2013 Synthesis and application of terpolymer scale inhibitor in the presence

The synthesis of several chiral ATRP initiators and their helix-sense-selective initiating function for ATRPCandidate Wang Shi-HaiSupervisor Professor Yang Nian-FaCollege Chemistry CollegeProgram Organic ChemistrySpecialization Asymmetric Organic SynthesisDegree Master of ScienceUniversity Xiangtan UniversityDate May, 2012湘潭大学学位论文原创性声明本人郑重声明：所呈交的论文是本人在导师的指导下独立进行研究所取得的研究成果。

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涉密论文按学校规定处理。

作者签名：日期：年月日导师签名：日期：年月日摘要螺旋聚合物因在手性分离、不对称催化等方面具有广泛的应用前景，而引起广泛关注。

在制备螺旋聚合物的各种方法中，为了有效的控制聚合物的立体结构，我们大多采用阴离子聚合和配位聚合。

随着近年来各种活性自由基聚合技术的发展，它对聚合物结构的调控能力大大增强，但运用原子转移活性自由基聚合（ATRP）法合成螺旋聚合物的报道却极少。

Journal of Experimental Botany , Vol. 64, No. 4, pp. 1005–1015, 2013doi:10.1093/jxb/ers380 Advance Access publication 10 January, 2013© The Author [2013]. Published by Oxford University Press [on behalf of the Society for Experimental Biology]. All rights reserved. For permissions, please email: journals.permissions@Abbreviations: ABA, abscisic acid; ABC, ATP-binding cassette; β-AS, β-amyrin synthase; EV , empty vector; GUS, β-glucuronidase; IFS, isoflavone synthase; LC/ESI/MS, liquid chromatography/electrospray ionization/mass spectrometry analysis; MAPK, mitogen-activated protein kinase; MeJA, methyl jasmonate; PAL, phenylalanine ammonia-lyase; PAMP , pathogen-associated molecular pattern; PDR, pleiotropic drug resistance; RNAi, RNA interference; SA, salicylic acid; SD, standard deviation.ReseaRch papeRA Medicago truncatula ABC transporter belonging to subfamily G modulates the level of isoflavonoidsJoanna Banasiak 1, Wanda Biała 2, Anna Staszków 1, Barbara Swarcewicz 1, Ewa K ępczy ńska 3, Marek Figlerowicz 1 and Michał Jasi ński 1,2*1Institute of Bioorganic Chemistry PAS, Noskowskiego 12/14, 61–704 Pozna ń, Poland 2Department of Biochemistry and Biotechnology, Pozna ń University of Life Sciences, Woły ńska 35, 60–637 Pozna ń, Poland 3Department of Plant Biotechnology, Faculty of Natural Science, University of Szczecin, Waska 13, 71–415 Szczecin, Poland * To whom correspondence should be addressed. E-mail: jasinski@ibch.poznan.plReceived 8 October 2012; Revised 22 November 2012; Accepted 12 December 2012AbstractFull-sized ATP-binding cassette (ABC) transporters of the G subfamily (ABCG) are considered to be essential compo-nents of the plant immune system. These proteins have been proposed to be implicated in the active transmembrane transport of various secondary metabolites. Despite the importance of ABCG-based transport for plant–microbe interactions, these proteins are still poorly recognized in legumes. The experiments described here demonstrated that the level of Medicago truncatula ABCG10 (MtABCG10) mRNA was elevated following application of fungal oli-gosaccharides to plant roots. Spatial expression pattern analysis with a reporter gene revealed that the MtABCG10 promoter was active in various organs, mostly within their vascular tissues. The corresponding protein was located in the plasma membrane. Silencing of MtABCG10 in hairy roots resulted in lower accumulation of the phenylpropa-noid pathway-derived medicarpin and its precursors. PCR-based experiments indicated that infection with Fusarium oxysporum , a root-infecting pathogen, progressed faster in MtABCG10-silenced composite plants (consisting of wild-type shoots on transgenic roots) than in the corresponding controls. Based on the presented data, it is proposed that in Medicago , full-sized ABCG transporters might modulate isoflavonoid levels during the defence response associ-ated with de novo synthesis of phytoalexins.Key words: ABCG transporters, immune system, isoflavonoids, Medicago truncatula , PDR transporters, phytoalexin.IntroductionATP-binding cassette (ABC) transporters form one of the largest and most evolutionarily conserved families of proteins in all kingdoms. They possess a conserved domain-based structure and are classified into eight subfamilies (ABCA–H) (Verrier et al ., 2008). Full-sized ABC transporters of the ABCG subfamily [formerly called pleiotropic drug resist-ance (PDR)] have been identified in plants, fungi, oomycetes, brown algae, and slime molds (Kang et al ., 2011).Several full-sized ABCG proteins play a role in the response to biotic stress, especially in a non-specific manner, which con-fers protection against a wide group of pathogens. For example, RNA interference (RNAi)-mediated silencing of NpPDR1 causes Nicotiana plumbaginifolia to be more sensitive to infec-tion with fungal (Botrytis cinerea and Fusarium oxysporum ) and oomycete pathogens (Phytophthora nicotianae ) (Bultreys et al ., 2009). Expression of Nicotiana tabacum NtPDR1 was shownat Huazhong Agricultural University on May 13, 2013/Downloaded from1006|Banasiak et al.to be induced by treatment with various general elicitors such as flagellin Psto, yeast extract, and INF1 elicitin (Sasabe et al., 2002). I n Arabidopsis, the mRNA level of AtPDR8/PEN3/ AtABCG36 is elevated during plant infection with virulent and avirulent strains of the bacterial pathogen Pseudomonas syrin-gae. Knockout of AtPDR8 decreases Arabidopsis resistance to inappropriate pathogenic fungi (Kobae et al., 2006; Stein et al., 2006). Expression of Arabidopsis PDR12/AtABCG40, signifi-cantly increases after infection with compatible (Sclerotina sclerotiorum) and incompatible (Alternaria brassicicola) fungal pathogens, as well as after treatment with salicylic acid (SA), ethylene, or methyl jasmonate (MeJA) (Campbell et al., 2003). In wheat (Triticum aestivum), a putative full-size ABCG trans-porter (LR34) confers a durable resistance to multiple fungal pathogens (Krattinger et al., 2009). Recently, a new opening for the role of ABCG transporters in response to biotic stress has come with the finding of the involvement of the N. tabacum ABCG5 transporter in resistance to Manduca sexta herbivory (Bienert et al., 2012). It was also shown that ABCG32/PEC1 in Arabidopsis and HvABCG31/Eibi1 in barley are required for the formation of a functional cuticle, which can act as the first barrier against abiotic and biotic stresses (Bessire et al., 2011; Chen et al., 2011).Legume ABC transporters additionally attract attention as being possibly implicated in the establishment of symbioses (Sugiyama et al., 2006; Takanashi et al., 2011). Their identi-fication has been accelerated by deciphering of the genome sequences of the model legumes Glycine max and Medicago truncatula (Schmutz et al., 2010; Y oung et al., 2011). Two M. truncatula so-called half-sized ABCG transporters (STR and STR2) that are present in peri-arbuscular membranes were found to be indispensable for arbuscule development in mycorrhizal symbiosis (Zhang et al., 2010). Expression of several legume ABCG genes was shown to be induced upon treatment with molecules such as SA or with pathogenic fungi (Eichhorn et al., 2006; Jasinski et al., 2009).The proposed role of ABCGs in the immune system is modulation of the transmembrane transport of signalling/ defensive compounds. Thus, efforts have been made to iden-tify the phytochemicals transported by the various ABCGs (Badri et al., 2008; Badri et al., 2009). Recently, it was reported that secretion of strigolactones, signalling molecules found in the initiation of arbuscular mycorrhizae, is the contribu-tion of the full-sized ABCG transporter (Kretzschmar et al., 2012). Additionally, Arabidopsis ABCG29 has been found as a p-coumaryl alcohol transporter, and it has been suggested that proper function of this protein has a complex impact on phenolic compounds and glucosinolate levels in this plant (Alejandro et al., 2012). Dysfunction of certain ABCG trans-porters in Arabidopsis results in the accumulation of flavonoid glycosides (kaempeferol and quercetin) in the root tissues (Badri et al., 2012). Flavonoids play a particular role in biotic stress responses. This multifaceted group of plant secondary products can function as antimicrobial agents, UV protect-ants, pollinator attractants, floral pigments, and inducers of the nodulation genes in symbiotic soil bacteria known as rhizobia. A special subclass of flavonoids is composed of iso-flavonoids, which are limited primarily to the Leguminosae. Isoflavonoids are thought to represent the majority of phy-toalexins produced by legume plants (Hassan and Mathesius, 2012). For instance, soybean partial resistance to Fusarium solani seems to be associated with the ability of soybean rootsto produce the phytoalexin glyceollin in response to fungal infection (Lozovaya et al., 2004). It has been proposed thatABC-type transporters can be involved in the secretion of (iso)flavonoids from soybean roots (Sugiyama et al., 2007).In this study, a full-sized ABCG plasma membrane trans-porter from M. truncatula was characterized. Spatial expres-sion pattern analysis with the β-glucuronidase (GUS) reportergene revealed the activity of the MtABCG10 promoter in vari-ous organs including, roots, leaves, flowers, and fruits. Silencingof MtABCG10 in hairy roots resulted in a lower accumulationof isoflavone precursors of the phytoalexin medicarpin. I n addition, faster spreading of F. oxysporum in MtABCG10-silenced Medicago was observed compared with control plants. Materials and methodsPlant materialM. truncatula (Jemalong J5) seedlings were germinated on water-saturated Whatman discs in Petri plates and grown under controlled greenhouse conditions with a mean temperature of 22°C, 50% humidity, and a 16 h photoperiod.Leaf-originated Medicago suspension cell cultures were main-tained in a 16 h photoperiod at 22 °C on an orbital shaker (150 rpm).The cultures were grown in medium (Murashige and Skoog mediumplus Gamborg’s vitamins supplemented with 30 g l–1 of saccharose,2 mg l–1 of 2,4-dichlorophenoxyacetic acid, and 0.25 mg l–1 of kine-tin), and were diluted 1:2 every 2 weeks.Plants with silenced MtABCG10 expression were obtained fromM. truncatula after infection of a radicle with Agrobacterium rhizo-genes Arqua1 (/medicagohandbook).Hairy-root cultures were initiated by cutting off the roots and growing them in the dark at 22 °C on solid Fahraeus medium, sup-plemented with saccharose (10 g l–1), myoinositol (100 mg l–1), thi-amine (10 mg l–1), pyridoxine (1 mg l–1), biotin (1 mg l–1), nicotinicacid (1 mg l–1), and glycine (2 mg l–1). Fragments of hairy roots were transferred onto fresh medium every 3 weeks.Fungal elicitor and MeJA treatmentThe Phoma medicaginis oligosaccharide elicitor was prepared as described previously (Hahn et al., 1992). The concentration of the elic-itor was determined by the phenol/sulphuric acid method (Fry, 1994).Five-d-old Medicago seedlings were transferred to solid 0.5× Gamborg’s medium supplemented with elicitor (25 µg ml–1) or MeJA (10 µM). Water and DMSO were used as controls, respec-tively. Samples were collected at 1, 2, 3, and 6 h after transfer and immediately frozen.For metabolomic analysis, 3-week-old root cultures (250 ± 50 mg)were transferred into liquid medium (5 ml) and acclimatized for 24 h. Samples (hairy roots and medium) were collected at 6, 24, and 72 hafter treatment with elicitor (25 µg ml–1) or water and immediately frozen.Real-time quantitative RT-PCR (qRT-PCR) analysisRNA was isolated from plant material with an RNeasy Extraction kit (Qiagen). Genomic DNA was removed by on-column DNase treatment. Total RNA (500 ng) was converted to cDNA with Omniscript reverse transcriptase (Qiagen), accord-ing to the manufacturer’s protocol. Real-time PCR analysis wasat Huazhong Agricultural University on May 13, 2013/Downloaded fromMedicago ABCG and (iso)flavonoids | 1007performed in Rotor-Gene Q Real Time PCR machine (Corbett Research), using the MESA Green qPCR MasterMix Plus SYBR (Eurogentec). Primers sequences were as follows: MtABCG10:forward, 5’-AACTACTGTTATGTCGACCG-3’, and reverse5’-CACTATCTTTCATTGATGATC-3’; and actin (GenBank no.JQ028731): forward, 5’-TTCTCTCAGTACTTTCCAGC-3’, andreverse 5’-AAGCATCACAATCACTCC-3’. The threshold cyclemethod was used as described by Ruocco et al . (2011).Quantitative transcript abundance analysisRNA was isolated from Medicago roots and converted to cDNA as described for qRT-PCR analysis. The genomic DNA was extracted with a DNeasy kit (Qiagen). PCRs on DNA and cDNA as templates (30 cycles) were performed in an MJ Mini Personal Thermal Cycler (Bio-Rad). The sequences of the primers used for the amplification were as follows: forward, 5’-CATATTGGTATTGGATAGGCG-3’, and reverse 5’-CACTTACACCCATCAAAGC-3’. PCR/RT-PCR products were cloned into pGEM-T Easy (Promega) and 80 ran-domly selected clones were sequenced with Sp6/T7 primers.Preparation of microsomal and plasma membrane fractionsMicrosomal fractions were isolated from 150 mg of Medicago hairy-root culture or 4 g of suspension cell culture as described previously (Jasinski et al ., 2001). The plasma membranes were purified from microsomal fractions of M. truncatula suspension cell cultures by partitioning in an aqueous two-phase partition system (6 ml of phase mixture), as described by Larsson et al . (1987).Western blot analysisProteins (5 µg) were separated by SDS-PAGE and transferred to aPVDF membrane (Millipore) by electroblotting (semi-dry appara-tus; BioRad). The membrane was incubated either with primary pol-yclonal antibodies against a peptide corresponding to Glu2–Glu27of MtABCG10 (Eurogentec) or with primary antibodies specific forthe H +-ATPase (W1G) (Morsomme et al ., 1998). The secondaryantibodies were alkaline phosphatase-conjugated goat anti-rabbitIgG (Sigma).Genetic constructs and plant transformation The promoter region of MtABCG10 (710 bp) was amplified with the primers 5’-ATGAATTCAAGAAGCTGCCACTAAAGC-3’and 5’-TAGGATCCATTTTTTGTGCTGTTGTG-3’. The PCRproduct was cloned via Eco RI and Bam HI restriction sites into thepPR97 binary vector carrying the uidA reporter gene (Szabadoset al ., 1995).The cDNA fragment (139 bp) used for MtABCG10 RNAisilencing was amplified using the primers 5’-GGGGACAAGTTTG T A C A A A A A A G C A G G C T C T A T A A T T T T T A TGGATGAGCC-3’ and 5’-GGGGACCACTTTGTACAAGAAAGCTGGGTTCAAATATGTCAATGCTAGGC-3’, cloned intopDONR TM /Zeo (nvitrogen), and recombined into a modifiedGateway pK7GWI WG2(I I )-p35S ::DsRed binary vector (Limpenset al ., 2005).The binary vectors pPR97 and pK7GWI WG2(I I )-p35S ::DsRedwere transferred into the Agrobacterium tumefaciens strain EHA105and Agrobacterium rhizogenes strain Arqua1, respectively. Finally,the constructs were used to transform M. truncatula according tothe procedures described in M. truncatula handbook (http://www./medicagohandbook ).Transgenic plants carrying the MtABCG10P::GUS reporter con-struct were stained for GUS using 5-bromo-4-chloro-3-indolyl-β-d -glucuronide, according to the protocol described by Gallagher (1992). To identify transgenic roots carrying the silencing construct,the plant material was scanned with a Fluor I mager Fla-5100 (Fujifilm) using a 532 nm green laser and an LPG filter.In situ immunodetection of protoplasts and cells from M. truncatula suspension cultures Protoplasts from 6-d-old leaf-originated Medicago suspensioncell cultures were isolated as described previously (He et al ., 2007),with the exception that the digestion was carried out for 24 h in anenzyme solution consisting of 1.5% cellulase R10 (Serva), 0.6% mac-erozyme R10 (Serva), and 