爱丽丝梦游仙境英语专业论文

第一篇：爱丽丝梦游仙境英语专业论文

Alice adventures in wonder land 主要内容

《爱丽丝奇境历险记》讲述了小姑娘爱丽丝追赶一只揣着怀表、会说话的白兔，掉进了一个兔子洞，由此坠入了神奇的地下世界。在这个世界里，喝一口水就能缩得如同老鼠大小，吃一块蛋糕又会变成巨人，在这个世界里，似乎所有吃的东西都有古怪。她还遇到了一大堆人和动物：渡渡鸟、蜥蜴比尔、柴郡猫、疯帽匠、三月野兔、睡鼠、素甲鱼、鹰头狮、丑陋的公爵夫人。兔子洞里还另有乾坤，她在一扇小门后的大花园里遇到了一整副的扑克牌，牌里粗暴的红桃王后、老好人红桃国王和神气活现的红桃杰克（J）等等。在这个奇幻疯狂的世界里，似乎只有爱丽丝是唯一清醒的人，她不断探险，同时又不断追问“我是谁”，在探险的同时不断认识自我，不断成长，终于成长为一个“大”姑娘的时候，猛然惊醒，才发现原来这一切都是自己的一个梦境。

《爱丽丝穿镜奇幻记》讲述的是小姑娘爱丽丝刚下完一盘国际象棋，又对镜子里反映的东西好奇不已，以致穿镜而入，进入了镜子中的象棋世界。在这里，整个世界就是一个大棋盘，爱丽丝本人不过是这个棋盘中的一个小卒。小姑娘从自己所处的棋格开始，一步一步向前走，每一步棋都有奇妙的遭遇：爱丽丝会脚不沾地地飞着走路，那里的花朵和昆虫都会说话，白王后变成了绵羊女店主，她手中的编织针变成划船的桨，等等。镜中的故事大多取材于英国传统童谣，作者通过自己的想象加以展开，并详细叙述，童谣里的人和物活灵活现地呈现在读者面前：为一丁点儿小事打架的对头兄弟，行止傲慢的憨蛋和为争夺王冠而战的狮子和独角兽。看来只有发明家兼废品收藏家白骑士无法归类，但他恰好是作者本人的化身。等到爱丽丝终于走到第八格，当了王后之后，为所有这些人准备了一次盛大的宴会，宴会上的烤羊腿会鞠躬，布丁会说话，盛宴最终变成了一片混乱，忍无可忍的爱丽丝紧紧捉住摇晃的红后最后变成了一只小黑猫，爱丽丝也在摇晃中醒来，开始追问这到底是自己的梦呢，还是红国王的梦？ 作者介绍

刘易斯·卡罗尔（Lewis Carroll），原名查尔斯·路德维希·道奇逊，与安徒生、格林兄弟齐名的世界顶尖儿童文学大师。原名查尔斯·路德维希·道奇逊。1832年1月出生于英国柴郡的一个 牧师家庭，1898年卒于萨里。曾在牛津大学基督堂学院任教达30年之久，业余爱好非常广泛，尤其喜爱儿童肖像摄影。他的第一本童书《爱丽丝奇境历险记》于1865年出版，当时就引起了巨大轰动，1871年又推出了续篇《爱丽丝穿镜奇幻记》，更是好评如潮。两部童书旋即风靡了整个世界，成为一代又一代孩子们乃至成人最喜爱的读物。

如果说刘易斯·卡罗尔因为这两部童书而被称为现代童话之父，丝毫没有夸大的成分。至少他的两部《爱丽丝》一改此前传统童话（包括《安徒生童话》、《格林童话》）充斥着杀戮和说教的风格，从而奠定了怪诞、奇幻的现代童话基调。仅从这点来说，就堪称跨时代的里程碑。故事简介

