End-group modulation of phenazine based non-fullerene acceptors for efficient organic solar cells with high open-circuit voltage

Phenazine-based non-fullerene acceptors(NFAs)have demonstrated great potential in improving the power conversion efficiency(PCE)of organic solar cells(OSCs).Halogenation is known to be an effective strategy for increasing optical absorption,refining energy levels,and improving molecular packing in organic semiconductors.Herein,a series of NFAs(Pz IC-4H,Pz IC-4F,Pz IC-4Cl,Pz IC-2Br)with phenazine as the central core and with/without halogen-substituted(dicyanomethylidene)-indan-1-one(IC)as the electron-accepting end group were synthesized,and the effect of end group matched phenazine central unit on the photovoltaic performance was systematically studied.Synergetic photophysical and morphological analyses revealed that the PM6:Pz IC-4F blend involves efficient exciton dissociation,higher charge collection and transfer rates,better crystallinity,and optimal phase separation.Therefore,OSCs based on PM6:Pz IC-4F as the active layer exhibited a PCE of 16.48%with an open circuit voltage(Voc)and energy loss of 0.880 V and 0.53 e V,respectively.Accordingly,this work demonstrated a promising approach by designing phenazine-based NFAs for achieving high-performance OSCs.

Cytotoxic phenazine and antiallergic phenoxazine alkaloids from an arctic Nocardiopsis dassonvillei SCSIO 502F

Microbes well-adapted to the Arctic Ocean are promising for producing novel compounds,due to their fancy strategies for adaptation and being under-investigated.Two new phenazine alkaloids(1 and 2)and one new phenoxa-zine(3)were isolated from Nocardiopsis dassonvillei 502F,a strain originally isolated from Arctic deep-sea sediments.AntiSMASH analysis of the genome of Nocardiopsis dassonvillei 502F revealed the presence of 16 putative biosynthetic gene clusters(BGCs),including a phenazine BGC.Most of the isolated compounds were evaluated for their antibacterial,antiallergic,and cytotoxic activities.Among them,compounds 4 and 5 exhibited potent in vitro cytotoxic activities against osteosarcoma cell line 143B with IC_(50) values 0.16 and 20.0μM,respectively.Besides,the results of antiallergic activities of compounds 6-8 exhibited inhibitory activities with IC_(50) values of 10.88±3.05,38.88±3.29,and 2.44±0.17μg/mL,respectively(IC_(50)91.6μM for the positive control loratadine).

Functional identification of phenazine biosynthesis genes in plant pathogenic bacteria Pseudomonas syringae pv. tomato and Xanthomonas oryzae pv. oryzae

Phenazines are secondary metabolites with broad spectrum antibiotic activity and thus show high potential in biological control of pathogens. In this study, we identified phenazine biosynthesis （phz） genes in two genome-completed plant pathogenic bacteria Pseudomonas syringae pv. tomato （Pst） DC3000 and Xanthomonas oryzae pv. oryzae （Xoo） PXO99A. Unlike the phz genes in typical phenazine-producing pseudomonads, phz homologs in Pst DC3000 and Xoo PXO99A consisted of phzC/D/E/F/G and phzC/E1/E2/F/G, respectively, and the both were not organized into an operon. Detection experiments demonstrated that phenazine-l-carboxylic acid （PCA） of Pst DC3000 accumulated to 13.4 IJg L-1, while that of Xoo PXO99A was almost undetectable. Moreover, Pst DC3000 was resistant to 1 mg mL-1 PCA, while Xoo PXO99A was sensitive to 50 IJg mL ~ PCA. Furthermore, mutation of phzF blocked the PCA production and significantly reduced the pathogenicity of Pst DC3000 in tomato, while the complementary strains restored these phenotypes. These results revealed that Pst DC3000 produces low level of and is resistant to phenazines and thus is unable to be biologically controlled by phenazines. Additionally, phz-mediated PCA production is required for full pathogenicity of Pst DC3000. To our knowledge, this is the first report of PCA production and its function in pathogenicity of a plant pathogenic P. syringae strain.