1% Driselase ® (Sigma-Aldrich). Cells werefixed with 3.7% formaldehyde in MS medium/MTSB buffer (50 mM PIPES, 5 mM MgSO 4.7 H 2O, 5 mM EGTA) (1:1) for 30 min and then washed with MS/MTSB. To reduce autofluorescence, the cells were treated with 0.1% NaBH 4. After washing with 0.5× MTSB, the cellwalls were partially digested (except for protoplast immunodetec-tion) with an enzyme cocktail (1.5% cellulase R10, 0.6% macerozyme, and 1% Driselase ® in 0.2 M mannitol, 20 mM KCl, and 20 mM MES, pH 5.8). The plasma membrane was permeabilized with 0.1% Triton X-100 and 0.05% Tween 20 in 0.5× MTSB. The samples were washed with PBS and saturated for 1 h in PBS containing 0.05% Tween 20 and 2% BSA. Finally, the samples were incubated with the primary antibodies anti-MtABCG10 (diluted 1:50), pre-immune serum (1:50), and anti-H +-ATPase (1:400) overnight at 4 °C. The cells were washed as described above and treated with secondary antibody replace by[Alexa Fluor 488-conjugated goat anti-rabbit IgG (Invitrogen), diluted 1:600] for 2 h at room temperature. The cells were observed by laser-scanning confocal microscopy (Nikon A1R-si). Nuclei and vacuoles were stained with 0.1 mM DAPI and 0.1% neutral red, respectively .Extraction of phenolic compounds and liquid chromatography/electrospray ionization/mass spectrometry analysis (LC/ESI/MS)Frozen tissue (250 ± 50 mg fresh weight of roots) was ground at 4 °Cwith mortar and pestle and extracted with 4 ml of 80% methanol. Culture medium containing root exudates was subjected to solidphase extraction as described previously (Staszkow et al ., 2011).Dried extracted samples were dissolved in 80% methanol and sub-jected to LC/ESI/MS analysis. Profiles of phenolic compounds wereacquired using an AgilentRR 1200 liquid chromatograph micrOToF-Q mass spectrometer (Bruker Daltonics). Chromatographic separa-tion was performed using an acetonitrile/water gradient. The spectrawere recorded in the targeted mode within the m /z mass range of50–1000. Metabolite profiles were registered in the positive-ion mode. For details, see Staszkow et al . (2011).F . oxysporum infection of composite M. truncatula plants F. oxysporum f. sp. medicaginis strain 179.29 was purchased from theCentraalbureau voor Schimmelcultures, Utrecht, The Netherlands.F. oxysporum was grown on potato dextrose agar at 24 °C with aphotoperiod of 12 h. Suspensions of microconidia were obtained byflooding the Petri dish with sterile water. The spore concentrationwas determined by counting and was then adjusted to 1.3 × 106 sporesml –1. A 100 µl sample of spore suspension was deposit onto the rootsof 4-week-old composite M. truncatula plants grown on Fahraeusmedium. Eighteen empty vector -transformed control compositeplants and 18 MtABCG10-silenced composite plants in three biologi-cal repetitions were analysed. The infection efficiency was determinedas the level of fungal DNA in various Medicago organs. The sameamount of genomic DNA (40 ng) for each sample was used for qPCR.Reactions were conducted (as for qRT-PCR) using F. Oxysporum -specific primers (forward: 5’-ACCGTTGTAGACACCATTGC-3’;reverse: 5’-AGTGCGTAAGTGCTCATCG-3’) for the β-tubulingene (Genbank accession no. DQ092478.1) and M. truncatula spe-cific primers for actin .Results MtABCG10 (GenBank no. XM_003597771) has been described during studies dedicated to full-sized ABCGat Huazhong Agricultural University on May 13, 2013/Downloaded fromMedicago ABCG and (iso)flavonoids|1009(Fig. 2A–C, H, and I). In the leaves, a staining pattern was observed that was restricted to the junctions of three leaflets of the petiole and, to a lesser extent, the veinlets (Fig. 2D, E). In the flowers, GUS activity was observed in the anthers and in the pollen grains (Fig. 2F). In the fruit, GUS expression was seen in the conductive tissues (Fig. 2G).Subcellular localization of MtABCG10In situ immunolocalization of MtABCG10 in cultured Medicago suspension cells showed a clear signal coming from the plasma membrane (Fig. 3A). Under the same parameters of image acquisition, the control with pre-immune serum did not give any signal (Fig. 3B). These images were analogous to those observed for antibodies against H+-ATPase, a plasma membrane marker (Fig. 3C) and control with secondary antibodies (Fig. 3D), respectively. In situ immunolocaliza-tion with culture cells was performed because these do not require embedding, which was found to destroy antigenic epitopes. When protoplasts were used for MtABCG10 immu-nolocalization again, signals from membranes surrounding the cells were observed (Fig. 3E), compared with the control of pre-immune serum (Fig. 3F). The nucleus was visualized by DAPI staining (Fig. 3G). The absence of MtABCG10 from the vacuolar membrane (tonoplast) might be assumed as the vacuole in suspension culture used for immunolocal-ization can readily be stained by neutral red and appeared fragmented into several large vesicles that could not beFig. 2. Expression of the MtABCG10P::GUS reporter construct in M. truncatula. Whole mounts (A–F) of MtABCG10P::GUS transgenic plants were stained for GUS activity. (A–G) Root stele (A–C), leaf (D), young leaf (7-d-old) (E), flower (F), and fruit (G). (H, I) Longitudinal (H) and transverse (I) sections through a root of an MtABCG10P::GUS transgenic plant. Bars, 1.25 cm (A–C); 2.5 cm (D–G); 100 µm (H, I). at Huazhong Agricultural University on May 13, 2013 / Downloaded from1010 | Banasiak et al.misidentified as the plasma membrane. (Fig. 3H ). Finally, Western blot analyses confirmed that MtABCG10 accu-mulates in phase partition-purified plasma membrane frac-tions similarly to H +-ATPase (Fig. 3I ). The specificity of the MtABCG10 antibodies was assayed by Western blotting with protein extracts from MtABCG10-silenced and non-silenced plant material additionally treated or not with fungal oligo-saccharides (Supplementary Fig. S3 at JXB online).RNAi-mediated knockdown of MtABCG10 in Medicago hairy rootsA. rhizogenes -mediated RNAi is a fast and effective method to study gene function in legumes. Transformed hairy roots are a good alternative to stable transgenic lines and can be propagated clonally (Limpens et al ., 2004). To suppress MtABCG10 expression, a 139 bp fragment from the cod-ing region (nt 3156–3295 of the cDNA) was obtained and introduced into the pK7GWIWG2(II)-p35S ::DsRED binary vector (Limpens et al ., 2005). The ability of the RNAi con-struct (MtABCG10 RNAi) to silence the expression of the MtABCG10 gene in the roots was tested. A significant reduc-tion in the MtABCG10/MtABCG10 level was observed when assayed by real-time PCR and Western blotting (Supplementary Fig. S3).Upon elicitation, in the roots of Medicago , induction of MtABCG10 expression proceeded along with that of PAL and IFS (Supplementary Fig. S1). Because one of the pro-posed functions of the full-sized ABCG transporters in plants is the translocation of secondary metabolites (Jasinski et al ., 2001; Badri et al ., 2008; Sugiyama et al ., 2008), a search for phenotypic differences at the metabolome level was initiated. Hairy roots represent a fully differentiated tissue that tends to produce tissue-specific secondary metabolites and thus are a suitable material for such an approach (Pistelli et al ., 2010). Six independent control lines carrying empty vector (EV) and six MtABCG10-silenced lines of hairy roots were analysed. A strong reduction in MtABCG10 levels was not accompa-nied by any visible morphological changes in the transgenic roots (Supplementary Fig. S3). To mimic fungal infection, the transgenic roots were exposed to an elicitor (oligosaccha-rides isolated from P . medicaginis cell walls) that induces theexpression of MtABCG10 and the phenylpropanoid biosyn-thesis pathway.Both control and MtABCG10-silenced root tissue (treated or not with elicitor), as well as root exudates, were analysedby LC/ESI/MS. The profiling and identification of flavonoids and their glycoconjugates in the samples were based on stand-ards, LC retention times, and high-resolution mass spectra.LC/MS analysis revealed that free aglycones like the chalcone isoliquiritigenin and its derivatives liquiritigenin, 5-deoxyisoflavones (e.g. daidzein, formononetin, 2’-hydroksy-formononetin, and vestitone) and medicarpin differentially accumulated in elicited and non-elicited samples (Fig. 4, and Supplementary Figs. 4 and 5 at JXB online). This was also true for naringenin and 5-hydroxyisoflavone (e.g. biochaninA), although to a lesser extent (data not shown). This effect was visible in control and MtABCG10-silenced root tissueFig. 3. MtABCG10 is localized to the plasma membrane. (A–D) In situ immunodetection carried out on M. truncatula cells from suspension culture with secondary Alexa Fluor 488-conjugated antibodies, using primary antibodies against MtABCG10 (A), pre-immune serum (B), primary antibodies against H +-ATPase (C), and a control with secondary antibodies (D). (E, F) In situ immunodetection with protoplasts and secondary Alexa Fluor 488-conjugated antibodies, using primary antibodies against MtABCG10 (E) and pre-immune serum (F). (G, H) Neutral red staining of vacuoles (H) and DAPI staining of the nucleus (G). (I) Protein gel blot analysis of microsomal (Mi) and plasma membrane (PM) fractions (obtained by the two-phase partition method) prepared from M. truncatula cells grown in liquid medium. Protein samples (2.5 µg) were electrophoresed, blotted, and immunodetected using anti-MtABCG10 or anti-H +-ATPase antibodies. PM/Mi indicates the signal ratio for the two membrane fractions. at Huazhong Agricultural University on May 13, 2013/Downloaded fromMedicago ABCG and (iso)flavonoids|1013Owing to the pleiotropic substrate profiles that are often associated with ABCG proteins (e.g. AtABCG36/AtPDR8; Stein et al., 2006; Kim et al., 2007; Strader and Bartel, 2009), it cannot be excluded that MtABCG10 might transport sev-eral different molecules. The latter might be represented by isoliquiritigenin and/or liquiritigenin. These compounds strongly induced the expression of MtABCG10, and it has been shown that certain substrates for ABCG transporters (e.g. sclareolide) induce the expression of their transporter (e.g. NpABC1) (Jasinski et al., 2001).The relatively widespread expression of MtABCG10 in many organs might support the term ‘pleiotropic’, not only for the substrate profile but also for the function fulfilled by MtABCG10 in a particular organ. Apart from its role in roots and an effect on isoflavonoids as revealed by gene silencing, its precise role in other plant parts (e.g. flowers) remains to be elucidated.The translocation of phenolic compounds, especially fla-vonoids and isoflavonoids, is still a matter of debate. Several mechanisms have been proposed, including vesicle-mediated transport and membrane transporter-mediated transport (Hassan and Mathesius, 2012). To date, members of the ABCC [formerly multidrug resistance-associated protein (MRP)] sub-family of ABC proteins have been implicated in phenolic traffic (Goodman et al., 2004; Zhao and Dixon, 2010). However, data describing the transport of genistein in soybean (Sugiyama et al., 2008) and the fact that silencing of MtABCG10 is asso-ciated with changes in isoflavonoid composition bring new insights into the possible role of ABCG proteins in modulating the amount of phenolic compounds in legumes.It is also worth considering that the MtABCG10 substrate may be an unknown signalling molecule that regulates defence mechanisms that rely on isoflavonoid biosynthesis/transport. This regulatory mechanism probably does not affect, at least at the transcriptional level, key enzymes of isoflavonoid biosynthesis, such as PAL or I FS, because their expression profile does not vary in control and silenced lines follow-ing elicitation. The tissue expression pattern of MtABCG10 visualized with the GUS reporter system and its plasma membrane localization suggested that the MtABCG10 pro-tein might translocate such molecules through the stele. Membrane transporters are important players in the regula-tion of metabolite biosynthesis and fluxes (Zhao and Dixon, 2010). In view of the presented data, a new potential role for plant ABCGs as modulators of isoflavonoid levels in legumes during biotic stress can be postulated. Supplementary dataSupplementary data are available at JXB online.Fig. S1 RT-PCR time-course expression analysis of MtABCG10, PAL, IFS, and β-AS in M. truncatula seed-ling roots treated (+) or not (–) with P. medicaginis cell-wall oligosaccharides.Fig. S2 Phylogenetic tree of the MtABCG10 homologues. Fig. S3MtABCG10 silencing in hairy root cultures and specificity of the anti-MtABCG10 antibodies.Fig. S4 Relative levels of selected (iso)flavonoids and isoflavonoid conjugates in M. truncatula control (EV) and MtABCG10-silenced (RNAi10) hairy root cultures.Fig. S5 Relative levels of selected (iso)flavonoids and isoflavonoid conjugates in M. truncatula control (EV) and MtABCG10-silenced (RNAi10) root exudates.Fig. S6 Time-course expression analysis of MtABCG10 inM. truncatula seedlings roots treated (+) or not (–) with isoli-quiritigenin (100 µM) (A) or liquiritigenin (100 µM) (B).Fig. S7 Pictures of control and MtABCG10-silenced plants infected with F. oxysporum.Fig. S8 Time-course expression analysis of MtABCG10 transcript (A) and protein (B) levels in M. truncatula sus-pension cell cultures treated (+) or not (–) with ABA, SA,or MeJA.Fig. S9 Comparison of MtABCG genes expression in con-trol (EV) and MtABCG10-silenced (RNAi10) hairy roots1 h after treatment (+) or (–) with P. medicaginis cell-wall oligosaccharides.Fig. S10 Outline of the biosynthetic pathways leading tothe major classes of flavonoids in M. truncatula.AcknowledgmentsWe thankI. Femiak for excellent technical assistance,M. Stobiecki and D. Muth for their help with LC/MS work, M. Maruniewicz and I. Ziomkiewicz for their helpwith the confocal microscope, P. Bednarek for critical com-ments, M. Boutry for W1G and GPDR antibodies, andE. Limpens for the pK7GWIWG2(II)-p35S::DsRED binary vector. National Science Centre Grants supported this work:2011/03/B/NZ1/02840 and N301 392139.ReferencesAlejandro S, Lee Y, Tohge T, Sudre D, Osorio S, Park J, Bovet L,Lee Y, Geldner N, Fernie AR, Martinoia E. 2012. AtABCG29 is a monolignol transporter involved in lignin biosynthesis. Current Biology22, 1207–1212.Anderson JP, Lichtenzveig J, Gleason C, Oliver RP, Singh KB.2010. The B-3 ethylene response factor MtERF1-1 mediates resistanceto a subset of root pathogens in Medicago truncatula without adversely affecting symbiosis with rhizobia. Plant Physiology154, 861–873.Badri DV, Chaparro JM, Manter DK, Martinoia E, Vivanco JM.2012. Influence of ATP-binding cassette transporters in root exudationof phytoalexins, signals, and in disease resistance. Frontiers in PlantScience3, 149.Badri DV, Loyola-Vargas VM, Broeckling CD, et al. 2008. Alteredprofile of secondary metabolites in the root exudates of ArabidopsisATP-binding cassette transporter mutants. Plant Physiology146,762–771.Badri DV, Quintana N, El Kassis EG, Kim HK, Choi YH,Sugiyama A, Verpoorte R, Martinoia E, Manter DK, VivancoJM. 2009. An ABC transporter mutation alters root exudation of phytochemicals that provoke an overhaul of natural soil microbiota.Plant Physiology151, 2006–2017.at Huazhong Agricultural University on May 13, 2013/Downloaded from。

