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Recent advances in two-dimensional nanomaterials-based electrochemical sensors for environmental analysis

更新时间:2016-07-05

1.Introduction

Since the discovery of single-layer graphene in 2004,two dimensional(2D)nanomaterials,especial layered nanostructures nanomaterials,received more and more attention due to their unique chemical/physical properties during recent decades,such as boron nitride(BN)nanosheet,graphitecarbon nitride(g-C3N4)nanosheet and various transition metal dichalcogenides(TMDs)[1-3].These 2D nanomaterials generally have large surface area,high chemical stability,easy functionalization,high electrical conductivity and mechanical strength due to their graphene-like structures[4-7].Besides those,other 2D nanomaterials composed of two or more elements led to possess more novel properties.For example,BN nanosheet has superior thermal transport performance[8];molybdenum disulfide(MoS2),one of TMDs family,exhibits excellent hydrogen evolution reaction activities and tuned bandgap[9].Up to now,2D nanomaterials have been successfully applied in sensing,energy,catalysis,imaging and therapy[10-18].To further improve the performance,kinds of functional building blocks like noble metal nanoparticles,metal oxides,and organic compounds were introduced on the surface of 2D nano materials[16,19-25],forming novel nanohybrids with better chemical/physical properties due to their synergistic effect.

Environmental pollution is considered as a worldwide public problem,including heavy metals,inorganic/organic compounds,toxic gases,pesticides,antibiotics,bacteria,etc.,which becomes a serious threat to human health and natural environment[26,27].Therefore,different detection techniques have been developed for monitoring the environmental pollution,such as electrochemistry[28], fluorescence[29,30],chemiluminescence[31],surface-enhanced Raman scattering[32,33],plasma mass spectrometry[34]and so on.Among those methods,the electrochemical sensor for the detection of pollutants greatly attracted scientists'interest due to its remarkable advantages,such as simple,high sensitivity,fast response,low cost and easy integration with portable devices[35,36].To improve the sensitivity and stability of sensors,noble metal nanoparticles[37],metal oxides[38,39],carbon nanotubes[40,41],silicon nanowires[42],and graphene[43,44]have been introduced in constructing electrochemical sensors for pollutions detection.

In this review,we focus on summarizing the recent advances of 2D nanomaterials in environmental monitoring from 2010.We mainly review the development of electrochemical sensors for heavy ions,organic compounds,pesticides,antibiotics and bacteria detection based on graphene-and MoS2-based nanomaterials combined with different detection strategies.

2.Heavy metal ion detection

With industrial development,many metal ions have discharged into the natural environment.Unfortunately,metal ions,especial heavy metal ions,are easily caused soil and water polluted.Moreover,the toxicity of heavy metal ions could result in several diseases even cancers.More and more reports have proved the harmfulness of heavy metal ions pollutions,such as cancer villages.For the purpose of human health,World Health Organization(WHO)have announced guideline values of different metal ions for drinking water(such as 10 ppb Pb2+,6 ppb Hg2+and 2000 ppb Cu2+).Thus,it is very important to develop a rapid,sensitive,and simple analytical method for the detection and monitoring of heavy metal ions pollutants in water and soil.

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To improve the selectivity and sensitivity of antibiotics detection,unique recognition reaction was employed to determine antibiotics[100].Pei and co-workers fabricated an electrochemical aptasensors for kanamycin antibiotic detection by using thionine-decorated graphene and PtCu alloy(Fig.4B).The obtained aptasensor showed a wide linear range(5×10-7-5×10-2μg mL-1)and low detection limit(0.42 pg mL-1)with good selectivity and reproducibility[101].Similarly,Guo and co-workers used graphene-based nanocomoposites to construct electrochemical aptasensor for detection of penicillin.Under optimized conditions,the asprepared aptasensor could detect penicillin in buffer and real sample with accepted results[102].Besides aptasensors,Wei et al.developed an immunosensor for label-free detection of kanamycin based on graphene sheet-nafion/thionine/Pt nanoparticles composite(GS-Nf/TH/Pt).The good electrontransfer ability of graphene and Pt nanoparticles greatly improved the peak current of thionine,leading to good performance of the designed immunosensor for kanamycin detection.On the basis of results obtained in ideal buffer,the proposed immunosensor was applied to determine kanamycin in animal derived foods.Next year,Wei's group constructed graphene-based immunosensor for kanamycin detection(Fig.4C).They found the prepared immunosensor could efficiently determine kanamycin in pork meat sample due to its high sensitivity,selectivity and short analysis time(3 min)[103].

