Four new lanostane triterpenoids featuring extendedπ-conjugated systems from the stems of Kadsura coccinea

Four new 14(13→12)-abeolanostane triterpenoids featuring extendedπ-conjugated systems,kadcoccitanes E-H(1-4),were obtained from the stems of Kadsura coccinea through using a HPLC−UV-guided approach.Their structural and configurational determination was accomplished through extensive spectroscopic analysis coupled with quantum chemical calculations.Kadcoccitanes E-H were tested for their cytotoxic activities against five human tumor cell lines(HL-60,A-549,SMMC-7721,MDA-MB-231,SW-480)but none of them exhibited activities at the concentration 40μM.

Extended π-conjugated N-containing heteroaromatic hexacarboxylate organic anode for high performance rechargeable batteries

Organic electrode materials are desirable for green and sustainable Li-ion batteries(LIBs) due to their light-weight, low cost, abundance and multi-electron transfer reactions during battery operation. However, the successful utilization of organic electrodes is hindered by their poor electrical conductivity and low cyclic stability. Herein, a facile synthesis of π-conjugated N-containing heteroaromatic hexacarboxylate(Li6-HAT) compound and its electrochemical performance as an anode material in LIBs is reported.The as-synthesized Li6-HAT electrode renders an ultrahigh initial capacity of 1126.3 m Ah g^(-1) at the current density of 100 m A g^(-1). Moreover, π-conjugated N-containing heteroaromatic center provide excellent reversibility of(de)lithiation process, resulting in excellent capacity retention. Furthermore, a combination of density functional theory(DFT) calculations, in-situ Fourier transform infrared(FTIR) and ex-situ X-ray photoelectron spectroscopy(XPS) characterization reveal that the π-conjugated nitrogen and carboxyl oxygen act as electrochemically active sites during the charge/discharge process. The current work provides novel insights into the charge storage mechanism of organic electrodes and opens up avenues for further development and utilization of organic electrodes in Li-ion batteries.

π-conjugated chromophore functionalized high-nuclearity titanium-oxo clusters containing structural unit of anatase for photocatalytic selective oxidation of sulfides

N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(2+),which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.

Combination of methylthio-chemistry with living crystallization-driven self-assembly toward uniformπ-conjugated nanostructures with antibacterial activity,surface tailorability,tunable morphology and dimension

Living crystallization-driven self-assembly(CDSA)provides robust access to uniformπ-conjugated nanostructures(CNSs)from block copolymers(BCPs)containing a crystallineπ-conjugated segment with controlled dimension,morphology and composition,which show appealing applications in biomedicine,photocatalysis and microelectronics.To further expand the application spectrum of these CNSs,the development of facile strategies toward diverse CNSs with varying structures/functionalities is highly desired.Herein,BCPs consisting of oligo(p-phenylene ethynylene)-b-poly(polypropyl-3-methanethiol acrylate)(OPE_(9)-bPMTPA35and OPE_(9)-b-PMTPA_(58);the subscript represents the number of repeat unit of each block)consisting of a crystallineπ-conjugated core-forming OPE_(9)segment and a corona-forming PMTPA block are synthesized.By efficient“click-type”alkylation of methylthio groups,OPE_(9)-b-PMTPA with varying contents of sulfonium unit is obtained.Uniform ribbon-like micelles with different widths and lengths can then be generated in a controlled manner via the self-seeding approach of living CDSA.Additionally,negatively charged polymeric and Ag nanoparticles can be immobilized on sulfonium/methylthio-containing shells by taking advantage of electrostatic attraction and coordination interaction,respectively.Interestingly,the ribbon-like micelles with positively charged shells exhibit antibacterial activity against E.coli.Given the ease of modification of PMTPA-based shell and attractive opto-electronic/photocatalytic properties ofπ-conjugated units,the combination of methylthio-chemistry and living CDSA opens a new avenue to generate multi-functional CNSs for widespread applications from biomedicine to photocatalysis.