专利名称：Thermoplastic compositions, process for their preparation and their application inobtaining industrial objects发明人：AUDUREAU, JOEL,CRENNA, VINCENT申请号：EP88401094.3申请日：19880505公开号：EP0294253B1公开日：19950118专利内容由知识产权出版社提供摘要：The compositions contain: < / p & gt; & lt; p > a) less than 90 and at least 2 by weight of at least one polymer of ethylene and, if any, of at least one - olefin having from 3 to 12 carbon atoms, said polymer containing at least 70 mole of units derivatives of the ethylene, and < / p & gt; & lt; p & gt; b) more than 10 and up to 98% by weight of at least one polymer (b) containing at least 85 mol of patterns derivatives of at least one -olefin having from 3 to 12 carbon atoms and at most 15, in moles, of derivatives of the ethylene, and are distinguished in that the modified polymer a is a polymer whose viscosity limits measured is between 1,3 and 100 times its viscosity limits calculated from the distribution of the masses molecular. < / p & gt; & lt; p & gt; they are obtained by a method consisting in placing a polymer of ethylene and, if any, of at least one - olefin having from 3 to 12 carbon atoms in the presence of: - on the one hand, of at least one free radical initiator, in a quantity of between 0,001 and 0,3 parts by weight of initiator to 100 parts by weight of said polymer has a temperature which is greater at the temperature of melting of the polymer during a time at the upper or the same tenth of the time of half - life of the initiator is the temperature considered and - of the otherhand, of at least one polymer b. < / p & gt; & lt; p & gt; application for the preparation of industrial articles by extrusion - blowing conduits or of a hollow body, the extrusion of the films by filiere flat roto -, injection molded or coating.申请人：ECP ENICHEM POLYMERES FRANCE,ENICHEM POLYMERES FRANCE,ECP ENICHEM POLYMERES FRANCE地址：FR国籍：FR代理机构：Chaillot, Geneviève更多信息请下载全文后查看。