Alice, sitting with her sister, is bored.A White Rabbit scurries by, muttering to himself and pulling a watch from his waistcoat pocket.Curious, Alice follows the animal down a rabbit hole, the first of many instances in which she is propelled by her curiosity.Alice falls, landing in a pile of leaves.She finds herself in a hall and discovers a tiny key to a tiny door leading to a garden.She drinks from a bottle labeled DRINK ME, and shrinks down to ten inches tall.Too short to unlock the garden door, Alice begins to cry.She eats some cake, grows unusually tall, then fans herself and becomes exceedingly small.She finds herself swimming in a pool of her own giant tears.A group of animals gathers around her on the shore.A Mouse gives a speech and then a foot race ensues.Alice is soon left alone and begins to cry again.The White Rabbit approaches.Thinking Alice is his housemaid, he sends her on an errand to fetch some things from his house.Alice drinks from a bottle she finds inside and grows until she fills the house, spilling out windows and bumping her head against the ceiling.Frightened, the Rabbit and his friends throw pebbles at Alice.The pebbles become cakes, which Alice eats to shrink.She escapes and meets a Caterpillar sitting on a mushroom, smoking.While he questions her identity and learning, Alice experiments with eating parts of the mushroom to alter her height.After a brief conversation with a Pigeon, she visits the highly

peppered house of the ill-tempered Duchess and encounters the Cheshire Cat, traveling next to the house of the March Hare.Here the Hare, the Mad Hatter, and the Dormouse have tea.Confused, she leaves the party in disgust and finds her way to the garden she could not reach earlier.In the garden, Alice encounters a very curious croquet game and a Queen of Hearts who threatens to chop off everyone's heads.Alice talks with the moralizing Duchess until the Queen threatens to execute the woman.At the Queen's orders, a Gryphon leads Alice to the Mock Turtle.She listens to his life story and his instructions for dancing the Lobster

Quadrille.The two creatures ask Alice to recount her own adventures, which she does, until a Trial is announced in the distance.The Trial concerns some tarts stolen from the Queen.When she is called to the witness stand, Alice begins to grow again and knocks over the jury box.The King orders her to leave the court because of her height.She refuses and continues to grow as the White Rabbit introduces more evidence.The Queen threatens to chop off Alice's head.Having grown to her full size, Alice calls the Queen and her soldiers a mere deck of cards, at which point the entire pack of them rises up and flies down upon her.Alice awakes.Her sister is brushing off some leaves from Alice's face.She recounts her Adventures and runs off.Her sister watches Alice and begins to dream herself, imagining that the White Rabbit rushes by through the grass.梗概：Alice's Adventures in Wonderland(commonly shortened to Alice in Wonderland)is an 1865 novel written by English author Charles Lutwidge Dodgson under the pseudonym LewisCarroll。[1]It tells of a girl named Alice who falls down a rabbit hole into a fantasy world(Wonderland)populated by peculiar, anthropomorphic creatures.The tale plays with logic, giving the story lasting popularity with adults as well as children.[2] It is considered to be one of the best examples of the literary nonsense genre,[2][3] and its narrative course and structure have been enormously influential,[3] especially in the fantasy genre.

第二篇：英语专业论文

英语专业文学方向本科毕业论文写作问题探究

[摘 要]英语毕业论文由于从事英美文学教学的教师理论水平参差不齐、教师对学生文艺理论接受能力的怀疑、商品经济时代文学和文艺理论曲高和寡等因素,造成文学学习和文学方向毕业论文写作中缺乏科学的分析方法。本研究将探索将文艺理论引入本科毕业生的论文写作课程中的必要性和可行性,从而建构以文艺理论为中心的英语专业文学方向毕业论文写作的新模式。

[关键词]文学理论;读者反映理论;认知教学法

依据《高等教育法》(1998)的本科教育学业标准,学生应比较系统地掌握本专业所必需的基础理论知识、基本技能和相关知识,并“具有从事本专业实际工作和研究工作的初步能力”。这一标准强调了研究性教学(research-oriented teaching)的重要性,无疑为英美文学教学中理论研究与实践的有机融合提出了要求,而这种融合往往体现在学生文学论文写作的能力之中。然而,高校中实用主义风气、急功近利思想和“重技能,轻人文”弊端的集中体现冲击着文学课教学,助长了学生轻视与人文修养有关的课程,助长了他们对文学作品敬而远之的倾向(马爱华, 2006)。作为全面考核毕业生综合素质的有效途径,毕业论文写作是本科学生毕业前必须经受的考验关口,是师生教学相长的过程。本文将从文学课教学的现状出发,通过毕业论文写作的过程,在揭示现象、总结经验的基础上,提出重视文艺理论的教学,提高学生的文学素养,培养研究性学习能力的意义。