Layered(C_(5)H_(6)ON)_(2)[Sb_(2)O(C_(2)O_(4))_(3)]with a large birefringence derived from the uniform arrangement of π-conjugated units

An organic-inorganic hybrid antimony(Ⅲ)oxalate(C_(5)H_(6)ON)_(2)[Sb_(2)O(C_(2)O_(4))_(3)]has been successfully obtained by simultaneous combination of a-conjugated 4-hydroxypyridine and(C_(2)O_(4))^(2-)group with stereochemical active Sb(Ⅲ)cation.The compound features a layered structure,and the equatorial planes of SbO6 units,π-conjugated(C_(2)O_(4))^(2-)and(C5H6ON)+groups are closer to a planar arrangement,representing strong structural anisotropy that favors a large birefringence.As expected,(C_(5)H_(6)ON)_(2)[Sb_(2)O(C_(2)O_(4))_(3)]exhibits a large birefringence of 0.279 at 546 nm.Structural and theoretical analyses indicate that the combination of multipleπ-conjugated units is a feasible approach for designing and exploring new superior birefringent materials.

Living Crystallization-Driven Self-Assembly of Oligo(p-phenylene vinylene)-Containing Block Copolymers:Impact of Branched Structure of Alkyl Side Chain ofπ-Conjugated Segment

The structure of side chains ofπ-conjugated segments is a critical factor determining living crystallization-driven self-assembly(CDSA),a versatile platform to generate fiber-like nanostructures with precise length and composition.Herein,we design and synthesize three block copolymers(BCPs)containing same corona-forming poly(N-isopropyl acrylamide)(PNIPAM)segment,but different core-formingπ-conjugated oligo(p-phenylene vinylene)(OPV)with linear pentyl(l-OPV),racemic 2-methyl butyl(r-OPV)and stereo-regular chiral(S)-2-methyl butyl(c-OPV)side chains,respectively.By using these BCPs of l-OPV-b-PNIPAM_(47),r-OPV-b-PNIPAM_(47)and c-OPV-b-PNIPAM_(47)as model,we aim to get a deep insight into how steric and stereo-regular effect induced by branched alkyl side chains of OPV segment affects the living CDSA.The results showed that l-OPV-b-PNIPAM_(47)exhibits typical characteristics of self-seeding and seeded growth of living CDSA to give uniform fiber-like micelles of controlled length.On the contrary,r-OPV-b-PNIPAM_(47)and c-OPV-b-PNIPAM_(47)with branched racemic and stereo-regular chiral alkyl side chains are more prone to self-nucleation during the micellar elongation to give short and polydisperse fiber-like micelles.The obvious selfnucleation during the micellar elongation of r-OPV-b-PNIPAM_(47)and c-OPV-b-PNIPAM_(47)is due to the increase of steric repulsion with OPV units induced by branched alkyl side chains,not the stereo-irregular effect of racemic alkyl side chains.

Compounds consisting of coplanar π-conjugated B_(3)O_(6)-typed structures:An emerging source of ultraviolet nonlinear optical materials

Nonlinear optical(NLO)materials as a crucial part of the laser science have attracted increasing attention from researchers because of their wide applications in information storages,modern science and technologies,et al.Based on the anionic group theory,theπ-conjugated 6-membered rings(6-MRs),B_(3)O_(6)-typed structures have key contributions to the superior optical properties ofβ-Ba_(2)B_(2)O_(4)(β-BBO).In recent years,the organic coplanarπ-conjugated B_(3)O_(6)-typed structures have caught researchers'attention due to similar configurations to the(B_(3)O_(6))groups,which are the potential sources for expending the(B_(3)O_(6))groups with outstanding optical properties.Up to know,researchers have obtained many ultraviolet(UV)NLO crystals with excellent properties withπ-conju-gated B_(3)O_(6)-typed groups.Herein,these B_(3)O_(6)-typed groups could be divided into different categories according to the atoms constituting the 6-MRs:(H_(x)C_(3)N_(3)O_(3))^(x-3)(x=0-3)(cyanurate ion),(H_(x)C_(4)N_(2)O_(3))^(x-4)(x=2,3)(barbi-turate ion),(C_(3)H_(7)N_(6))^(+)(melamine ion),(C_(5)H_(6)ON)^(+)(4-hydroxypyridine cation),and(C_(4)H_(6)N_(3))^(+)(2-amino-pyrimidinium cation).In this review,we introduced the research advances of NLO materials withπ-conjugated B_(3)O_(6)-typed groups,and summarized the crystal structures,synthetic methods,optical performances,as well as the relationships between structures and properties.This work provided a clear perspective for understanding the coplanarπ-conjugated B_(3)O_(6)-typed groups with their optical functional properties and promote the searches to develop potential NLO functional crystals.