第6卷　第4期2013年8月　 中国光学 Chinese Optics Vol.6　No.4Aug.2013 收稿日期:2013⁃04⁃11;修订日期:2013⁃06⁃13 基金项目:国家自然科学基金面上项目(No.31270680,No.61076064);江苏省“六大高峰人才”资助项目(No.2011⁃XCL⁃018);江苏高校优势学科建设工程资助项目文章编号　1674⁃2915(2013)04⁃0490⁃11激光诱导击穿光谱技术及应用研究进展侯冠宇1,王　平1∗,佟存柱2(1.南京林业大学化学工程学院,江苏南京210037;2.中国科学院长春光学精密机械与物理研究所发光学及应用国家重点实验室,吉林长春130033)摘要:激光诱导击穿光谱(LIBS)技术是一种基于原子发射光谱学的元素定性、定量检测手段。

本文介绍了LIBS 技术的原理、应用方式、检测元素种类及检测极限;综述了该项技术在固体、液体、气体组分检测方面的技术发展,以及在环境检测、食品安全、生物医药、材料、军事、太空领域的应用进展。

最后,提出了高功率、高稳定的激光光源和准确的定量分析方法是LIBS 技术目前所面临的问题和挑战。

关　键　词:激光诱导击穿光谱;激光产生等离子体;元素分析;检测限中图分类号:O433.54;O657.319 文献标识码:A doi:10.3788/CO.20130604.0490Progress in laser⁃induced breakdown spectroscopyand its applicationsHOU Guan⁃yu 1,WANG Ping 1∗,TONG Cun⁃zhu 2(1.College of Chemical Engineering ,Nanjing Forestry University ,Nanjing 210037,China ;2.State Key Laboratory of Luminescence and Applications ,Changchun Institute of Optics ,Fine Mechanics and Physics ,Chinese Academy of Sciences ,Changchun 130033,China )∗Corresponding author ,E⁃mail :wp_lh@ Abstract :Laser⁃induced Breakdown Spectroscopy(LIBS)based on atomic emission spectral technology is a kind of convenient and sensitive approach for the qualitative and quantitative detection of elements.In this pa⁃per,the mechanism,detecting element types,detection limit and the recent progress of LIBS technology are reviewed.The progress of LIBS technology in component testing for solid,liquid and gas samples is expoundedin detail.The applications of LIBS in the environment test,food security,biological and medicines,material sciences,military and space fields are also presented.Finally,the challenges and problems for the LIBS tech⁃nology in high power and stable laser sources and accurately quantitative analysis method are discussed.Key words :laser⁃induced breakdown spectroscopy;laser⁃induced plasmon,element analysis;detection limit1　引　言 激光诱导击穿光谱(Laser⁃Induced Breakdown Spectroscopy,简称LIBS)技术是利用激光照射被测物体表面产生等离子体[1⁃2],通过检测等离子体光谱而获取物质成分和浓度的分析技术。