一、研究现状

部分专家认为英语专业(张冲, 2003)是“英语语言技能的专业训练和对英语语言文化的专门研究”,其特征为“技能加专业,复合而开放”,其培养目标为“纯熟的语言能力,深度的专题研究”。这一专业定位除了强调语言技能之外,着重强调了“文化”和“研究”。文化理解和专题研究的基础在于学生文学课程的给养过程,其中,文学理论分析则既指导了文学课程的学习,又加深了学生对文学作品的理解。文学作品的学习与文艺理论的关系好比材料和工具的关系,“工欲善其事,必先利其器”,如果学生没有相关的文艺理论的学习,就好比一个没有工具的工匠,只能望天兴叹。

二、问题成因

文艺理论是学习英美文学的分析和鉴赏工具,研究生阶段的文艺理论教学已经有了一定的历史,但在英语专业本科教学中文艺理论的教学目前尚未展开。这直接导致学生的文学毕业论文的写作难度增大,出现了许多亟待解决的问题。主要成因如下:

1.从事英美文学教学的教师理论水平参差不齐。部分教师讲授英美文学,而其自身很少涉及文艺理论的使用,或者说自己的文学批评理论知识匮乏,因此不可能在授课时有意识地将文艺理论融入到教学中去。

2.轻视或放低对学生的人文素质和评析能力的生成要求。有些教师担心学生的接受能力,甚至害怕因为学生不能正确理解文艺理论的精髓而将其误用或者滥用。《高等学校英语专业英语教学大纲》(2000)明确规定了文学课程的教学目的“在于培养学生阅读、欣赏、理解英语文学原著的能力,掌握文学批评的基本知识和方法。通过阅读和分析英美文学作品,促进学生语言基本功和人文素质的提高,增强学生对西方文学及文化的了解”,显而易见,加大文学批评理论的讲授和研讨是符合《大纲》要求的。

3.所学知识与研究性写作存在三个“不和谐”关系:文学课的教与学脱节;文学课与语言实践脱节;文学教学理论的研究与外语教学实践脱节(马爱华, 2006)。学生习得的知识孤立于其写作实践之外。人才培养目标不明确,学生急功近利,一成不变的文学课程教学脱离实际人才

培养模式。学生将文艺理论视为纸上谈兵。因而,导致“文学理论教材和教学实践逐渐偏离当今消费时代的审美精神”以及“文学理论的教学被大学生们冷落”(李迪江, 2002)。

三、文艺理论在文学论文写作中的意义

1.文学理论的专业知识学习,铺垫了文学论文的研究能力。“文学理论教学应该优先地培养大学生的理论素养,更多地培养大学生的应用能力,如从文学作品的分析讨论中,来培养大学生的理解能力、分析能力和表达能力等(李迪江, 2002)”。本科学生已经有了一定的文学常识,至少对于著名作品的情节有了一定程度的了解,文学名著选读课使用文学名著的原版书籍作为教材,使得学生有机会对文学文本进行仔细研读,为文艺理论的学习奠定了基础。

2.毕业论文写作,完成学生从读者到理论分析的升华。Guerin认为,“读者参与在文本的创作中”。作品的意义是文本和读者相互作用的结果,它强调读者在阅读过程中的不同参与方式。这一理论代表人物之一伊瑟尔指出,所有文学篇章都有“空白”或“缺口”,这些空白和缺口必须由读者在解读过程中填补或具体化(刘辰诞, 1999)。文学作品须由接受者内化和心灵化,即需要接受者的理解、体验、加工、补充和创造,融入接受者的思想和情感、倾向和评价,只有这样,作品中的时间、人物形象等才会活生生地呈现在自己的头脑中(郭宏安, 1997)。从这个角度暴露了英语专业教育中一贯的“知识单一和技能单一”问题,带来的思考是应该如何培养学生多种语言技能,满足其独立学习的需要。

3.文学史学习为文艺理论的学习奠定基础。心理学、原型批判、女权主义、马克思主义的文学评论等可将传统文学史中作家、作品按照时间排序的方式打破。从各种文艺理论的角度对作家、作品重新排序,不同的文学作品可以用相同的文艺理论进行分析,既起到梳理文学史和文学作品的目的,又使学生对文学作品甚至文学史的认识提升到一个新的高度。如:莎士比亚的《哈姆雷特》,尤金?奥尼尔《榆树下的欲望》,劳伦斯的《儿子与情人》等作品中都蕴含着恋母情结的心理学分析。以此为基础,给学生补充讲述古希腊剧作家索福克里斯的著名悲剧作品《俄狄浦斯王》,能帮助学生探究作品人物的内心世界,为论文写作奠定基础的同时,也有助于选择一个更为可行的题目。