Ba(SO_(3)CH_(3))-(2):A Deep-Ultraviolet Transparent Crystal with Excellent Optical Nonlinearity Based on a New Polar Non-π-Conjugated NLO Building Unit SO_(3)CH_(3)^(−)

In this study,the first methyl sulfonate deepultraviolet(DUV)nonlinear optical(NLO)crystal,Ba(SO_(3)CH_(3))_(2),was successfully synthesized with the polar non-π-conjugated tetrahedron,SO_(3)CH_(3)^(−),as a novel DUV NLO building unit.Results showed that Ba(SO_(3)CH_(3))_(2)not only had a very short absorption edge of 159 nm,which is the shortest among reported phase-matchable sulfates or sulfonates,but also exhibited excellent optical properties.(Powder X-ray diffractionwas ca.1.5×KH_(2)PO_(4)and birefringence was 0.04 at 589.3 nm.)It also exhibited high thermal stability and remarkable stability against air and moisture.Additionally,bulk Ba(SO_(3)CH_(3))_(2)crystal could be obtained conveniently from a simple solution evaporation process.Therefore,Ba(SO_(3)CH_(3))_(2)should have great potential as a DUV NLO crystal in the near future.

Efficient and stable tin-based perovskite solar cells by introducing π-conjugated Lewis base

Tin-based perovskite solar cells(TPSCs)as the most promising candidate for lead-free PSCs have incurred extensive researches all over the world.However,the crystallization process of tin-based perovskite is too fast during the solution-deposited process,resulting in abundant pinholes and poor homogeneity that cause serious charge recombination in perovskite layer.Here,we employed theπ-conjugated Lewis base molecules with high electron density to systematically control the crystallization rate of FASnI3 perovskite by forming stable intermediate phase with the Sn-I frameworks,leading to a compact and uniform perovskite film with large increase in the carrier lifetime.Meanwhile,the introduction of theπ-conjugated systems also retards the permeation of moisture into perovskite crystal,which significantly suppresses the film degradation in air.These benefits contributed to a stabilizing power conversion efficiency(PCE)of 10.1%for the TPSCs and maintained over 90%of its initial PCE after 1000-h light soaking in air.Also,a steady-state efficiency of 9.2%was certified at the accredited test center.

Optically actuating ultra-stable radicals in a large π-conjugated ligand constructed photochromic complex

Producing ultra-stabilized radicals via light irradiation has raised considerable concern but remains a tremendous challenge in functional materials. Herein, optically actuating ultra-stable radicals are discovered in a sterically encumbered and large π-conjugated tri(4-pyridyl)-1,3,5-triazine(TPT) ligands constructed photochromic compound Cu_(3)(H-HEDP)_(2)TPT_(2)·2H_(2)O(QDU-12;HEDP=hydroxyethylidene diphosphonate). The photogeneration of TPT· radicals is the photoactive behavior of electron transfer from HEDP motifs to TPT units. The ultra-long-lived radicals are contributed from strong interchain π-π interactions between the large π-conjugated TPT components, with the radical lifetime maintained for about 18 months under ambient conditions. Moreover, the antiferromagnetic couplings between TPT· radicals and Cu^(2+)ions plummeted the demagnetization to 35% of its original state after light irradiation, showing the largest room temperature photodemagnetization in the current radicalbased photochromic materials.

Newπ-conjugated cyanostilbene derivatives:Synthesis,characterization and aggregation-induced emission

Two novel Jr-conjugated cyanostilbene derivatives, FLU-CNPH and TPE-CNPH, were designed aria synthesized by introducing the strong electron donor 1, 4-dihydropyrro[3,2-b]indole and AIE electron donor tetraphenylethylene （TPE） to the （3＇,5＇-bis（trifluoromethyl）-biphenyl-4-yl）-acetonitrile, respec- tively, Both of them were fully characterized and their AIE behaviors were investigated using fluorescence spectroscopy and FE-SEM images. Their optimized structures and frontier molecular orbitals were calculated with the DFT by using Materials Studio 7,0 software to study the relationship between the structure and properties.

