜精矿.     

Metal Al produced by H2 plasma reduction of AlCl3: a thermodynamic and kinetic study on the plasma chemistry

In this paper we reported that low temperature plasma may reverse the direction of a chemical reaction. The thermodynamically forbidden reaction between H 2 and AlCl 3 was able to take place with the assistance of low temperature plasma, yielding metal Al. The plasma chemistry of the reaction was investigated by optical emission spectroscopy, which suggested that the dissociation of H 2 and AlCl 3 molecules by plasma led the reaction to a thermodynamically favorable one by creating reaction channels with low Gibbs free energy change. The addition of Ar promoted the reaction kinetics dramatically, which was attributed to the enhanced dissociation of AlCl 3 molecules by excited Ar species.     

Separation and determination of inorganic cations in beverages by capillary electrophoresis with indirect UV detection

A rapid, simple and reliable capillary electrophoresis method for the separation and quantitation of inorganic cations with indirect UV detection at 214 nm was developed. The electrolyte was: 12 mM imidazole as background absorbance provider; 5 mM malic acid and 1.0 mM 18-crown-6 ether as complexing agents; and 20% D₂O (v/v) to improve ion mobility. The pH was 4.25. The applied voltage was 22 kV at 22°C. Nine ions were completely separated and determined with correlation coefficients of 0.9979-0.9992. The relative standard deviations (RSD) were less than 0.5% for migration time and less than 5.2% for peak area (n=8). The detection limits (S/N=3) were from 0.08 mg L⁻¹ (for Na⁺) to 0.51 mg L⁻¹ (for Cu²⁺). To assess the reliability atomic absorption (AA) was also used to determine the same samples. Satisfactory results were obtained for real samples of jasmine tea drink and coconut milk.      

Complexation study of brilliant cresyl blue with beta-cyclodextrin and its derivatives by UV-vis and fluorospectrometry

The complexation reactions of brilliant cresyl blue (BCB) with beta-cyclodextrin (beta-CD), mono[2-O-(2-hydroxypropyl)]-beta-CD (2-HP-beta-CD), mono[2-O-(2-hydroxyethyl)]-beta-CD (2-HE-beta-CD), and heptakis(2,6-di-methyl) -beta-CD (DM-beta-CD) were investigated using UV-vis and fluorospectrometry. The complexation between BCB and CDs could inhibit the aggregation of BCB molecules and could cause its absorbance at 634nm gradually increasing. The fluorescence of BCB was also enhanced with the addition of CDs. The fluorescence enhancement was more notable in neutral and acidic media than in basic media. Hildebrand-Benesi equation was used to calculate the formation constants of beta-CDs with BCB based on the fluorescence differences in the CDs solution. The stoichiometry ratio was found to be 1:1. The complexing capacities of beta-CD and its three derivatives were compared and the results followed the order: 2-HP-beta-CD>2-HE-beta-CD>DM-beta-CD>beta-CD. The effect of temperature on the formation of BCB-beta-CD inclusion complexes has also been examined. The results revealed that the formation constants decreased with the increase of temperature from 1038.9 to 491.6l/mol. Enthalpy and entropy values were calculated and the values were -25.77kJ/mol and 35.04J/kmol, respectively. The thermodynamic measurements suggest that the inclusive process was enthalpic favor. The release of high-energy water molecules and Van der Waals force played an important role in the inclusive process.     

Impact of carbon structure and morphology on the electrochemical performance of LiFePO4/C composites

The electrochemical performance of LiFePO₄/C composites in lithium cells is closely correlated to pressed pellet conductivities measured by AC impedance methods. These composite conductivities are a strong function not only of the amount of carbon but of its structure and distribution. Ideally, the amount of carbon in composites should be minimal (less than about 2 wt%) so as not to decrease the energy density unduly. This is particularly important for plug-in hybrid electric vehicle applications (PHEVs) where both high power and moderate energy density are required. Optimization of the carbon structure, particularly the sp²/sp³ and disordered/graphene (D/G) ratios, improves the electronic conductivity while minimizing the carbon amount. Manipulation of the carbon structure can be achieved via the use of synthetic additives including iron-containing graphitization catalysts. Additionally, combustion synthesis techniques allow co-synthesis of LiFePO₄ and carbon fibers or nanotubes, which can act as “nanowires” for the conduction of current during cell operation.