4.结合文本与文艺理论,丰富学生的论文选题。学生文学专业毕业论文选题往往单一,如选择:《伟大的盖茨比》中美国梦破灭的主题或美国梦的悲剧一类的主题;《呼啸山庄》、《傲慢与偏见》中的爱情主题等。选择经典作家的代表作品为研究对象并不是不可以,但对于一般本科生而言,要就这些作品的某一方面进行较为深入、有创意的探讨,还是有相当难度的。因为,对于某一经典文本的某些问题,国内外评论界可能早有定论,而一般的学生“尚不能用当代文论的新视角去解读,很难提出自己的新解”(杜志卿, 2005)。

5.研读诗歌,理论先行。在历届本科英语专业毕业生的论文中,有关诗歌的论文很少有人涉及。究其成因,主要是在较短篇幅的诗歌中大量运用意象和象征等写作手法,再加上诗人用特有的音韵感和

第三篇：英语专业论文题目参考

英语专业论文题目

语言与语言学类

001 从历史文化的发展看某个英语词或短语的语义演变

002 英诗中常用的修辞

003 英语谚语的修辞手法

004 委婉语种

005 英语中的缩略语

006 英语词汇中的外来语单词

007 英语新词新意探究

008 美国英语的特色

009 如何正确把握英语定语从句（或其他各种从句或语法形式）在句子中的确切含义

010 Fuzzy Words and Their Uses in Human Communication

011 Ambiguity and Puns in English

012 Some basic consideration of style

013 English by Newspaper

014 English Personal Pronouns: a Preliminary Textual Analysis

015 Thematic Network and Text Types

016 An Inquiry into Speech Act Theory

017 On Lexical Cohesion in Expository Writing

018 The Inferences of Conversational Implications

019 Context and Meaning

020 The Construction and Interpretation of Cohesion in Texts 语言教学类

001 扩大词汇量和提高英语阅读能力的关系

002 提高英语阅读速度的主要障碍

003 英语阅读能力和阅读速度的关系

004 通过扩大知识面提高英语阅读能力

005 如何在阅读实践中提高英语阅读能力

006 阅读英文报刊的好处

007 如何处理精读和泛读的关系

008 如何对付英语阅读材料中的生词

009 如何通过阅读扩大词汇量

010 提高阅读能力和提高英语听力的关系

011 英语听说读写四种技能的关系

012 通过英语阅读提高英语写作能力

013 英语快速阅读能力的构成成分

014 中学生英语自主学习能力的培养

015 英语教学中的语言焦虑及解决策略

016 简笔画-英语教学中简单高效的教学手段

017 提高英语听力理解能力的策略和技巧

018 电子辞典与英语教学

019 普通话对英语语音的迁移作用

020 母语迁移在基础教育各阶段中的作用

021 提高大班课堂教学的效果

022 《英语课程标准》研究

023 口语教学中教师的角色

024 从心理学角度探讨少儿英语教学

025 英语课堂提问的策略研究

026 英语后进生产生的原因以及补差方法研究

027 英语词汇教学方法探讨

028 小学生英语口语能力评估方法研究

029 朗读在英语教学中的作用

030 任务型教学法研究

031 方言对学生英语语音的影响

032 英语阅读课堂教学模式探讨

033 英语课堂的合作学习策略研究

034 中学生英语学习策略的培养

035 探究式教学法在中学英语教学中的应用

036 现代信息技术在英语教学中的应用

037 教师教学行为对高中生英语学习的影响

038 实施成功教育减少两极分化

039 小学英语活动课教学模式研究

040 中学英语听力训练最佳方案

041 原版电影与英语学习

042 中学生英语兴趣的培养

043 《疯狂英语》（或各种教学方式）的利与弊

044 张思中教学法实践调查报告

045 如何杜绝中式英语

046 英语教师的文化素养

047 网络时代如何学好英语

048 背景知识与阅读理解

049 上下文在阅读理解中的作用

050 家庭教师在中学生英语学习中的利弊

051 中学英语教学现状分析

052 中学英语课堂上的Daily Report

053 中外教师解释课文方法比较

054 中外教师课堂提问方法比较

055 中外教师课堂鼓励性用语比较

056 中外教师对学生总体要求之比较

057 计算机辅助英语教学中的诸问题

058 不同种类的计算机辅助英语教学方式

059 计算机辅助英语教学中的教学法原则

060 The Instructive Meaning of Inter-language Pragmatics for foreign Language Teaching

061 Pedagogical Translation and Translation Teaching

062 The Importance of Cultural Authenticity in Teaching Materials

063 Micro-teaching and Student Teacher Training

064 How to Evaluate the Teacher www.xiexiebang.com Performance-A Case Study 065 English Test Design 066 The Interference of Native Language in English Writing or Translation 067 Translation Methods and English Teaching