As we know,most of heavy metal ions could be detected at bulk electrodes by anodic stripping voltammetry(ASV)technique.Unfortunately,the poor sensitivity,poor detection limit and high reduction potential limited the application.Therefore,graphene and graphene-like nanomaterials have been introduced into constructed electrochemical sensors to improve the detection performances.Nowadays,Hg(II),Pb(II),Cd(II),Cu(II),Zn(II)and Fe(III)have been simultaneously and individually determined with ultrasensitivity at kinds of 2D nanomaterials-based modified electrodes[45,46].For instance,Wang's group synthesized Cu7S4-Au nanocatalysts supported MoS2nanocomposite as a sensing platform to sensitively and selectively detect Hg(II)by using anodic stripping voltammetric technique.They found the synergistic effects of both Au domains and active edge sites of monolayer MoS2played a vital role in the high-performance for detection of Hg(II)with a limit of detection of 190 nM[47].Huang and co-workers developed a SnO2/reduced graphene-based electrochemical sensor,which could simultaneously and selectively detect four heavy metal ions including Cd(II),Pb(II),Cu(II)and Hg(II).As expectedly,the detection limit of the proposed electrochemical sensor for Cd(II),Pb(II),Cu(II)and Hg(II)were 1.015×10-10M,1.839×10-10M,2.269×10-10M and 2.789×10-10M,respectively[48].Similarly,Chaiyo et al.constructed a graphene-based electrochemical sensor for simultaneous determination of zinc,cadmium and lead using screen-printed carbon.As shown in Fig.1A,the functionalized graphene-based nanocomposite modified electrode showed better detection performance for Zn(II),Cd(II)and Pb(II)than bare electrode by square wave anodic stripping voltammetry.The detection limits of such sensors for Zn(II),Cd(II) and Pb(II) detection were 0.09 ng mL-1,0.06 ng L-1and 0.08 ng L-1,respectively[49].The proposed electrochemical sensor was also used to determine trace metal ions in drinking water samples with accepted results,which was comparable to that obtained by plasma mass spectrometry.

Besides direct detection,specific interaction between heavy metal ions and other compounds was employed to determine heavy metal ions selectively.For example,Mao's group utilized cysteamine-functionalized graphene oxide as detection platform to detect mercury ion(Hg2+).As shown in Fig.1B,the mercapto groups of cysteamine selectively interact with Hg2+,making the designed strategy could detect as low as 3 nM(0.6 ppb)Hg2+with high selectivity[50].Inspired by the exciting strategy,several interesting detection strategies were developed for Hg2+detection based on the specific interaction,such as thymine-Hg2+-thymine(T-Hg2+-T)coordination chemistry[51]and polypyrrole-Hg2+interaction[52].Zhang and co-workers constructed an ultrasensitive electrochemical for the detection of Hg2+based on THg2+-T coordination chemistry.On the basis of nanoAu amplification,the developed sensor could detect 0.001 aM Hg2+with high selectivity.As expectedly,the analysis results of three different environmental samples by the graphenebased sensor was comparable to that from an atomic fluorescence spectrometry[53].Using the same interaction,Zhou's group developed a label-free sensing strategy for Hg2+detection in drinking water based on three-dimensional reduced graphene oxide and chitosan particles(CS@3D-rGO,Fig.1C).Under the optimal condition,the obtained biosensor exhibited low detection limit with high repeatability and selectivity,which could determine Hg2+in tap water and river water samples[54].Another interesting interaction between DNAzyme and heavy metal ions was also employed to environmental monitoring.As shown in Fig.1D,Zhang's group immobilized both ion specific DNA and DNAzyme on amino-functionalized reduced graphene oxide modified electrode to selectively detect Pb(II)and Hg(II).Due to the specific interaction of T-Hg2+-T and DNAzyme-Pb2+,the constructed sensor could determine as low as 7.8 pM Pb2+and 5.4 pM Hg2+,respectively[55].

3.Detection of organic compounds

Fig.1.(A)Schematic illustration of graphene-based modified electrode for Zn(II),Cd(II)and Pd(II)detection.(B)Schematic illustration of the reaction procedures for Hg2+determination.(C)Schematic diagram of Hg2+detection using the developed electrochemical biosensor based on CS@3D-rGO@DNA nanocomposite.(D)Schematic of Pb2+and Hg2+detection using the electrochemical biosensor based on amino-modified reduced graphene oxide(NH2-rGO).