Synthesis,Crystal Structure and Magnetic Behavior of a New Manganese(Ⅱ) Coordination Polymer [Mn(DPPZ)(PZDC)(H_2O)] (DPPZ=Dipyrido[3,2-a:2',3'-c]-phenazine and H_2PZDC=Pyrazine-2,3-dicarboxylic Acid)

The title complex, [Mn（DPPZ）（PZDC）（H2O）] 1 （DPPZ = dipyrido[3,2 -a：2＇,3＇- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid）, has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842（5）, b = 7.5741（6）, c = 20.5755（15）A, α = 90.1160（10）, β = 97.0560（10）, γ = 97.3350（10）°, V= 1025.16（13）A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F（000） = 530, μ（MoKa） = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O（1W） is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0（4） at （x＋ 1, y＋1, z） and symmetric PZDC nitrogen atom N（6） at （1-x, 1-y, 1-z）, which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.

The Interaction of Cobalt (Ⅲ) Mixed-Ligand Coordination Compound Containing Dipyrido[3,2-a:2′,3′-c] phenazine With Calf Thymus DNA -

The binding of Co (phen)2dppz3+ to calf thymus DNA,as investigated using absorption spectroscopy. viscosity and electrophoresis measurements,here dppz is dipyrido[3, 2-a: 2'3'-c]phenazine. The compound shows absorption hypochromicity and the specific viscosity increased upon binding to calf thymus DNA The complex is also shown to be more efficient photosensitisers for single strand breaks in plasmid DNA

Hydrothermal Syntheses and Crystal Structures of Cobalt(Ⅱ) Complexes Constructed by Dipyrido[3,2-a:2',3'-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.

Synthesis,Structure and Photoluminescence of a Binuclear Zinc(Ⅱ) Coordination Polymer Based on 2-Carboxycinnamic Acid and Dipyrido[3,2-a:2′,3′-c]-phenazine

A binuclear zinc（Ⅱ） complex with 2-carboxycinnamic acid （2-ccm） and dipyrido- [3,2-a：2＇,3＇-c]phenazine （DPPZ）, {[Zn2（2-ccm）2（DPPZ）2]·2H2O}n, was synthesized and characterized by elemental analysis, IR, single-crystal X-ray diffraction, thermal gravimetry and fluo- rescent emission. It crystallizes in monoclinic, space group P21/c with a = 13.409（4）, b = 25.530（7）, c = 13.952（4） A, β = 99.554（3）°, V= 4710（2） A3, Z= 4, C56H36N8O10Zn2, Mr= 1111.67, Dc = 1.568 g/cm3, μ（MoKα） = 1.093 mm^-1, F（000） = 2272, R = 0.0422 and wR = 0.0895. In the crystal, the basic unit of 1 is a binuclear Zn2 entity which is linked by 2-ccm ligand to form a 1D double chain along the a axis. The O-H...O hydrogen bonding and π-π interactions lead to a 3D supramolecular motif. In addition, thermal and luminescent properties of complex 1 have also been investigated.

Studies on the Interaction of Cobalt Mixed-Ligand Coordination Compound Containing Tetrapyrido [3,2-a:2′,3′-c:3″, 2″-h:2■,3■-j] phenazine with DNA

A new monometallic complex [Co(phen)_2tpphz]^(3+) (where tpphz is tetrapyrido [3,2-a:2′,3′-c:3″,2″-h:2′″,3′″-j] phenazine) was synthesized by the reaction of 5, 6-diamino-1,10-phenanthroline with [Co(phen)_2(phendione)]^(3+). It was characterized by elemental analysis, molar conductivity, IR, ~1H NMR, ultraviolet and fluorescence spectroscopy. The interaction of the complex with DNA was also investigated. The complex shows the absorption hypochromicity, fluorescence enhancement, the specific viscosity increased when bound to calf thymus DNA. The cyclic voltammetry (CV) measurement showed a change in peak current with the addition of DNA. All the results provide the support for the intercalative binding mode of the mononuclear complex.