第43卷第2期2024年2月硅㊀酸㊀盐㊀通㊀报BULLETIN OF THE CHINESE CERAMIC SOCIETYVol.43㊀No.2February,2024磷石膏的综合利用及其在建筑材料领域的应用研究进展周㊀武1,2,李㊀杨1,2,冯伟光3,苏㊀轶1,2,揭伟哲1,2,张㊀华1,2,倪红卫1,2 (1.武汉科技大学钢铁冶金与资源利用省部共建教育部重点实验室,武汉㊀430081;2.武汉科技大学钢铁冶金新工艺湖北省重点实验室,武汉㊀430081;3.青岛睿海兴业管理咨询服务有限公司,青岛㊀266041)摘要:磷石膏是湿法制备磷肥工艺过程中的副产物,主要物相是CaSO4㊃2H2O㊂我国磷石膏产量居世界第一,综合利用率却不到50%,堆存量已达8亿吨,对生态环境造成了严重破坏,因此,探索磷石膏的有效利用途径已迫在眉睫㊂本文对磷石膏综合利用主要领域的研究现状进行了分析,其中磷石膏在化工领域的利用率仅有5%,在农业领域的利用率也只有2%,而建筑材料领域是目前磷石膏的主要应用领域㊂目前将磷石膏应用于水泥缓凝剂㊁石膏砌块和水泥砂浆已经实现了工业化;将磷石膏应用于胶凝材料和路基材料,由于浸出毒性的问题,并未大规模应用;将磷石膏用作填充剂则因为材料强度较低,仅仅停留于实验室探索阶段㊂最后展望了未来无害化利用磷石膏技术研究的发展趋势,以期为解决磷石膏的堆存问题提供参考㊂关键词:磷石膏;综合利用;应用领域;建筑材料;研究现状;发展趋势中图分类号:X781㊀㊀文献标志码:A㊀㊀文章编号:1001-1625(2024)02-0534-09 Research Progress on Comprehensive Utilization of Phosphogypsum and Its Application in the Field of Building MaterialsZHOU Wu1,2,LI Yang1,2,FENG Weiguang3,SU Yi1,2,JIE Weizhe1,2,ZHANG Hua1,2,NI Hongwei1,2 (1.Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education,Wuhan University of Science and Technology,Wuhan430081,China;2.Hubei Provincial Key Laboratory for New Processes of Ironmaking and Steelmaking,Wuhan University of Science and Technology,Wuhan430081,China;3.Ruihai Xingye Management Consulting Service Co.,Ltd.,Qingdao266041,China)Abstract:Phosphogypsum is a byproduct in the wet process of phosphate fertilizer production,with its main phase being CaSO4㊃2H2O.Despite China being the world s largest producer of phosphogypsum,its comprehensive utilization rate is below50%.The accumulated stock has reached800million tons,causing severe ecological damage.Therefore,exploring effective utilization methods for phosphogypsum is urgently needed.This article analyzes the current research status of the comprehensive utilization of phosphogypsum in various fields.Currently,the utilization rate of phosphogypsum in the chemical industry is only5%,and in agriculture is a mere2%,while the building materials sector remains its primary application field.Industrial applications such as using phosphogypsum as a cement retarder,gypsum block,and cement mortar have been industrialized.However,its application in cementitious materials and subgrade materials has not been widely adopted due to concerns about leaching toxicity.The use of phosphogypsum as a filler is still in the experimental exploration phase due to the relatively low strength of material.The paper concludes by envisioning the future trends in the research on environmental friendly utilization of phosphogypsum,aiming to provide references for resolving the stockpile issue of phosphogypsum.Key words:phosphogypsum;comprehensive utilization;application field;building material;research status;development trend收稿日期:2023-09-11;修订日期:2023-11-10基金项目:国家自然科学基金面上项目(52374344)作者简介:周㊀武(1998 ),男,硕士研究生㊂主要从事固废回收利用的研究㊂E-mail:2528548316@通信作者:李㊀杨,博士,副教授㊂E-mail:liyang2468@第2期周㊀武等:磷石膏的综合利用及其在建筑材料领域的应用研究进展535㊀0㊀引㊀言中国作为农业大国,大多数耕地缺少作物所必需的磷元素[1],对磷肥的需求量约为850万吨/年㊂一般来说,湿法是生产磷肥最主要的工艺[2]㊂该工艺以硫酸和磷矿石为原料,将磷矿石置于硫酸中分解,经萃取㊁分离等工艺后制得磷酸;再向磷酸中加入不同种类的原料(如磷矿石㊁氨气㊁石灰等)制得磷肥,湿法制磷肥工艺流程如图1所示,反应如式(1)所示㊂Ca 3(PO 4)2+2H 2SO 4ң3CaSO 4+2H 3PO 4(1)生产经验表明,每生产1t 的磷肥就会伴生近5t 的磷石膏[3]㊂我国磷石膏产地较为集中,基本上分布在云贵地区㊁长江中下游地区以及山东地区[4](见图2)㊂据中国磷复肥工业协会统计,2021年中国磷石膏产量突破8000万吨,2022年总堆存量已达8亿吨[5],而2021年巴西的产量只有1237万吨,塞尔维亚的产量仅有81万吨[6]㊂中国磷石膏产量居世界第一,综合利用率却不到50%,相比日本等国家近100%的利用率,中国的磷石膏综合利用能力亟须增强[7](见表1)㊂图1㊀湿法制磷肥工艺流程图[2]Fig.1㊀Flowchart of wet process for phosphate fertilizer production[2]图2㊀中国磷石膏产地分布[4]Fig.2㊀Distribution of phosphogypsum producing areas in China [4]表1㊀部分国家磷石膏综合利用现状[7]Table 1㊀Comprehensive utilization status of phosphogypsum in some countries [7]地区主要处置措施比利时约90%用于石膏建筑材料,8%左右用于农业,少量临时堆存巴西主要用于农业,使用量已超过产生量加拿大磷酸生产已停止,堆场表层 人造土 后复垦种植人造林芬兰堆存为主,少量用于农业㊁道路等试点哈萨克斯坦主要用于农业土壤改良波兰少量用于农业印度约45%用于制造水泥,10%用于农业摩洛哥排入海洋菲律宾部分用于水泥㊁农业,少量进行稀土元素回收试点俄罗斯农业㊁道路应用已实现商业化美国堆存为主,少量用于农业日本100%用于石膏建筑材料及水泥缓凝剂1㊀磷石膏的性质及危害1.1㊀磷石膏的性质磷石膏一般呈灰色粉末状,受杂质的影响也可能呈黄白色㊁浅灰白色或黑灰色(见图3(a)),其粒径一般为5~150μm,晶体形貌有针状㊁单分散板状㊁多晶核和密实四种形态,但以板状晶体为主[8](见图3(b))㊂磷石膏的成分十分复杂,其主要化学组成是CaO 和SO 3,还有少量的Al 2O 3㊁Fe 2O 3㊁SiO 2等(见表2)㊂此外,磷石膏中还存在一些有机物㊁氟化物㊁重金属离子以及微量的放射性元素[9]㊂磷石膏的XRD 谱如图4所536㊀资源综合利用硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷示,其主要物相结构是CaSO 4㊃2H 2O,还有少量的共晶磷(CaHPO 4㊃2H 2O)和SiO 2[10]㊂另外,部分磷石膏中还含有难溶磷(Ca 3(PO 4)2)以及难溶氟(CaSiF 6㊁CaF 2)等杂质[11]㊂图3㊀磷石膏的实物图与SEM 照片[8]Fig.3㊀Physical and SEM images of phosphogypsum [8]表2㊀磷石膏的化学成分[9]Table 2㊀Chemical composition of phosphogypsum [9]Composition CaO SiO 2Al 2O 3K 2O SO 3Fe 2O 3P 2O 5TiO 2MgO F LOIMass fraction /%27.0508.336 1.2730.81237.9490.5780.8020.1320.113 1.30321.652图4㊀磷石膏的XRD 谱[10]Fig.4㊀XRD pattern of phosphogypsum [10]1.2㊀磷石膏的危害未经处理的磷石膏含有P㊁F㊁重金属以及放射性元素,长时间的堆存对环境和人类都有较大的危害㊂研究[12]表明,磷石膏中的有毒元素会在雨水的冲刷下进入水循环,破坏生态平衡㊂此外,磷石膏中放射性元素虽然含量极低,但长期处于堆存区域仍会引起身体不适甚至癌变㊂本着废弃物资源化利用的原则,人们采用各种手段对磷石膏加以利用,均取得了不错的效果㊂例如利用磷石膏生产化工原料㊁改性土壤㊁生产建筑材料等㊂但相较于国内日渐增长的堆存量,这些利用手段对磷石膏的利用量显得杯水车薪,整个行业亟须一种更高效的方法来应对这种情况㊂2㊀磷石膏的回收利用目前磷石膏的综合利用主要在化工㊁农业以及建筑材料三个领域[13]㊂化工领域消耗量占比5%左右,农业领域消耗只占2%左右,除22%左右用于外供联营,其余磷石膏基本投入建筑材料领域㊂该领域消纳磷石膏的手段种类较多,可用于生产各种水泥㊁砌砖㊁凝胶材料㊁路基㊁填充剂等[14],虽然生产的建筑材料存在强度较低㊁浸出毒性大的问题,但该领域前景广阔,是目前解决磷石膏堆存问题的最有效手段㊂2.1㊀化工领域磷石膏在化工领域的利用一般是利用其中的Ca㊁S 等元素生产硫酸钙㊁硫酸氢钙等,但是过多的杂质使得生产成本较高,只能局限于实验室或者小规模试验生产,难以处理堆存量巨大的磷石膏㊂Xu 等[15]以磷石膏为原料,在100ħ条件下利用硫酸溶液制备出短柱状无水微米CaSO 4,该材料经NaOH-硬脂酸改性后,用作聚氯乙烯(PVC)的填充剂可显著提高其综合力学性能㊂Zdah 等[16]以磷石膏和LiOH㊃H 2O 为原料,在常温常压的水溶液中反应制得Ca(OH)2和Li 2SO 4㊃H 2O,发现反应时间为3h㊁磷石膏和LiOH㊃H 2O 浓度分别为2.0和4.1mol /L 