Structural Isomers:Small Change with Big Difference in Anion Storage

Organic electrode materials are promising for batteries.However,the reported organic electrodes are often facing the challenges of low specific capacity,low voltage,poor rate capability and vague charge storage mechanisms,etc.Isomers are good platform to investigate the charge storage mechanisms and enhance the performance of batteries,which,however,have not been focused in batteries.Herein,two isomers are reported for batteries.As a result,the isomer tetrathiafulvalene(TTF)could store two monovalent anions reversibly,deriving an average discharge voltage of 1.05 V and a specific capacity of 220 mAh g−1 at a current density of 2 C.On the other hand,the other isomer tetrathianaphthalene could only reversibly store one monovalent anion and upon further oxidation,it would undergo an irreversible solid-state molecular rearrangement to TTF.The molecular rearrangement was confirmed by electrochemical performances,X-ray diffraction patterns,nuclear magnetic resonance spectra,and 1H detected heteronuclear multiple bond correlation spectra.These results suggested the small structural change could lead to a big difference in anion storage,and we hope this work will stimulate more attention to the structural design for boosting the performance of organic batteries.

Co-Harvest Phase-Change Enthalpy and Isomerization Energy for High-Energy Heat Output by Controlling Crystallization of Alkyl-Grafted Azobenzene Molecules

Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization.This article reports two series of asymmetrically alkyl-grafted azobenzene(Azo-g),with and without a methyl group,that have an optically triggered phase change.Three exothermic modes were designed to utilize crystallization enthalpy(△H_(c))and photothermal(isomerization)energy(△H_(p))at different temperatures determined by the crystallization.Azo-g has high heat output(275-303 J g^(-1))by synchronously releasing△H_(c)and△H_(p)over a wide temperature range(-79℃to 25℃).We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6℃at a temperature of-8℃.The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.

Li-promoted C_(3)N_(4) catalyst for efficient isomerization of glucose into fructose at 50℃ in water

Efficient and selective glucose-to-fructose isomerization is a crucial step for production of oxygenated chemicals derived from sugars,which is usually catalyzed by base or Lewis acid heterogeneous catalyst.However,high yield and selectivity of fructose cannot be simultaneously obtained under mild conditions which hamper the scale of application compared with enzymatic catalysis.Herein,a Li-promoted C_(3)N_(4) catalyst was exploited which afforded an excellent fructose yield(40.3 wt%)and selectivity(99.5%)from glucose in water at 50℃,attributed to the formation of stable Li–N bond to strengthen the basic sites of catalysts.Furthermore,the so-formed N_(6)–Li–H_(2)O active site on Li–C_(3)N_(4) catalyst in aqueous phase changes the local electronic structure and strengthens the deprotonation process during glucose isomerization into fructose.The superior catalytic performance which is comparable to biological pathway suggests promising applications of lithium containing heterogeneous catalyst in biomass refinery.

Critical approaches in the catalytic transformation of sugar isomerization and epimerization after Fischer-History,challenges,and prospects

The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.

Isomeric fluorescence sensors for wide range detection of ionizing radiations

In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer(PET)effect.Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized,and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry(HRMS),nuclear magnetic resonance hydrogen and carbon spectroscopy(~1H and~(13)C NMR).The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration.The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process.Despite the similarities in chemical structures,the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine.In the direct irradiation experiments of ionizing radiation,the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4,respectively.Furthermore,density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 e V and 1.13 e V,respectively.A wider energy range has a stronger driving force on electrons,which is conducive to fluorescence quenching.Both femtosecond transient absorption spectroscopy(fs-TAS)and transient fluorescence spectroscopy(TFS)tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant.Although both isomers can significantly reduce LOD during PET process,PDI-B with aromatic amine has a wider detection range of 0.118—240 Gy due to its larger emission enhancement,which is a leap of three orders of magnitude.It breaks through the detection range of gamma radiation reported in existing studies,and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.