The discharge of organic compounds has caused increasing problems in the past decades.Nowadays,they are spreading all over the world,including soil,water and atmosphere.They accumulate in plants or animal body due to the difficult degradation of organic compounds,which could do harm to natural environment and human health.For example,catechol(1,2-dihydroxybenzene,CC)is a phenolic compound which is extensively used in dye,petroleum refinery,plastic,antioxidant,cosmetics,medicines,pesticides,and photography.The high toxicity and low degradability cause eczematous dermatitis,depression of the central nervous system(CNS)and a prolonged rise of blood pressure with the increasing doses of CC.Therefore,accurate,sensitive,fast and low-cost detection of organic compound is very meaningful to environmental monitoring and human health.

Besides S.aureus and E.coli,other bacteria were also sensitively and selectively determined by 2D nanomaterialsbased electrochemical sensors,including genus Shewanella[107],Staphylococcus arlettae[108],marine pathogenic sulphate-reducing bacteria[109],Salmonella pullorum[110],Enterobacter sakazakii[111],Salmonella[112],Mycobacterium tuberculosis[113]and so on.Like S.aureus detection,several detection strategies have been successfully applied to determine these bacteria,such as direct detection,label-free detection and amplification detection.As shown in Fig.5C,Wen et al.constructed a graphene-based nanoamplifier to ultrasensitively detect Shewanella oneidensis based on a classical sandwich-type immunosensor.The effect of silver enhancement strategy,the designed immunosensor showed an excellent analysis performance for S.oneidensis detection with a detection limit of 12 cfu mL-1.They also used the immunosensor to detect S.oneidensis in water samples and obtained accepted results[107].

Fig.2.(A)Illustration of MoS2-based electrochemical sensors for catechol detection.(B)Illustration of graphene-based electrochemical sensors for simultaneous detection of catechol and hydroquinone.(C)Illustration of graphene nanoribbon-supported PtPd concave nanocubes for electrochemical detection of TNT.(D)Illustration of graphene-based electrochemical sensors for phenols detection.

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Up to now, many nanomaterials have been employed to construct electrochemical sensors for pesticides detection, such as noble metal nanoparticles, metal oxides, carbon nanotubes, silicon nanowires and so on [41,42,77]. Like them, sensing platforms were also extensively developed based on 2D nanomaterials for pesticides detection with enzyme-assisted or nonenzyme. As shown in Fig. 3A, Lin and co-workers assembled AChE on gold nanoparticles-chemical reduced graphene oxides nanosheets (AChE/AuNPs/cr-Gs) to detect organophosphate pesticide. The experimental data showed only 0.1 pM paraoxon could apparently inhibit the catalysis activity of AChE to acetylthiocholine (ATCh) [78]. In 2014, the same group utilized graphene-based nanocomposite to rapidly and sensitively detect paraoxon-ethyl [79]. In 2016, Moga et al. immobilized AChE in zirconium oxide-decorated reduced graphene oxide nanohybrid to determine chlorpyrifos. They found the proposed sensor could detect as low as 10-13Mchlorpyrifos(with 28%enzyme inhibition)[80].Using the same detection strategy,many pesticides have been determined by electrochemical sensors,such as dichlorvos[81],methyl parathion[82],carbofuran[83],triazophos[84],carbaryl[85],etc.

Other organic compounds also have been determined by 2D nanomaterials-based electrochemical sensors, such as p-dihydroxybenzene [69], nitromethane [70], 4-chlorophenol [71], 4- nitrophenol [72], honokiol [73], bisphenol A [74,75]and so on.As shown in Fig. 2D, Wu et al. used one-step N-methyl-2- pyrrolidone (NMP) exfoliated graphene nanosheets as a sensing platform for phenols detection, including hydroquinone, catechol, 4-chlorophenol, and 4-nitrophenol. Such NMP-exfoliated graphene nanosheets showed better electrocatalytic activity toward the oxidation of phenols than that obtained by multistep chemical oxidation[71].The developed sensing platform could determine as low as 0.012 μM,0.015 μM,0.01 μM,and 0.04 μM for hydroquinone,catechol,4-chlorophenol,and 4-nitrophenol,respectively.Huang and co-worker used layered MoS2-graphene composite as sensing platform for acetaminophen detection.The robust composite structure and the synergistic effect of MoS2and graphene brought the developed sensor excellent detection performance,which could detect as low as 2.0×10-8M acetaminophen(S/N=3)[76].