One-Pot Synthesis of 3-to 15-Mer π-Conjugated Discrete Oligomers with Widely Tunable Optical Properties

Main observation and conclusion A series of all-donor type alternating(D1-D2)monodisperse oligomers based on cyclopentadithiophene(CPDT)and 1,4-difluoro-benzene(DFB)with gradually increasing chain lengths containing 3 to 15 monomers were successfully synthesized via one-pot C-H direct arylation reaction.As confirmed by various structural characterizations,all these long-chain oligomers are monodispersed with defined structures.The length-dependent optical and electrochemical properties with the evolution from the shortest oligomer(01)to the longest oligomer(07)and their parent polymer P1 have been studied in details.By simply tuning the mixing ratio of discrete oligomers,the photoluminescence(PL)in a wide range of color emissions extending to near-white can be facilely modulated,ilus-trating the potential of these monodisperse conjugated oligomers for light emission application.The atom-,step-and pot-economic synthetic strategy here developed will open the door toward efficient and controllable synthesis ofπ-conjugated oligomers for accu-rate structure-property relationship study and optic&electronic device applications.

Covalent Organic Frameworks with trans-Dimensionally Vinylene-linked π-Conjugated Motifs

Vinylene-linked covalent organic frameworks(COFs) are a class of promising porous organic materials that feature fully π-conjugated structures, high crystallinity, permanent porosity, ultrahigh chemical stability, and extraordinary optoelectronic properties. Over the past 5 years, this kind of material has been witnessed rapid development either in chemical synthesis or in potential applications. In this review, we summarize the chemistry to synthesize vinylene-linked COFs, especially the synthetic strategies involving activation of aryl methyl groups for condensation reaction. We then scrutinize the state-of-the-art development in properties and functions of this kind of COFs. Our own opinions on the further development of the vinylene-linked COFs are also presented for discussion.

Three New -CF3, -CN Containing <i>π</i>-Conjugated Heteroaromatic Compounds: Synthesis, Crystal Structure and Photoelectronic Properties

Three new π-conjugated hetero aromatic materials consisting of pyridine 3a, furan 3b, and thiophene 3c have been synthesized by Knoevenagel condensation reaction. These molecules have been characterized by 1H NMR, EI-MS and single crystal X-ray diffraction analysis. Molecule 3a crystallized under monoclinic system with space group C2/c, molecule 3b crystallized under triclinic system with space group P-1 and the molecule 3c crystalized under triclinic system with space group P-1. The optoelectronic properties of these compounds have been studied.Molecules 3a, 3b and 3c showed strong absorption maxima wavelengths at 300, 419 and 418 nm, respectively. The molar extinction coefficients (ε) of the compounds 3a, 3b and 3c suggested that molecule 3b has better ability to absorb UV light;molecule 3a has better fluorescence intensity than molecule 3b and 3c. Low energy gaps of HOMO and LUMO energy levels of these compounds suggests that these compounds may be a promising new class of lead compounds for developing high performance semiconductor materials. Compounds 3a, 3b and 3c has emissions near to blue light, a slight modification of the structures by extending conjugation may find important applications in optoelectronic devices as blue light emitters in organic light-emitting devices for the development of new generation organic semiconducting materials.

EFFECT OF CIS-9, TRANS-11-CONJUGATED LINOLEIC ACID ON CELL CYCLE OF MAMMARY ADENOCARCINOMA CELLS(MCF-7)