Developing a highly scalable synthetic strategy for 5-amino-4-nitrobenzo[1,2-c:3,4-c']bis([1,2,5]oxadiazole)1,b-dioxide(CL-18)and investigating the influence of crystal engineering and positional isomerization on its safety and laser ignition performance

5-amino-4-nitrobenzo[1,2-c:3,4-c']bis([1,2,5]oxadiazole)1,6-dioxide(CL-18)exhibits significant potential as an initiating explosive.However,its current synthesis process remains non-scalable due to low yields and safety risks.In this study,we have developed a simple and safe synthetic route for CL-18.It was synthesized from 3,5-dihaloanisole in a four-step reaction with an overall yield exceeding 60%,surpassing all reported yields in the literature.Subsequently,recrystallization of CL-18 was successfully achieved by carefully selecting appropriate solvents and antisolvents to reduce its mechanical sensitivity.Ultimately,when DMF-ethanol was employed as the recrystallization solvent system,satisfactory product yield(>90%)and reduced mechanical sensitivity(IS=15 J;FS=216 N)were obtained.Additionally,CL-18 is derived from the rearrangement of oxygen atoms on i-CL-18 furoxan,and a comparative analysis of their physicochemical properties was conducted.The thermal stability of both compounds is similar,with onset decomposition temperatures recorded at 186 and 182℃respectively.Similarly,they exhibit 5 s breaking point temperatures of 236 and 237℃.Additionally,we present novel insights into the positional-isomerization-laser-ignition performance of CL-18 and its isomer i-CL-18 using laser irradiation for the first time.Remarkably,our findings demonstrate that i-CL-18 exhibits enhanced laser sensitivity,as it can be directly ignited by a 1064 nm wavelength laser,whereas CL-18 lacks this characteristic.

Simulation of nuclear isomer production in laser-induced plasma

Nuclear isomers play essential roles in various fields,including stellar nucleosynthesis,nuclear clocks,nuclear batteries,clean nuclear energy,and-ray lasers.Recent technological advances in high-intensity lasers have made it possible to excite or de-excite nuclear isomers using table-top laser equipment.Utilizing a particle-in-cell code,we investigate the interaction of a laser with a nanowire array and calculate the production rates of the^(73m)Ge(E_(1)=13.3 keV)and^(107m)Ag(E_(1)=93.1 keV)isomers.For^(73m1)Ge,production by Coulomb excitation is found to contribute a peak efficiency of 1.0×10^(19) particles s^(−1)J^(−1),while nuclear excitation by electron capture(NEEC)contributes a peak of 1.65×10^(11)particles s^(−1)J^(−1).These results indicate a high isomeric production ratio,as well as demonstrating the potential for confirming the existence of NEEC,a long-expected but so far experimentally unobserved fundamental process.

Synthesis of Pt/PMA-MIL-101 Catalyst and Its Performance in n-Heptane Isomerization

Hydroisomerization of n-heptane is an efficient method for producing gasoline with a high octane number.The focus of this study was to find a highly efficient catalyst that could both promote the conversion of n-heptane and inhibit the cracking side reaction.MIL-101(Cr)is a chromium-based metal-organic framework(MOF)with good hydrothermal stability,and exhibits a three-dimensional pore structure that is similar to that of zeolites.Using phosphomolybdic acid(PMA;H3PMo12O40·xH2O)can increase the number of Brønsted acid sites on MIL-101(Cr),which contributes to improving the catalytic performance during isomerization.In this study,0.4%Pt/PMA-MIL-101(Cr)catalyst was successfully crystallized at 220℃using a hydrothermal synthetic method.The results showed that the synthesized samples were mesoporousmicroporous composite materials with the typical octahedral structure,and the MIL-101(Cr)framework was not damaged following modification with PMA.It was found that 0.4%Pt30%PMA-MIL-101(Cr)exhibited the best performance for isomerization of n-heptane,with a conversion rate and selectivity at 260°C of 47.6%and 96.6%,respectively.After five hours of reaction,the conversion rate and selectivity of the catalyst remained above 38%and 80%,respectively.

Highly efficient isomerization of glucose to fructose over Sn-doped silica nanotube

Isomerization of glucose to fructose is a fundamental and key intermediate process commonly included in the production of valuable chemicals from carbohydrates in biorefinery.Enhancement of fructose yield is a challenge.In this work,Sn-doped silica nanotube(Sn-SNT)was developed as a highly efficient Lewis acid catalyst for the selective isomerization of glucose to fructose.Over Sn-SNT,69.1%fructose yield with 78.5%selectivity was obtained after reaction at 110◦C for 6 h.The sole presence of a large amount of Lewis acid sites in Sn-SNT without Brønsted acid site is one of the reasons for the high fructose yield and selectivity.Otherwise,high density of SiOH groups in Sn-SNT can ensure the presence of SiOH groups near the Sn sites,which is important for the isomerization of glucose to fructose,leading to the high fructose yield and selectivity.Furthermore,the Sn-SNT is recyclable.