A kind of dangerous nitroaromatic compound was also detected by electrochemical sensors based on 2D nanomaterials, which greatly related with public security, human health and environmental protection. For example, Chen's group found that PtPd concave nanocube-decorated graphene nanocomposite modified electrode had higher current signal for 2,4,6-trinitrotoluene (TNT) detection than graphene nanoribbons and bare electrode (Fig. 2C). As expectedly, the obtained electrochemical sensor exhibited a wide linear range from 0.01 to 3 ppm and low sensing limit of 0.8 ppb for TNT detection [63]. Similar detection strategy has been used for TNT detection by several groups, including Wang's [64], Pumera's [65], Yang's [66] and Xia's groups [67]. As mentioned above, kinds of explosives could be determined at graphene or graphene-based nanocomposites modified electrodes, such as 2,4-dinitrotoluene (2,4-DNT), 1,3- dinitrobenzene (1,3-DNB), and 1,3,5-trinitrobenzene (TNB). Guo et al. used porphyrin functionalized graphene modified electrode to monitor nitroaromatic explosives, which could detect as low as 1 ppb of 2,4-DNT, 0.5 ppb of TNT, 1 ppb of TNB and 2 ppb of 1,3-DNB, respectively [68]

4.Detection of pesticides

Pesticides pollution,especially organophosphorus pesticides,is seriously harmful to human health and animal survive due to their high insecticidal activity,which mostly generates from agricultural activity.Generally,pesticides easily accumulate or leave in vegetables and fruits,leading to potentially harmful to consumers.They may cause negative effect on the function of human body and even death via inhibition of acetylcholinesterase(AChE)activity.Therefore,development of simple,rapid,low-cost and user-friendly detection method attracted more and more attentions.

Fig.3.(A)Schematic illustration of AChE/AuNPs/cr-Gs nanoassembly generation by using PDDA for pesticide detection.(B)A reliable and robust methyl parathion sensor has been developed using heterostructured MoS2/graphene.

黎曼猜想在整数分布中的一个应用···························李宇芳 姚维利 (6,1014)

To avoid the negative effect of AChE activity,nonenzymatic electrochemical sensors have been developed for the detection of pesticides based on 2D nanomaterials due to their stability.For example,Wang and co-workers developed a nonoenzymatic electrochemical sensor for carbofuran(CBF)and carbaryl(CBR)detection based on cobalt(II)oxidesupported reduced graphene oxide (CoO/rGO) nanocomposite.Such nonenzymatic sensor could efficiently avoid the disadvantageous of AChE-based sensors,which showed a remarkable enhancement in electrocatalytic ability for CBF and CBR oxidation.The proposed sensor could simultaneously determine CBF and CBR with high sensitivity,selectivity and stability.More importantly,the detection results of fruit and vegetable samples obtained by the developed electrochemical sensor were comparable to that of high performance liquid chromatography(HPLC)[86].Chen's group also designed another nonenzymatic electrochemical sensor for organophosphate pesticides detection based on MoS2-graphene nanocomposite(Fig.3B).The synergetic effect of MoS2and graphene nanosheet facilitated the enrichment of methyl parathion(MP)onto the surface,resulting in a low detection limit of 3.2 nM.The nonenzymatic sensor showed accepted recoveries of MP detection in homogenized apple,kiwi,cabbage and tomato samples[87].Similarly,isoproturon,carbendazim,methyl parathion,ethyl parathion,fenitrothion,and paraoxon were also sensitively determined by graphenebased nonenzymatic electrochemical sensors[88-90].

5.Detection of antibiotic

Antibiotic is considered as a kind of serious pollution due to its abuse in human and animal growth.As we know,antibiotic is often employed to treat diseases and promote animal growth.However,antibiotic gradually residues in food products,drinking water and environment with the abuse,resulting in negative effect on human health,such as hearing loss,toxicity to kidneys,poordiseasestreatmentand even antibiotic-resistant bacteria.Therefore,reducing and monitoring the use of antibiotics is extremely important to protect human health and safety.