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a：2？,3？-c]phenazine and 2,4＇-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd（2,4＇-bpdc）（DPPZ）]2n·n H2O（1） and [Zn（2,4＇-Hbpdc）2（DPPZ）]· H2O（DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, 2,4＇-H2bpdc = 2,4＇-biphenyldicarboxylic acid） have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction（XRD） and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.

Hydrothermal Syntheses and Crystal Structures of Cd(Ⅱ) and Cu(Ⅱ) Complexes Constructed with 1,3,5-Benzenetricarboxylic Acid and Dipyrido[3,2-a:2?,3?-c]phenazine Ligands

Two novel coordination compounds, [Cd2（HBTC）2（DPPZ）2（H2O）3].2H2O （1） and [Cu2（HBTC）2（DPPZ）2（HEO）]n （2） based on 1,3,5-benzenetricarboxylic acid （H3BTC） and dipyrido[3,2-a：2＇,3＇-c]phenazine （DPPZ） ligands, have been constructed under hydrothermal conditions. Two complexes are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Structural analyses show that both complexes 1 and 2 present the three-dimensional supramolecular structures. In addition, two complexes exhibit luminescence property.

Phenazine Methosulphate Modulating the Expression of Genes Involved in Yeast to Hyphal Form Signal Transduction in <i>Candida albicans</i>

Candida albicans has ability to switch from yeast to hyphal form which is an important virulence factor. The objective of the research is to study the effect of Phenazine Methosulphate (PMS) on virulence factors and to study expression profile in yeast to hyphal form transition in C. albicans. Phenazine Methosulphate (PMS) acted as an inhibitor of yeast to hyphal form transition, adhesion and biofilm formation in C. albicans. RTPCR study demonstrated that PMS Modulate the expression of genes involved in Ras1-cAMP-Efg1 and Cek1-MAPK signal transduction pathways. Cell cycle of C. albicans was arrested at S phase on treatment of PMS. Hyphal suppressor genes like Tup1, Mig1 and Nrg1 were upregulated by PMS. Based on our data on expression of genes during yeast to hyphal form transition in presence and absence of PMS, we hypothesize that inhibition of hyphal formation may be due to the overexpression of negative regulators of hyphal growth. Targeting of hyphal specific genes involved in these pathways may be a promising strategy for anti-candida drug development.

Isolation and structural identification of two bioactive phenazines from Streptomyces griseoluteus P510

Phenazine antibiotics phenazine-l-carboxylic acid （PCA） and l-hydroxyphenazine （1-OH-PHZ） were purified from culture broth and mycelia ofStreptomyces griseoluteus P510, Both PCA and 1 -OH-PHZ exhibit strong antifun- gal activity against six plant pathogens, especially Fusarium oxysporium, with minimal inhibition concentrations less than I and 2/ag, ml- 1 for PCA and 1-OH-PHZ, respectively, The presence of PCA and 1 -OH-PHZ indicates that S. griseoluteus PSlO can be used as a potential source of pesticides,