Research on the Relationship between Three Isomers of Microcystins and Environmental Factors

[Objective] The relationship between three isomers of microcystins and environmental factors were studied in the fields.[Method] Three isomers of microcystins （MC-LR,RR and YR） from water of five sampling spots in a northern reservoir were observed for one year with High Performance Liquid Chromatography analytical method in order to study the relationship between three isomers and environmental factors.[Result] The three isomers of microcystins showed positive correlation with chlorophyll a;LR and YR isomers all had significant linear positive correlations with the water temperature,but the RR isomer showed no significant correlation with the water temperature;LR and YR isomers had relatively significantly correlativities with the contents of total nitrogen,nitrate nitrogen and organic nitrogen,while the RR isomer only showed a significant negative correlation with the content of nitrate nitrogen;LR and RR isomers both showed significant positive correlations with the contents of total phosphorus and organic phosphorus,while the phosphorus hardly affected the YR isomer and showed no evident correlation.[Conclusion] The relationship between three isomers of microcystins and environmental factors such as chlorophyll a,water temperature,nitrogen,phosphorus were studied and investigated the reasons,which might offered a reference for controlling the growth of blue algae in water and toxin synthesis.

Effects of Rotational Isomerism and Bond Length Alternation on Optical Spectra of FTC Chromophore in Solution

Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.

Three Novel Isomers of FCH_2CP System

Three new isomers of FCH2CP system, F(H)CCPH (1), F-cCPC-H(H) (2) and F-cCC(H)P-H (3), are predicted by means of B3LYP and CCSD(T) (single-point) methods with 6-311++G(d,p) and 6-311++G(2df,2p) basis sets, respectively. The three calculated isomers can isomerize into thermodynamically the most stable species F-cPC(H)C-H, which has been suggested in previous theoretical studies, with relatively higher reaction barriers. In view of their higher thermodynamic and kinetic stability, we believe that the three species can be detected in future experiments.

Selective 3-OH Isomerization of Resibufogenin by Cell Suspension Cultures of Ginkgo biloba

Aim To modify the structure of resibufogenin by using Ginkgo bilobasuspension. Methods Young leaves of Ginkgo biloba were differentiated into callus in MS medium withonly 2,4-D as plant growth regulator. The callus was then transferred aseptically to liquid MSmedium exoge-nously supplemented with appropriate concentration of 6-BA, NAA and 2,4-D to establishsuspension cell culture system. Resibufogenin was administered into the well-grown cell cultures andincubated for 4 d. The products dissolved in the liquid phase of the cultures were extracted andpurified by silica gel column chromatography gradiently eluted with petroleum ether and acetonesystem. Results One transformed product was obtained in 40% yield after 4 d incubation, which wasidentified as 3-epi-resibufogenin on the basis of FAB MS, ~1H NMR and ^(13)C NMR spectroscopicanalysis and corresponding data reported in literature. Conclusion G. biloba suspension cultures canbe used as an enzyme system to biotransform resibufogenin, an animal-originated bufadienolide, into3-epi-resibufogenin.

Isomerization of linear C5–C7 over Pt loaded on protonated fibrous silica@Y zeolite（Pt/HSi@Y）

A novel fibrous silica Y zeolite (HSi@Y) loaded with Pt has been studied based on its ability to produce protonic acid sites originating from molecular hydrogen. The Pt/HSi@Y was prepared using seed assisted crystallization followed by protonation and Pt-loading. The product formed had a spherical morphology with bicontinuous lamellar with a diameter in the range of 500-700 nm. The catalytic activity of the Pt/HSi@Y has been assessed based on light linear alkane (C5-C7) isomerization in a micro-catalytic pulse reactor at 423-623 K. A pyridine IR study confirmed that the introduction of fibrous silica on Y zeolite increased the Lewis acid sites corresponding with the formation of extra-framework Al which led to the generation of more protonic acid sites. A hydrogen adsorbed IR study showed that the protonic acid sites which act as active sites in the isomerization were formed via dissociative-adsorption of molecular hydrogen releasing electrons to the nearby Lewis acid sites. Thus, it is suggested that the presence of Pt and HSi@Y with a high number of Lewis acid as well as weak Bronsted acid sites improved the activity and stability in C5, C6 and C7 isomerization via hydrogen spill-over mechanism.