For the purpose,several electrochemical active antibiotics were monitored and detected by electrochemical technique,such as metronidazole,chloramphenicol[91],midecamycin[92],azithromycin[93],penicillin[94],linezolid[95],tetracycline[96],levofloxacin[97]and ofloxacin [98].For example,Zhang and co-worker directly detected metronidazole based on silver nanoparticles-decorated petal-like graphene nanohybrid(Fig.4A).The designed sensor showed a good detection performance with a low detection limit of 28 nM(S/N=3),which was applied to detect metronidazole in human urine and local lake water samples.Furthermore,they also discussed the mechanism and the electron transfer kinetics constant of the electrochemical reaction process[98].Besides graphene,Chen et al.used MoS2/polyaniline nanocomposite as an electrochemical sensing platform to determine chloramphenicol.The synergistic effect of MoS2and polyaniline made the developed sensor possess excellent detection performance,exhibiting a wide detection range from 1×10-7M to 1×10-4M with a low detection limit of 6.9×10-8M[99].

(1) 本文以甘肃省华池县为研究区,基于地质灾害详细调查数据,分析了对区内地质灾害发育起控制作用的各个因素,从内因与外因综合考虑,选定了地形地貌、地质构造、工程岩组、水系、降雨、植被覆盖率和人类工程活动7个指标构建本区易发性评价指标体系。

Fig.4.(A)Schematic diagram of the kanamycin aptasensor.(B)Schematic illustration of the stepwise procedure for the fabrication of the immunosensor.(C)Scheme for the preparation process of p-GR-Ag/GCE for electrocatalytic reduction of metronidazole.

本文对旧混凝土路面共振碎石化技术进行了介绍,对路面的弯沉进行了分析,对碎石化的级配进行比较,得出了相应的结论。同时还对碎石化路面的加铺沥青路面的类型进行不同情况的分析,介绍了可参考的方案。旧混凝土路面共振碎石化技术是一种多面技术的综合体,包含旧水泥混凝土破碎效果、路面的弯沉、回弹模量、地基的强度、投资的成本等众多因素,必须依靠当地的基础资料,全面、合理、科学地确定方案,才能丰富完善旧混凝土路面共振碎石化技术。

6.Detection of bacteria

Microbiological contamination,especial bacterial pollution,has attracted more and more attention because it can cause food and water-borne diseases.More importantly,bacteria proliferate fastly in a suitable environment,resulting in serious infection.Forexample,Staphylococcus aureus(S.aureus)is a gram-positive bacterium,which disturbed in air,water and perishable food.A certain amount of S.aureus would cause a wide range of diseases,such as food poisoning toxic shock syndrome,gastrointestinal tract infections and septicemia.Therefore,bacterial pollution monitoring with simple detection method is beneficial to human health.

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The authors declare no competing financial interests.

Fig.5.(A)Response mechanism diagram of proposed sensor for S.aureus detection.(B)Schematic representation of the preparation of sulfonated graphene-poly-(3,4-ethylenedioxythiophene)-gold nanoparticles(SG-PEDOT-AuNPs)modified electrode for sensitive detection of E.coli O157:H7.(C)Schematic representation of the procedure of the electrochemical immunoassay for Shewanella oneidensis detection.

Gram-negative bacteria were also sensitive detected by electrochemical sensors based on 2D nanomaterials.For example,Ying's group constructed a label-free impedimetric immunosensor for Escherichia coli O157:H7 using gold nanoparticles supported graphene paper.The immobilization of anti-Escherichia coli O157:H7 antibody could efficiently and selectively capture target bacterial,resulting in a low detection limit of 1.5×102cfu mL-1with excellent specificity[106].To enhance the detection performance,signal amplification strategies were gradually employed to determine bacteria.Wang and co-worker developed an electrochemical immunosensor assay for E.coli O157:H7 detection based on sulfonated graphene decorated gold nanoparticles.As shown in Fig.5B,a classical sandwich-type immunosensor was formed in the presence of E.coli O157:H7.Combined with the advantages of graphene-gold nanoparticles nanocomposite and signal amplification effect,the designed immunosensor showed a wide linear range from7.8×10to 7.8×106cfu mL-1and a low detection limit of 34 cfu mL-1.Furthermore,the proposed immunosensor had evaluated by synthetic samples for detection of E.coli O157:H7[57].