时磷石膏的转化率最高㊂李冬丽等[17]以磷酸与磷石膏制备㊀第2期周㊀武等:磷石膏的综合利用及其在建筑材料领域的应用研究进展537的硫氢化钙为原料,合成出饲料级硫酸氢钙,为综合利用磷石膏提供了宝贵的指导意见㊂目前制约这一领域发展的最主要原因就是杂质去除问题,如何低成本㊁高效率净化磷石膏是打破瓶颈的关键因素,也是未来科学工作者们需要突破的方向㊂2.2㊀农业领域农业领域主要利用磷石膏中的酸性成分改良盐碱地,或利用其中所含的P㊁Ca等元素来增强土壤肥力㊂也有部分学者逆向思维,通过改性工艺使磷石膏能够改良酸性土壤㊂Sagna等[18]在探究磷石膏对盐碱土壤的调理效果时发现有机改良剂配合磷石膏能够显著降低盐碱土壤的碱化度㊂Panda等[19]另辟蹊径,在700ħ的条件下通过共热解香蕉花梗和磷石膏制备出一种生物炭磷石膏复合材料,该材料应用于酸性红壤可提高土壤中硫酸盐的含量,增强土壤肥力㊂此外,由于磷石膏在未经处理之前难以用于酸性土壤改良,严建立等[20]通过向磷石膏中配加石灰制得酸性土壤改良剂,发现在磷石膏掺量较少的情况下,该酸性土壤改良剂能够有效降低土壤中Cd㊁Cr㊁Pb的含量㊂综合上述分析可知,未经除杂的磷石膏不但没有调节土壤环境的能力,其中所含有的有毒元素反而会污染土壤和地下水,危害生态环境和人类健康㊂因而利用磷石膏对土壤进行改性的适用范围较窄,发展潜力不足㊂2.3㊀建筑材料领域建筑材料领域是目前回收利用磷石膏的主要途径,也可能是未来解决磷石膏堆存问题的发展方向㊂该领域主要利用磷石膏中的Ca㊁Si等有效元素,通过添加水泥或耦合其他固废,在碱性环境下发生火山灰反应制备得到各类建筑材料[21],反应原理如下:CaO+H2OңCa(OH)2ңCa2++OH-(2)Ca2++2OH-+SiO2ңC-S-H(3)Ca2++2OH-+Al2O3ңC-A-H(4)SiO2+OH-+H2Oң[H3SiO4]-(5)AlO2-+OH-+H2Oң[H3AlO4]2-(6)[H3SiO4]-+[H3AlO4]2-+Ca2+ңC-A-S-H(7)反应生成的C-S-H㊁C-A-H以及C-A-S-H具有很强的胶结作用,在脱水固化后能够大幅度提高材料的强度[22]㊂目前,磷石膏在建筑材料领域的利用有以下几种手段:制成胶凝材料以替代部分水泥的使用;制成填充剂以降低建筑材料孔隙率;直接制造水泥,降低生产成本;制造石膏砌块减少烧结砖的生产;制造路基材料㊁水泥缓凝剂等㊂2.3.1㊀胶凝材料胶凝材料能在水化反应后形成坚固的石状体,并胶结其他物料,在建筑材料领域具有广泛的应用㊂利用磷石膏制备胶凝材料不但可以减少水泥的使用,还能有效缓解磷石膏的堆存压力㊂魏兴[23]以磷石膏㊁无水石膏㊁钢渣和硅酸盐水泥(P㊃Ⅱ52.5)为原料,添加少量增效剂制备出一种复合胶凝材料,该胶凝材料28d抗压强度可达51.5MPa,一定程度上可减少P㊃C32.5水泥的使用㊂而胡修权等[24]向磷石膏基胶凝材料中掺入聚丙烯酸系高分子进行改性,发现磷石膏质量分数为40%时,样品28d抗压强度达到47.5MPa,相比未改性样品提高了25%以上㊂Gong等[25]以水泥和磷石膏为原料,探究了磷石膏制备复合胶凝材料的潜力,发现磷石膏质量分数为10%时,复合胶凝材料28d抗压强度可达49.8MPa㊂刘冬梅等[26]以质量比为20ʒ72ʒ8的磷石膏㊁磷渣㊁水泥熟料为原料,掺入质量分数为1.5%的水玻璃,制备出的复合胶凝材料28d抗压强度可达43MPa㊂虽然磷石膏制备的胶凝材料强度达标,但其对有毒元素的固化效果却不尽如人意,并不能够完全替代水泥在生产中的地位㊂2.3.2㊀建筑材料填充剂建筑材料填充剂通常不与物料组分发生反应,但又可以有效改善物料性能㊂近年来发现利用磷石膏制备建筑材料填充剂可以有效固化其中的有害元素,其固化原理如图5所示㊂黄琬等[27]以磷石膏为原料压制团粒,并对团粒的填充效应进行多角度验证,结果表明团粒填充试样较538㊀资源综合利用硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷粉末在有害元素的固定效果上更为理想,90d 试样浸出液中F -浓度为0.035mg /L,P 5+浓度也仅有0.35mg /L,满足一级排放标准㊂陈秋松等[28]为比较不同温度下磷石膏充填体的浸出毒性,采用磷石膏㊁硅酸盐水泥等原料制备样品并进行浸出毒性测试,结果表明30ħ条件下P 元素浸出浓度仅有0.05mg /L,符合国家标准㊂但可惜的是该工艺生产的材料强度并不理想,且磷石膏的利用量也比较少,难以消纳大量的磷石膏㊂图5㊀磷石膏充填体对毒害离子固化示意图[28]Fig.5㊀Schematic diagram of immobilization of toxic ions by phosphogypsum filling body [28]2.3.3㊀水泥砂浆水泥砂浆在建筑工程中主要用作粘合剂以及室内外抹灰㊂研究表明,磷石膏的主要成分CaSO 4能够用于生产水泥,有望通过这一手段来减少磷石膏的堆存量㊂但不容乐观的是,磷石膏的大量掺入会导致水泥凝结时间延长,强度急剧下降㊂图6㊀不同磷石膏掺量水泥砂浆的抗压强度[30]Fig.6㊀Compressive strength of cement mortar with different phosphogypsum content [30]Gong 等[29]为考察磷石膏掺量对水泥强度的影响,采用800ħ煅烧的磷石膏替代部分水泥制备新型水泥,结果显示,煅烧磷石膏对水泥强度的影响随掺量的增加呈先增强后减弱的趋势,在磷石膏质量分数为30%时,新型水泥的28d 抗压强度达到最大值(41.0MPa)㊂张敏等[30]同样采用高温煅烧的磷石膏,探究了其掺入量对水泥强度的影响,结果如图6所示,在磷石膏质量分数为10%时,水泥强度最大,随着掺量的增加,水泥强度降幅十分明显,这显然并不符合大量利用磷石膏的预期目标㊂2.3.4㊀石膏砌块石膏砌块作为建筑石膏制品(见图7),在墙体材料应用上具有较优异的性能㊂近年来,使用磷石膏代替建筑石膏制备砌块也成为综合利用该大宗固废的热门研究方向㊂图7㊀轻质石膏砌块与普通石膏砌块Fig.7㊀Lightweight gypsum block and ordinary gypsum block㊀第2期周㊀武等:磷石膏的综合利用及其在建筑材料领域的应用研究进展539 Wu等[31]以磷石膏为原料,采用常规机械压制法制备磷石膏砌块,发现当压制压力为300MPa㊁砌块中水的质量分数为5%㊁添加单质铁或单质铝的质量分数为1%时,磷石膏砌块的3d抗折强度可达8.0MPa㊂此外,为耦合其他固废,Oubaha等[32]采用质量比为52ʒ40ʒ8的磷矿废渣㊁磷石膏与水泥进行磷石膏砌块的制备,结果表明,磷石膏砌块28d抗压强度可达8.1MPa㊂不同于以上磷石膏砌块的传统制备工艺,骆真等[33]采用 先成型 再蒸压 后湿养 的新工艺,以改性磷石膏和α-半水石膏为原料,添加发泡剂制备出一种轻质石膏砌块,结果表明,当α-半水石膏与改性磷石膏质量比为1ʒ4㊁蒸压温度为140ħ时,新型砌块7d 抗折强度可达7.0MPa㊂遗憾的是,磷石膏砌块在强度等方面虽然达到了要求,但是其浸出毒性及长期稳定性仍然存在缺陷,这对于建筑材料来说这是一个不容忽视的问题㊂2.3.5㊀路基材料路基作为路面带状构造物,是铁路和公路的基础㊂由于磷石膏主要成分与路基原料成分相近,人们开始研究利用磷石膏耦合其他冶金固废来制作路基材料,并在这方面取得了较大成果㊂Dutta等[34]以质量比为90ʒ8ʒ2的粉煤灰㊁石灰和磷石膏为原料,制备出一种复合路基材料,结果表明该材料28d抗压强度为2.2MPa,满足美国国家公路与运输官员协会采用的碎石和沙土材料的强度标准㊂Zmemla等[35]以质量比为46.5ʒ46.5ʒ7的混合沙子㊁磷石膏与水泥为原料,制备出一种新型路基材料,测试结果表明该材料的28d抗压强度达到2.2MPa,满足路基材料的要求㊂同样地,吕伟等[36]以质量比为88ʒ6ʒ6的改性磷石膏㊁水泥和矿渣粉为原料,使用团粒工艺制成的轻骨料60d筒压强度达到5.8MPa,并在实际应用中取得了一定的效果(见图8),其中B-3为普通碎石道路稳定层,B-1和B-2为轻骨料部分替代碎石制备的磷石膏基道路稳定层㊂图8㊀不同配比的磷石膏基道路稳定层试样和工程应用[36]Fig.8㊀Samples and engineering applications of phosphogypsum-based road stabilizing layer with different ratios[36] 2.3.6㊀水泥缓凝剂水泥缓凝剂能延长水泥的凝结时间,且不对其后期各项性能造成不良影响㊂使用磷石膏替代天然石膏生产水泥缓凝剂,既可为企业开源节流,又可循环利用固废㊂刘骥等[37]使用磷石膏作为水泥缓凝剂,探究了磷石膏掺量对水泥凝结时间以及强度的影响,发现在26ħ环境下,水泥初凝时间从128min延长至276min,但磷石膏中可溶磷会降低水泥早期强度㊂此外,研究发现使用不同改性工艺制备的磷石膏缓凝剂性能各有侧重,王银等[38]采用蒸压法改性磷石膏与天然石膏制备缓凝剂,测试表明该缓凝剂侧重水泥强度,掺入缓凝剂后水泥28d抗压强度可达50.3MPa,各项指标均满足P㊃O42.5水泥质量标准㊂而He等[39]使用 两步晶化法 改性磷石膏制备的缓凝剂则更侧重有害元素的去除,当一次晶化硫酸质量分数为30%㊁二次晶化固液比为7ʒ1时,改性磷石膏中P2O5的质量分数仅有540㊀资源综合利用硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷0.02%,并且部分重金属元素含量为0%㊂2.3.7㊀磷石膏在建筑材料领域不同利用方法的对比磷石膏在建筑材料领域的利用方法按实际应用进度可分为工业化㊁暂未工业化和实验室探索阶段三种,其中制备水泥缓凝剂㊁石膏砌块以及水泥砂浆已实现了工业化利用,对磷石膏的利用量占比达到33%;生产路基及胶凝材料由于其浸出毒性较高,暂未大规模应用;制备建筑材料填充剂由于材料强度较低,仍在实验室探索中㊂这些利用方法的优缺点对比如表3所示㊂表3㊀磷石膏在建筑材料领域不同利用方法的对比Table3㊀Comparison of different utilization methods of phosphogypsum in the field of building materials 应用情况利用方法优点缺点水泥缓凝剂替代部分天然石膏使用,降低成本需要除杂处理,掺量过多会降低水泥性能工业化石膏砌块强度高,磷石膏用量大浸出毒性大,长期稳定性差水泥砂浆替代部分水泥的生产,减少碳排放磷石膏掺量少暂未工业化路基材料水稳性好,符合强度要求浸出毒性及长期稳定性不明胶凝材料强度高,可协同其他固废进行利用浸出毒性易超标实验室探索阶段建筑材料填充剂有毒元素固化效果好材料强度低,磷石膏用量少3㊀结语与展望磷石膏的综合利用主要在化工㊁农业以及建筑材料三个领域,其中利用磷石膏制备建筑材料是目前消纳磷石膏的最有效手段,按应用进度可分为工业化㊁暂未工业化㊁实验室探索阶段三种㊂制备水泥缓凝剂㊁石膏砌块以及水泥砂浆已经实现工业化应用,但仍存在磷石膏掺入量少㊁强度低㊁浸出毒性大的问题;生产路基及胶凝材料也同样存在浸出毒性大的问题,因而未大规模工业化应用;而制备填充剂由于材料强度低,磷石膏用量少,仅停留在实验室探索阶段㊂针对以上磷石膏回收利用的难题,为解决磷石膏堆存问题,未来可以从以下几个方向进行探索:1)寻找高效㊁低成本的磷石膏除杂工艺,尽量降低杂质元素对建筑材料强度以及浸出毒性的影响;2)综合利用其他固废,通过协同作用提升建筑材料强度以及对有害元素的固化效果㊂参考文献[1]㊀赵亚丽,杨春收,王㊀群,等.磷肥施用深度对夏玉米产量和养分吸收的影响[J].中国农业科学,2010,43(23):4805-4813.ZHAO Y L,YANG C S,WANG Q,et al.Effects of phosphorus placement depth on yield and nutrient uptake of summer maize[J].Scientia Agricultura Sinica,2010,43(23):4805-4813(in Chinese).[2]㊀何宾宾,魏立军,谢德龙,等.中国湿法磷加工产业现状与可持续发展[J].无机盐工业,2020,52(1):1-4+16.HE B B,WEI L J,XIE D L,et al.Current situation and sustainable development of wet process phosphorus processing industry in China[J].Inorganic 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自由基聚合引发剂的研究进展徐诚;唐华东【摘要】Free radical polymerization is an effective method for the polymerization of vinyl monomer, it can synthesis a variety of homo- and copolymers. The initiators of radical polymerization can be divided into azo initiators, peroxide initiators, redox initiators, multifunctionalinitiatior,macroinitiators and photoinitiators. This paper presents the progress of these initiators.%自由基聚合是乙烯基类单体的有效聚合方法，可合成多种均聚物和共聚物。