Novel endo-to exo-isomerization of dicyclopentadiene

Endo-dicyclopentadiene was isomerized to exo-isomer by thermal treatment at evaluated temperature and pressure. The reaction temperature and pressure are key factors for this novel isomerization. This result may have great potential for practical application.

Modeling of Isomerization of C_8 Aromatics by Online Least Squares Support Vector Machine

The least squares support vector regression (LS-SVR) is usually used for the modeling of single output system, but it is not well suitable for the actual multi-input-multi-output system. The paper aims at the modeling of multi-output systems by LS-SVR. The multi-output LS-SVR is derived in detail. To avoid the inversion of large matrix, the recursive algorithm of the parameters is given, which makes the online algorithm of LS-SVR practical. Since the computing time increases with the number of training samples, the sparseness is studied based on the pro-jection of online LS-SVR. The residual of projection less than a threshold is omitted, so that a lot of samples are kept out of the training set and the sparseness is obtained. The standard LS-SVR, nonsparse online LS-SVR and sparse online LS-SVR with different threshold are used for modeling the isomerization of C8 aromatics. The root-mean-square-error (RMSE), number of support vectors and running time of three algorithms are compared and the result indicates that the performance of sparse online LS-SVR is more favorable.

Isomerization of n-pentane catalyzed by amide-AlCl3-based ionic liquid analogs with various additives

The isomerization of n-pentane to generate high-quality blending components for clean gasoline was catalyzed by several amide-AlCl3-based ionic liquid(IL) analogs with various amides as donor molecules. The catalytic performance of these IL analogs was evaluated in a magnetic agitated autoclave operated in batch mode.IL analog based n-methylacetamide(NMA)-AlCl3 with the amide/AlCl3 molar ratio of 0.65 showed excellent performance toward n-pentane isomerization because 0.65 NMA-1.0 AlCl3 had a low viscosity and bidentate coordination structure. The influences of reaction time, reaction temperature, and stirring speed on the catalytic performance were also investigated. Optimal reaction conditions comprised the reaction time of 1 h, the reaction temperature of 40 °C, and the stirring speed of 1500 r·min-1. Under optimal condition, the n-C5 conversion,research octane number(RON) increment, total liquids yield, and isoparaffin yield in isomerized oil were56.80%, 13.51, 89.90 wt%, and 44.32 wt%, respectively. A new mathematical model was constructed to predict the relationships among RON increment, RON increment/n-C5 conversion ratio, and n-C5 conversion. The new model indicated that an appropriate conversion per pass of n-C5 did not exceed 50%–55%. Various cycloparaffin additives were used to improve the catalytic performance of 0.65 NMA-1.0 AlCl3. The n-C5 conversion increased from 56.80% to 67.32%. The RON increment, total liquids yield, and isoparaffin yield reached 17.83, 97.36 wt%,and 63.74 wt%, respectively.

Experimental and kinetic study of n-heptane isomerization on nanoporous Pt-(Re,Sn)/HZSM5-HMS catalysts

Pt-（Sn,Re）/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200–350 ℃.To characterize the catalyst,X-ray diffraction,X-ray fluorescene,Fourier transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,temperature-programmed reduction of H2,temperature-programmed desorption of NH3,infrared spectroscopy of adsorbed pyridine,H2 chemisorption,nitrogen adsorption-desorption,scanning electron microscopy and thermogravimetric analysis were performed.Kinetics of n-C7 isomerization were investigated under various hydrogen and n-C7 pressures,and the effects of reaction conditions on catalytic performance were studied.The results showed that bi-and trimetallic catalysts exhibit better performance than monometallic catalysts for this reaction.For example,a maximum i-C7 selectivity（ 〉74%） and multibranched isomer selectivity（40%） were observed for Pt-Sn/HZSM5-HMS at 200 ℃.

Hydrocracking diversity in n-dodecane isomerization on Pt/ZSM-22 and Pt/ZSM-23 catalysts and their catalytic performance for hydrodewaxing of lube base oil

Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.