2D nanomaterials have been extensively employed to construct electrochemical sensors for organic compounds detection,such as graphene and MoS2[56-58].To improve detection performance, Wang's group used different noblemetal nanoparticles-supported MoS2nanocompositesas sensing platform for CC detection.As shown in Fig.2A,the detection performance of gold-platinum core-shell nanoparticles decorated MoS2nanosheet(MoS2-Au@Pt)modified electrode was better than that obtained at pure MoS2nanosheet,gold nanoparticles-and platinum-decorated MoS2 nanosheet modified electrodes due to their synergistic effect.The MoS2-Au@Pt modified electrode showed wide linear range from 2 to 1000 μM and low detection limit of 0.44 μM,which could determine CC in river water and local tap water samples with accepted results[59].Similarly, many graphenebased nanomaterials also were used to determine CC with high sensitivity, such as reduced graphene oxide [60], silver nanoparticles polydopamine-graphene [61], gold nanoparticlesgraphene [62], etc. It should be noted that catechol and hydroquinone (HQ) often co-exist because they are two dihydroxybenzene isomers. It is difficult to simultaneously determine CC and HQ due to their overlapping peaks at ordinary electrode. Therefore, 2D nanomaterials-based electrodes pave a way to detect them simultaneously. For example, Ma et al. developed a gold-graphene nanocomposite modified electrode, which could efficiently distinguish CC and HQ using cyclic voltammetric (CV) method (Fig. 2B) [62]. Besides two isomers, Ai and co-workers prepared a graphenechitosan composite modified electrode, which possessed excellent electrocatalytic ability towards the oxidation of CC, resorcinol (RS) and HQ. The enough peak-to-peak potential separations made the proposed electrochemical sensors simultaneously determine CC, RS and HQ with high sensitivity and reproducibility, which could apply to detect CC, RS and HQ in local tap water, river water, lake water and sanitary wastewater samples with satisfactory results.

7.Conclusions and perspective

Nowadays,great advances of 2D nanomaterials have been achieved to address the environmental challenges.The unique properties of graphene-and MoS2-based nanocomposites offer new candidates to construct better electrodes for environmental monitoring studies.Though obtained such exciting progress,it still has many challenges to be faced.First,synthesis of novel functionalized graphene-and MoS2-based nanocomposites with better performance is still a challenge.Second,integration of detection strategies for detection of multiplexed target pollutions could efficiently maximize the use of graphene-and MoS2-based electrochemical sensors.Third,it is urgent to development of low-cost,portable and integrated detection devices with mobile phone for real-time and on-site detection.It can be foreseen that commercial 2D nanomaterials-based devices would be on the market in future.

Conflict of interest

As shown in Fig.5A,Lian et al.developed a fast electrochemical sensor for S.aureus detection based on aptamer and graphene.The S.aureus aptamer was used as biological recognition element to guarantee the selectivity of the designed sensor.As expectedly,the constructed sensor showed an excellent detection performance with a low detection limit of 41 cfu mL-1,which was applied to determine S.aureus in milk samples[104].Similarly,Wang's group constructed an impedimetric aptasensor for S.aureus based on gold nanoparticles-decorated graphene oxide.The synergistic effect of graphene oxide,gold nanoparticles and S.aureus aptamer improved the detection capability,resulting in lower detection limit(10 cfu mL-1)than some published works[105].

(数码照片)并非单一的、不容争辩的比人类记忆更真的指示物,在相互支持或矛盾的图像、声音与文本之网中,它能充当一种要素,也可以是一份可能的诠释的菜单,一场可塑的梦境和一块记忆的磁铁。在数码环境里,一张照片可以轻易链接到当天的报纸头条(当地的或全球的),也可以链接到天气预报、日记和日程簿,或家庭其他成员乃至任何人的照片与文字。最重要的是,他人也能链接到这张照片,增强或反驳其初始作者宣称的含义。这真是Web2.0的中心原则。整体来看,这张照片生长出电子的根与枝,反过来,又被其他媒介缠绕其中。[1]56

1.3 统计学分析 数据采用SPSS 22.0统计学软件对数据进行分析,计量资料呈正态分布,数据用均数±标准差表示,组间比较采用独立样本t检验,同组治疗前后比较用配对样本t检验。相关性采用Pearson相关分析法,P<0.05为差异有统计学意义。

Acknowledgements

This work funded by the National Natural Science Foundation of China(61671250,21475064,21373260 and 21305070),the Ministry of Science and Technology of China(2013CB933802),Natural Science Fund for Colleges and Universities in Jiangsu Province(16KJB150032)and the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,YX03002).

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《Green Energy & Environment》2018年第2期文献

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