自由基聚合的引发剂可分为偶氮类引发剂、过氧化物类引发剂、氧化还原引发体系、多官能度引发剂、大分子引发剂和光敏引发剂。

本文主要介绍了这些引发剂的研究进展。

【期刊名称】《浙江化工》【年(卷),期】2015(000)006【总页数】4页(P34-37)【关键词】自由基聚合;引发剂;偶氮引发剂;氧化还原引发剂;光敏引发剂【作者】徐诚;唐华东【作者单位】浙江工业大学，浙江杭州 310014;浙江工业大学，浙江杭州310014【正文语种】中文自由基聚合为乙烯基类单体通过不断增长的自由基引发的聚合反应，可以生产众多均聚物、二元及多元共聚物产品，自上世纪50年代以来，已成为工业上生产高分子产品的重要技术，目前利用自由基聚合生产的烯烃聚合物已占到其总产量的70%左右［1-3］。

自由基聚合的优点为：适用单体广，反应条件要求不高，相关理论研究成熟，反应重现性好，易于操作控制，适于本体、悬浮和乳液聚合等工艺，便于大规模工业化生产［4-5］。

生物活性分子terpestacin的研究进展王清龙;王建玲;吕全建【摘要】真菌来源的活性天然产物为药物研发过程提供结构新颖、活性优良的先导化合物,因此在药物开发过程中具有重要的作用.真菌来源的二倍半萜类化合物terpestacin,是由一个十五元环和一个五元环稠合而成的双环化合物.由于其在具有抗癌、抗HIV等方面的活性,被认为是一种非常有前景的抗癌和抗HIV药物的先导化合物.因此自其被发现以来,科研工作者对该类化合物的生物活性、生物合成及化学合成方面开展了很多研究.本文收集了来自1993年以来关于terpestacin的文献报道,对该类化合物的生物来源、活性、生物合成途径及化学合成研究进行了简要综述.%The fungal metabolites,a kind of important compounds in the research and development of drugs for the novel structure and pretty bioactivity. Terpestacins,a kind of sesterpenoid from fungi,was structured with fifteen-membered ring and five-membered ring. For the interesting biological activities at anti-cancer,and anti-HIV,terpestacin was a potential lead compound for the development drugs of anticancer as well as anti-AIDS chemotherapeutics. Many researches on bioactivities biosynthesis and chemical synthesis of terpestacin have been conducted. This review focuses on the biological sources for the production,bioactivities biosynthesis and chemical synthesis of terpestacin on basis of the researching the literatures from the year 1993.【期刊名称】《河南科学》【年(卷),期】2017(035)011【总页数】6页(P1762-1767)【关键词】二倍半萜类天然产物;terpestacin;生物活性;生物合成;化学合成【作者】王清龙;王建玲;吕全建【作者单位】河南牧业经济学院基础部,郑州 450011;河南牧业经济学院基础部,郑州 450011;河南牧业经济学院基础部,郑州 450011【正文语种】中文【中图分类】O629.9天然产物（natural products）能为现代药物研究和开发过程提供结构新颖、活性优良的先导化合物（lead compound），在创新药物开发过程中占据着十分重要的地位.根据Newman等的统计，1981—2014年上市的1211个小分子药物中有65%的药物来源于天然产物或以天然产物骨架为模板合成的类似物或拟药［1］.尤其是真菌来源的天然产物，迄今发现的50万个天然产物中，约6～8万个来源于微生物，其中50%具有一定的生物活性［2］.临床应用的抗生素青霉素类（penicillins）、免疫抑制剂环孢菌素（cyclosporin）、降血脂药物洛伐他汀（lovastatin），抗寄生虫药伊维菌素（ivermectin）等均是真菌来源的天然产物或其衍生物，尤其青霉素的研制成功极大增强了人类抵抗细菌性感染的能力，带动了抗生素家族的诞生，开创了人类用抗生素治疗疾病的新纪元.真菌来源的天然产物在药物研究中的广泛应用，为人类健康做出了重大贡献，在很大程度上改变了我们的世界［3］.天然产物结构多样，主要分为苯丙素、醌类、黄酮、萜类以及生物碱等，其中萜类化合物（terpenes）是小分子天然产物中最大的一类化合物，到目前为止已发现超过60 000多种［4］，在生物来源上是一类分子由异戊二烯单元倍数组成的烃类及其含氧衍生物，是一大类具有高度结构多样性的天然产物，根据所含异戊二烯单位数目不同可分单萜（monoterpene）、倍半萜（sesiquiterpene）、二萜（diterpene）、二倍半萜（sesterterpene）、三萜（triterpene）等.许多萜类衍生物，例如青蒿素（artemisinin）、紫杉醇（taxol）等，已被发展为治疗疟疾、癌症以及其他各种人类疾病的重要药物，因此萜类的发现与合成就显得非常的重要. 目前二倍半萜报道的较少，只占萜类总数不到2%，主要分布在植物、真菌、海绵、地衣及昆虫分泌物中，海绵来源占绝大多数［5］.Terpestacin是从真菌分离的二倍半萜类化合物，具有很好的抗癌，抗HIV病毒等生物活性，并且已经展开了较深入的相关工作.为了更系统深刻地了解terpestacin研究进展，本文对其生物活性、生物合成及化学合成等研究进行了综述.在1993年由Bristol-Myers研究所Masahisa Oka等最先在Arthrinium sp.真菌的菌丝体的乙酸乙酯萃取物中分离得到terpestacin（1）［6-7］，该化合物由一个十五元环和一个五元环稠合而成的双环骨架，其中，十五元环上有三个反式三取代双键，同时具有四个手性中心，其中包括一个季碳手性中心，而五元环为官能团密集的 1，2-双酮结构，其中一个羰基呈现烯醇式结构. 该化合物后来又在Cochliobolus sp.［8］、Phomopsis sp.［9］、Embellisia sp.［10］、Ceratostigma griffithii［11］等真菌中有过报道 .有研究也报道过一些terpestacin（1）天然来源的衍生物，11-epi-terpestacin （2）是2002年Nihashi等从Bipolaris sorokiniana NSDR-011的terpestacin 的11位立体异构体［12］.其结构不同之处在于11位碳的手性由R型变成了S型.化合物3是2015年从Ceratostigma griffithii分离到的terpestacin的24位葡萄糖苷化的结构.Terpestacin另外还有24位乙酰化的结构fusaproliferin以及11位羟基进攻7（8）位双键形成的7，11位醚键以及8，11位醚键的fusaprolifins A和B［13］.目前该类化合物通过化学合成已经得到了许多类似物，但对其天然来源的结构仍然需要不断丰富.Terpestacin具有一定的抗癌和抗HIV的活性，并具有良好的生物选择活性，因而作为一种非常有前景的药物的先导化合物受到广泛的关注.目前对其生物活性主要有以下几个方面.血管生成需要内皮细胞重构、新血管生长的一系列过程，是许多生物事件，如生长、繁殖、组织修复的先决条件.然而，病理状态的血管生成却会导致或加重一些疾病，如癌症的生长和转移，糖尿病性视网膜病变，还有风湿性关节炎等［14-15］.实体瘤的形成与血管的生成密不可分［12］，抑制血管生成是抗癌的焦点策略［16-17］.血管内皮生长因子VEGF（vascular endothelial growth factor）是一类相对分子质量介于34 000到46 000的糖蛋白，是非常重要的促血管生成因子.许多肿瘤细胞可以通过分泌VEGF，而VEGF主要通过与受体VEGFR2（VEGF receptor type 2，也被叫作KDR/Flk-1）的相互作用来诱导肿瘤血管的生成［18-19］，为肿瘤细胞提供充足氧气的同时，通过增加大血管的通透性从而协助肿瘤细胞进入脉管系统.研究表明，VEGF的高表达与肿瘤的形成、转移、复发密切相关，而对VEGF通路的抑制是目前一种治疗癌症的强有力策略［20-21］. VEGFR2的激活可以导致特定的下游信号转导效应分子的磷酸化，以及信号调节激酶ERK（signal-regulated kinase）和蛋白激酶Akt的磷酸化，这是VEGF诱导的血管内皮细胞的增殖、迁移和生存是必要条件［22-23］.抑制VEGFR2的激酶活性可以阻碍VEGF通路从而抑制VEGF在ECs中对血管生成的诱导作用，是对癌症非常有前途的治疗方法［14，24-26］.血管的生成对于氧浓度非常敏感.线粒体是细胞的能量工厂，也是氧感受中不可或缺的细胞器线粒体是氧气的消耗位点，所以血管的生成与线粒体的功能相关［27］.UQCRB（Ubiquinolcytochrome c reductase binding protein，人类中为UQCRB；收录号NM_006294；酵母中为QCR7；牛或鸡中为Sub 6），大小为13.4-kDaH.［27-28］，是线粒体复合体Ⅲ的一个亚基，是低氧诱导的感受器，可以通过增加线粒体活性氧ROS （reactive oxygen species）的水平正向调控VEGFR2的水平，从而促进VEGF诱导血管的生成［29-30］.Terpestacin是VEGF通路的抑制剂，体内及体外实验都证明terpestacin可以通过特异性识别并靶定肿瘤细胞线粒体复合体Ⅲ中的UQCRB，导致ROS的降低，从而降低VEGFR2水平并抑制VEGF通路，进而阻碍肿瘤血管的生成，对肿瘤的增殖和转移起到抑制作用［28］是抗癌化学疗法的先驱药物［31］.艾滋病AIDS是由HIV引起的传染性疾病，自1981年Micheal S Gettlieb报道首例AIDS以来，世界各国实验室都在寻求其有效防治的方法［32］，而有效的抗病毒药物仍然迫在眉睫.HIV为逆转录病毒，其靶细胞主要为CD+细胞，特别是CD+T细胞，同时也可侵染CD+细胞如脑细胞、恶性胶质瘤细胞等.HIV侵染成功后，便会逆转录整合到细胞DNA中，而其自我复制产生的新病毒极易出现变异，成为欠缺型病毒，而使得HIV病毒壳里的蛋白质外壳产生变异——这使得杀伤性T细胞的识别变得困难.HIV周而复始的复制逼迫T细胞循环往复产生新的特异性，最终导致机体T细胞的衰竭，免疫系统逐渐崩溃［33］.其中，艾滋病毒HIV的包膜糖蛋白gp-160对于HIV病毒进入细胞的过程至关重要，并且在艾滋病毒感染细胞中表达的gp-120与靶定在人类T细胞的表面抗原CD4的相互作用中起到不可或缺的作用.gp-120与CD4的相互作用通过HIV跨膜蛋白gp-41调节的反结合融合（a post-binding fusion event）完成，从而导致名为syncytium1的多核巨细胞的最终死亡［34］.因此，合胞体形成抑制剂是十分重要的抗艾滋病毒制剂.Terpestacin可以有效抑制导致HIV病灶的细胞合胞体（syncytia）的形成（ID50=0.46 μg/mL），因而在预防AIDS上作为抗病毒制剂而被广泛关注［6-7］.Terpestacin还可以抑制呼吸道合胞体病毒（respiratory syncytial virus，RSV）的合胞体形成［35-36］.Liu dong等开展过terpestacin对Alternaria brassicae，Coniella diplodiella，Fusarium oxysporum，Physalospora piricola等真菌抑制活性研究，但是并未发现明显的抗真菌效果［13］.Liu dong等开展了terpestacin对Staphylococcus aureus，Bacillus subtilis等细菌的抗菌活性的研究，最小抑制浓度MIC值在100 mg/L左右，其抗菌活性并不是十分理想［13］.同样Meca等也未发现fusaproliferin对上述细菌产生很好的抗菌活性［37］.目前对于terpestacin类化合物的生物合成途径研究还比较少.1993年Masahisa等利用同位素标记法将13C标记的醋酸盐饲喂到Arthrinium sp.FA 1744的培养液中，结果分到的terpestacin都被标记，证明该化合物最初都来自于乙酰基；对乙酸乙酯的不同1位和2位碳分别标记，得到了12C与13C交替的产物，证明化合物中乙酰基连接方式是首尾连接的.然后根据核磁数据分析，推测化合物terpestacin来自于甲羟戊酸途径［38］.该研究结果虽然证明了该类化合物来自于甲羟戊酸途径，但是，催化合成过程的酶并未找到.根据现有的研究成果，二倍半萜的生物合成过程总体上分为4步：1）通过甲羟戊酸（MVA）途径合成，五碳单体二甲基丙烯焦磷酸（Dimethylallyl diphosphate，DMAPP）和异戊烯焦磷酸（Isopentenyl diphosphate，IPP）；2）以DMAPP 起始，在异戊烯基转移酶（Prenyltransferases，PT）作用下与4个IPP 首尾连接形成线性聚异戊烯焦磷酸前体，牻牛儿基法尼基焦磷酸（Geranylfarnesyl diphosphate，GFPP）；3）萜类环化酶（Terpene cyclase，TC）对这些焦磷酸前体进行环化或重排形成萜类骨架；4）通过脱水氧化等进一步骨架的修饰得到各种萜类化合物［39］.由于目前为止只报道了3个丝状真菌来源的二倍半萜合成酶和1个改造后的二倍半萜合成酶［40］.对terretonins生物合成酶仍还有待认识，因此只能对该类化合物骨架合成中的环化部分做出推测（图2）.环化部分主要分为三部分，第一步，C1与GFPP中的第4个双键加成（C1-Ⅳ），连接成环；第二步，在第一次成环的基础上碳正离子直接进攻双键形成新环.最后，碳正离子通过脱去相邻碳上的氢离子或者从H2O中获取OH-平衡电荷，完成环化反应.对该类化合物合成酶挖掘与研究可以用来指导二倍半萜天然产物的发现.有利于指导利用代谢工程和合成生物学手段进行二倍半萜化合物的人工合成.由于该类化合物的生物合成酶研究较少，因此后续还有很多路要走.（-）-terpestacin的母核是由五元环和十五元大环通过反式稠合（［3，0，13］双环骨架体系）而形成的二倍半萜类化合物，十五元大环上含有三个反式三取代双键.该分子中有四个手性中心（即C-1，C-11，C-15，C-23）. 五元环为官能团密集的1，2-双酮结构，其中一个羰基呈现烯醇式结构.上述复杂的立体构型特征使得该分子进行全合成具有较大的挑战性.但是由于该分子具有良好的生物活性和结构特点，吸引着许多化学家去完成其合成工作.目前已经有多篇关于其化学合成的报道［41-46］.下面选择其中几篇代表性的报道进行简要综述.1998年Tatsuta等首次报道了全合成了terpestacin，其利用结构简单的二环内酯（bicyclic lactone）合成β-酮内酯（β-keto lactone）同时利用甲基硅烷取代的法尼基醇O-silylated farnesol为原料合成15个碳的侧链，然后两部分利用烷基化反应连接在一起并后续多步反应得到terpestacin［41］.由于该合成过程并未考虑化学立体选择性，所以得到的产物是光学纯度上的混合物.2002年Myers等利用不对称合成首次合了光学纯度的（-）-terpestacin和（-）-fusaproliferin.该课题组利用假麻黄碱（pseudoephedrine amide）经过一系列的立体选择性的烯醇化氢化反应得到构型保持的五元环内酯，并与十五碳的环氧醇侧链结合进一步反应最后得到了化合物吸收率为5.8%的（-）-terpestacin和5.3%的（-）-fusaproliferin［42］.通过CD以及旋光等对化合物的光学纯度进行测定.2012年邱发洋课题组使用的是两种廉价且常见的商业原料左旋香芹酮和全反式-金合欢醇作为起始原料实现了（-）-terpestacin的全合成.其在构建该分子的关键位点如1位的季碳手性中心、11位手性羟基和23位的手性甲基时，使用巧妙简洁的方法，使全合成效率大大提高［46］.由于该合成路线仅涉及简单试剂和常规反应，便于实验室较大规模合成，为针对该化合物的进一步结构改造奠定基础. 虽然邱发洋研究组所研究的合成方法，仅涉及廉价试剂和常规反应，便于实验室较大规模合成，且已经比国际上使用的方法的效果要好很多，但还是需要几万元才能合成1 g产品.目前，如何进一步提高该化合物的合成效率，降低成本，获取更多的生物活性数据和更多的生物学信息，仍然是有机化学家们努力的目标. Terpestacin由于具有独特的化学结构，以及具有抗癌、抗HIV、抗菌和抗病毒等活性，是一个非常有前景的抗癌和抗HIV的先导化合物.目前对其虽然开展了较多的研究，但是其化学合成产率低无法经济低廉地应用于进一步实验中，另外其生物合成酶仍然也没有被报道，所以利用遗传学的方法改造成高产工程菌，通过发酵作为该类化合物的来源也只停留在设想阶段.所以对该类化合物的研究仍然有很多工作要做，最主要的便是经济低廉地获得该化合物.如何高产率地合成光学纯度的terpestacin，以及发掘其生物合成基因，仍需要化学家和生物学家们继续努力.随着对其更加深入的研究，相信该类化合物终将造福于人类健康.【相关文献】［1］NEWMAN D J，CRAGG G M.Natural products as sources of new drugs from 1981 to 2014［J］.Journal of Natural Products，2016，79（3）：629-661.［2］BERDY J.Thoughts and facts about antibiotics：where we are now and where we are heading［J］.Journal of Antibiotics，2012，65（8）：385-395.［3］NICOLAOU K C，MONTAGNON T.Molecules that changed the world［M］.Journal of Chemical Education，2008，86：1372.［4］GUAN Z，XUE D，ABDALLAH II，et al.Metabolic engineering of Bacillus subtilis forterpenoid production［J］.Applied Microbiology&Biotechnology，2015，99（22）：9395-9406.［5］WANG L，YANG B，LIN X P.Sesterterpenoids［J］.Natural Product Reports，2013，30：455-473.［6］IIMURA S，OKA M，NARITA Y，et al.Terpestacin，a novel syncytium formation 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化工进展Chemical Industry and Engineering Progress2024 年第 43 卷第 3 期CeO 2-In 2O 3异质结复合材料的制备及其在三乙胺气敏监测中的应用钟彩丽，莫秋莲，孙建华，丁宁宁，廖丹葵，孙丽霞（广西石化资源加工及过程强化技术重点实验室，广西大学化学化工学院，广西 南宁530004）摘要：以In(NO 3)3∙4.5H 2O 和Ce(NO 3)3∙6H 2O 为原料，对苯二甲酸为配体，N ,N -二甲基甲酰胺为有机溶剂，通过热解金属有机骨架法（MOFs ）成功制备了CeO 2-In 2O 3复合材料。