Objective: To determine the effect of cis-9, trans-1 1-conjugated linoleic acid on the cell cycle of mammary cancer cells (MCF-7) and the possible mechanism of the inhibitory effect of c9,t11-CLA. Methods: Using cell culture and immunocytochemical techniques, we examined the cell growth, DNA synthesis, expression of PCNA, cyclin A, B1, D1, p16ink4a and p21cip/waf1 of MCF-7 cells at various c9,t11-CLA concentrations (25μM, 50μM, 100μM and 200μM), at 24h and 48h. 96% ethand was used as negative control. Results: The cell growth and DNA synthesis of MCF-7 cells were inhibited by c9,t11-CLA. After treatment with various doses of c9,t11-CLA mentioned above for 8 days, the inhibition frequency was 27.18%, 35.43%, 91.05%, and 92.86%, respectively. Inhibitory effect of c9,t11-CLA on DNA synthesis (except for 25μM, 24h) was demonstrated by significantly less incorporation of 3H-TdR than the negative control (P<0.05 and P<0.01). To further investigate the influence of the cell cycle progression, we found that c9,t11-CLA may arrest the cell cycle of MCF-7 cells. Immunocytochemical staining demonstrated that incubation with different concentration of c9,t11-CLA at various times significantly decreased the expression of PCNA, Cyclin A, B1, D1 in MCF-7 cells compared to the negative control (P<0.01), whereas the expression of p16ink4a and p21cip/waf1, cyclin-dependent kinases inhibitors (CDKI), were increased. Conclusions: The cell growth and proliferation of MCF-7 cells is inhibited by c9,t11-CLA via blocking cell cycle, accompanying reduced expression of cyclin A, B1, D1 and enhanced expression of CDKI (p16ink4a and p21cip/waf1).

Intramolecular Hydrogen Bond Improved Durability and Kinetics for Zinc‑Organic Batteries

Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.

Improving the performance of arylamine-based hole transporting materials in perovskite solar cells： Extending π-conjugation length or increasing the number of side groups？

In this work, we prepared three simple arylamine-based hole transporting materials from commercially available starting materials. The effect of extending z-conjugation length or increasing the number of side groups compared with reference compound on the photophysical, electrochemical, hole mobility properties and performance in perovskite solar cells were further studied. It is noted that these two kinds of molecular modifications can significantly lower the HOMO level and improve the hole mobility, thus improving the hole injection from valence band of perovskite. On the other hand, the compound with more side groups showed higher hole injection efficiency due to lower HOMO level and higher hole mo- bility compared with the compound with extending π-conjugation length. The perovskite solar cells with the modified molecules as hole transporting materials showed a higher efficiency of 15.40% and 16.95%, respectively, which is better than that of the reference compound （13.18%）. Moreover, the compound with increasing number of side groups based devices showed comparable photovoltaic performance with that of conventional spiro-OMeTAD （16.87%）.

Copper-mediated 1,4-conjugation reaction of functionalized alkylzinc iodides with derivatives of β-nitrostyrene

Functionalized alkylzinc iodides will undergo 1,4-conjugation reaction with derivatives of β-nitrostyrene in the presence of Cu(OAc)2/LiCl to afford a polyfunctional nitro-compound in high yield.

Synthesis and Molecular Structures of Two Novel π-Conjugation Extended Dithia[3.3]metacyclophanes

Two novel dithia[3.3]metacyclophanes substituted with ethynyl groups were synthesized as small-sized metacyclophanes from the corresponding brominated dithia-metacyclophanes via C-C bond formation reaction. These compounds were characterized by using 1H NMR, mass spectrometry and elemental analyses. The exact structures were determined by using X-ray diffraction analyses. X-ray diffraction analysis results revealed that these compounds have anti conformations because of existence of intermolecular π-π interaction and some short contacts in the crystal. The long wavelength fluorescence was observed for one of the compound having a pyrene moiety in solid state because of the existence of the intermolecular π-π interaction between two pyrene units.

Spontaneous decoration of ionic compounds at perovskite interfaces to achieve 23.38% efficiency with 85% fill factor in NiO_X-based perovskite solar cells

Inorganic hole transport materials, particularly NiO_X, have shown considerable promise in boosting the efficiency and stability of perovskite solar cells. However, a major barrier to commercialization of NiO_X-based perovskite solar cells with positive-intrinsic-negative architectures is their direct contact with the absorbing layer, which can lead to losses of photovoltage and fill factor. Furthermore, highly positive under-coordinated Ni cations degrade the perovskite at the interface. Here, we address these issues with the use of an ionic compound(QAPyBF_(4)) as an additive to passivate defects throughout the perovskite layer and improve carrier conduction and interactions with under-coordinated Ni cations. Specifically,the highly electronegative inorganic anion [BF_(4)]~- interacts with the NiO_x/perovskite interface to passivate under-coordinated cations(Ni^(≥3+)). Accordingly, the decorated cells achieved a power conversion efficiency of 23.38% and a fill factor of 85.5% without a complex surface treatment or NiO_X doping.