Phenazines:Natural products for microbial growth control

The unprecedented problem of antibiotic resistance has become a major challenge for public health,which has contributed to an increase in infections caused by such bacteria.These microbial infections,typically biofilm-related,are alsocoupled to an increase in human mortality and morbidity.However,the demand for new antimicrobial agents hasincreased along with the evolution of microbial resistance mechanisms.Natural products produced by bacteria,such as phenazines,have been recognized as an important source for the development of new antimicrobial agents,through the exploitation of their capacity to increase oxidative stress in other organisms.Phenazines are a large groupof nitrogen-containing heterocyclic compounds and are essential for several cellular processes including iron acquisition,signaling events,enzymatic processes,and biofilm formation.Phenazine-inspired antibiotics(i.e.,2-bromo-1-hydroxyphenazine,2,4-dibromo-1-hydroxyphenazine,bromophenazine-21,phenazine-13,and phenazine-14)are veryactive against a wide range of gram-positive and gram-negative bacteria,including those associated with severe infections.In this study,mechanisms of phenazine-inspired antibiotics in the cellular processes of planktonic and sessilebacteria are reviewed.Moreover,the application of phenazine-inspired antibiotics for the eradication of multidrugresistant planktonic and biofilm bacterial infections is also reviewed.

Phenazine-based supramolecular photosensitizing assemblies:A“smart”selectivity control on catalytic activity of Pd(Ⅱ)nanoparticles

Photosensitizing supramolecular assemblies based on a phenazine derivative(PPA)have been developed,which show a strong affinity toward Pd2+ions to generate supramolecular ensemble PPA@Pd nanoparticles(NPs).The PPA@Pd NPs catalyse the Suzuki cross-coupled reaction under mild conditions(aerial conditions,mixed aqueous media,and visible light radiations).Although PPA@Pd NPs exhibit a strong affinity for arylboronic acid and could catalyse homocoupling of arylboronic acid,the preference of PPA assemblies for aryl halide directed the course of reactions toward the formation of cross-coupled products.The electron-rich PPA assemblies not only facilitate the oxidative addition step through photoinduced electron transfer to Pd^(2+)ions but also bring the reactants closer to the catalytic sites by selective interactions with aryl halides in the presence of arylboronic acid under visible light irradiation.The efficiency of PPA@Pd NPs to catalyse the Suzuki crosscoupled reaction has been demonstrated for the synthesis of unsymmetrically substituted terphenyl derivatives.

Theophylline as a new and green catalyst for the one-pot synthesis of spiro[benzo[α]pyrano[2,3-c]phenazine]and benzo[α]pyrano[2,3-c]phenazine derivatives under solvent-free conditions

A green,convenient,high yielding and one-pot procedure for the synthesis of novel spiro[benzo[α]pyrano[2,3-c]phenazine]derivatives by domino multi-component condensation reaction between 2-hydroxynaphthalene-l,4-dione,benzene-l,2-diamines,ninhydrine,and malononitrile in the presence of a catalytic amount of 1,3-dimethyl-7H-purine-2,6-dione（theophylline） as an expedient,eco-friendly and reusable solid base catalyst under thermal,microwave irradiation and solvent-free conditions.This procedure has also been applied successfully for the synthesis of benzo[α]pyrano[2,3-c]phenazines.

A phenazine anode for high-performance aqueous rechargeable batteries in a wide temperature range

Aqueous rechargeable batteries are a possible strategy for large-scale energy storage systems.However,limited choices of anode materials restrict their further application.Here we report phenazine(PNZ)as stable anode materials in different alkali-ion(Li+,Na+,K+)electrolyte.A novel full cell is assembled by phenazine anode,Na0.44MnO2 cathode and 10 M NaOH electrolyte to further explore the electrochemical performance of phenazine anode.This battery is able to achieve high capacity(176.7 mAh·g^−1 at 4 C(1.2·Ag^−1)),ultralong cycling life(capacity retention of 80%after 13,000 cycles at 4 C),and excellent rate capacity(92 mAh·g^−1 at 100 C(30 A·g^−1)).The reaction mechanism of PNZ during charge—discharge process is demonstrated by in situ Raman spectroscopy,in situ Fourier transform infrared(FTIR)spectroscopy,X-ray photoelectron spectroscopy(XPS)and density functional theory(DFT)calculations.Furthermore,the system is able to successfully operate at wide temperature range from−20 to 70°C and achieves remarkable electrochemical performance.