采用X 射线双晶粉末衍射仪（XRD ）、透射电子显微镜（TEM ）、扫描电子显微镜（SEM ）、紫外-可见漫反射吸收光谱（UV-vis ）和比表面积与孔隙度分析仪（BET ）对材料的微观结构进行表征，研究了CeO 2-In 2O 3复合材料的气敏性能。

结果表明，当In/Ce 摩尔比为3∶1时，CeO 2-In 2O 3对1×105μg/L 三乙胺（TEA ）的响应值（48.37）最高，是纯In 2O 3（9.45）的5倍，响应/恢复时间缩短至36s/22s ，且该复合材料在173℃的最佳工作温度下具有优异的选择性和长期稳定性。

复合材料传感性能的增强可归因于热解金属有机骨架法提供的大比表面积以及n-n 异质结的形成。

关键词：CeO 2-In 2O 3；三乙胺；气敏性能；气敏机理；异质结中图分类号：O649 文献标志码：A 文章编号：1000-6613（2024）03-1446-10Preparation of CeO 2-In 2O 3 heterojunction composites for gas sensingmonitoring of triethylamineZHONG Caili ，MO Qiulian ，SUN Jianhua ，DING Ningning ，LIAO Dankui ，SUN Lixia(Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School ofChemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China)Abstract: CeO 2-In 2O 3 composites were synthesized by pyrolysis metal-organic framework method (MOFs) using In(NO 3)3∙4.5H 2O and Ce(NO 3)3∙6H 2O as raw materials, terephthalic acid as ligand and N , N -dimethylformamide as organic solvent. The microstructure of the obtained materials was characterized by XRD, TEM, SEM, UV-vis and BET. The gas sensitive properties of obtained CeO 2-In 2O 3 composites were studied. The results indicated that when the molar ratio of In/Ce was 3∶1, CeO 2-In 2O 3 to 1×105μg/L triethylamine (TEA) had the highest response values (48.37), which was 5 times that of pure In 2O 3 (9.45), response/recovery time was reduced to 36s/22s, and the composite had excellent selectivity and long-term stability at the optimum operating temperature of 173℃. The increased sensing performance can be attributed to the large specific surface area provided by pyrolytic metal-organic skeleton method and the formation of n-n heterojunction.Keywords: CeO 2-In 2O 3; triethylamine; gas sensitive performance; gas sensitive mechanism; heterojunction研究开发DOI ：10.16085/j.issn.1000-6613.2023-0495收稿日期：2023-03-31；修改稿日期：2023-05-30。