Formation and cytotoxicity of a new disinfection by-product (DBP) phenazine by chloramination of water containing diphenylamine

Disinfection by-products （DBPs） in drinking water have caused worldwide concern due to their potential carcinogenic effects. The formation of phenazine from diphenylamine （DPhA） chloramination was studied and its cytotoxicities for two human cancer cells were also investigated. Phenazine was detected synchronously with the consumption of DPhA by chloramination, which further confirmed that the new DBP phenazine can be produced along with N-nitrosodiphenylamine （NDPhA） from DPhA chloramination. The formation of phenazine had a maximum molar yield with solution pH increasing from 5.0 to 9.0, with phenazine as the main product for DPhA chloramination at lower pH, but higher pH favored the formation of NDPhA. Thus, solution pH is the key factor in controlling the formation of phenazine and NDPhA. Both the initial DPhA and chloramine concentrations did not show a significant effect on the molar yields of phenazine, although increasing the chloramine concentration could speed up the reaction rate of DPhA with chloramines. The cytotoxicity assays showed that phenazine had significant cell-specific toxicity towards T24 （bladder cancer cell lines） and HepG2 （hepatic tumor cell lines） cells with IC50 values of 0.50 and 2.04 mmol/L, respectively, and T24 cells being more sensitive to phenazine than HepG2 cells. The ICs0 values of phenazine, DPhA, and NDPhA for T24 cells were of the same order of magnitude and the cytotoxicity of phenazine for T24 cells was slightly lower than that of NDPhA （IC50, 0.16 mmol/L）, suggesting that phenazine in drinking water may have an adverse effect on human health.

Deep insight into the charge transfer interactions in 1,2,4,5-tetracyanobenzene-phenazine cocrystal

A new charge transfer cocrystal of 1,2,4,5-tetracyanobenzene(TCNB)-phenazine(PTC)was prepared by solvent evaporation method.The donor and acceptor molecules of cocrystal are stacked face to face with a mixed-stacking,implying a strong charge transfer(CT)interactions in the cocrystal system.The spectroscopic studies,single-crystal X-ray diffraction structure,density functional theory(DFT)and Hirschfield surfaces calculations are carried out to explore the relationship between structure and properties of cocrystal system,which show that the intermolecular interactions in PTC are stronger than those of single components,leading to the stability and photophysical behaviors of cocrystal different from their constitute units.This study will be helpful for the design and preparation of multifunctional cocrystal materials.

Selective Recognition of Phenazine by 2,6-Dibutoxylnaphthalene-Based Tetralactam Macrocycle

A 2,6-dibutoxylnaphthalene-based tetralactam macrocycle was designed and synthesized.This macrocycle shows highly selective recognition to phenazine-a well-known secondary metabolite in bacteria and an emerging disinfection byproduct in drinking water.In contrast,the macrocycle shows no binding to the structurally similar dibenzo-1,4-dioxin.It was revealed that hydrogen bonding,π-π and σ-π interactions are the major driving forces between phenazine and the new tetralactam macrocycle.A perfect complementarity in electrostatic potential surfaces may explain the high selectivity.In addition,the macrocycle shows fluorescent response to phenazine,demonstrating its potential in fluorescent detection of phenazine.

Bioactive phenazines from an earwig-associated Streptomyces sp.

Three new phenazine-type compounds, named phenazines SA–SC(1–3), together with four new natural products(4–7), were isolated from the fermentation broth of an earwig-associated Streptomyces sp. NA04227. The structures of these compounds were determined by extensive analyses of NMR, high resolution mass spectroscopic data, as well as single-crystal X-ray diffraction measurement. Sequencing and analysis of the genome data allowed us to identify the gene cluster(spz) and propose a biosynthetic pathway for these phenazine-type compounds. Additionally, compounds 1–5 exhibited moderate inhibitory activity against acetylcholinesterase(AChE), and compound 3 showed antimicrobial activities against Micrococcus luteus.