第四篇：英语专业论文开场白

Good afternoon, Distinguished professors and teachers.I am Gu Danni From the class of English translation.First, I would like to express my sincere gratitude to my supervisor, Ms.Wang, for her intellectual guidance, invaluable instructions and comments on my thesis.It is with her valuable assistance that I have finally accomplished this paper.The title of my paper is Strategies in Humor Translation of American Sitcom Friends.As a vital part in translation, the translation of humor in subtitle is gradually capturing an increasing attention and developing into an independent research field.The purpose of the paper is to explore the interpretation of verbal humor in American sitcoms Friends under the guidance of the Functional Equivalence Theory, with the hope of helping people express humor and understand humor effectively.The final goal of translating a sitcom is to ensure that the target audience can get the humor and appreciate it in the exactly the same manner as the original audiences do,here is an outline of my presentation and I divide my paper into five parts.Part one and two presents an introduction of this study and Nida’s Functional Equivalence Theory, Part three makes a clear illustration of the different categories of humor in Friends，and discussed the features of language.Then I apply these strategies to the subtitling of Friends featuring humorous language.Part five draws some conclusions that translators should try to find appropriate strategies to convey the humorous effect and make the cross-cultural communication smoothly.I hope the paper can provide some insightful opinions for the improvement of humor translation in American sitcoms.However, due to limited time and resources, the paper may have some deficiency, and there is still a long way to go..I’m looking forward to your sincere comments and suggestions.That’s all.Thank you.

第五篇：英语专业论文翻译

A smart copper(II)-responsive binucleargadolinium(III)complex-based magnetic resonanceimaging contrast agent†

Yan-meng Xiao,ab Gui-yan Zhao,ab Xin-xiu Fang,ab Yong-xia Zhao,ab Guan-hua Wang,c Wei Yang*a and Jing-wei Xu*a A novel Gd-DO3A-type bismacrocyclic complex, [Gd2(DO3A)2BMPNA], with a Cu2+-selective binding unitwas synthesized as a potential “smart” copper(II)-responsive magnetic resonance imaging(MRI)contrast agent.The relaxivity of the complex was modulated by the presence or absence of Cu2+;in the absence of Cu2+, the complex exhibited a relatively low relaxivity value(6.40 mM1 s1), while the addition of Cu2+ triggered an approximately 76% enhancement in relaxivity(11.28 mM1 s1).Moreover, this Cu2+-responsive contrast agent was highly selective in its response to Cu2+ over other biologically-relevant metal ions.The influence of some common biological anions on the Cu2+-responsive contrast agent and the luminescence lifetime of the complex were also studied.The results of the luminescence lifetime measurements indicated that the enhancement in relaxivity was mainly ascribed to the increased number of inner-sphere water molecules binding to the paramagnetic Gd3+ core upon the addition of Cu2+.In addition, the visual change associated with the significantly enhanced relaxivity due to the addition of Cu2+ was observed from T1-weighted phantom images.Introduction Copper(II)ion is a vital metal nutrient for the metabolism of life and plays a critical role in various biological processes.1,2 Its homeostasis is critical for the metabolism and development of living organisms.3,4 On the other hand, the disruption of its homeostasis may lead to a variety of physical diseases and neurological problems such as Alzheimer's disease,5 Menkes and Wilson's disease,6 amyotrophic lateral sclerosis,7,8 and prion disease.9,10 Therefore, the assessment and understanding of the distribution of biological copper in living systems by noninvasive imaging is crucial to provide more insight into copper homeostasis and better understand the relationship between copper regulation and its physiological function.A wide variety of organic uorescent dyes have been exploited for the optical detection of ions in the last few decades.11–13However, optical imaging using organic uorescent dyes hasseveral limitations such as photobleaching, light scattering,limited penetration, low spatial resolution and the disturbance of auto uorescence.14 By comparison, magnetic resonance imaging(MRI)is an increasingly accessible technique used as a noninvasive clinical diagnostic modality for medical diagnosis and biomedical research.15 It can provide high spatial resolution three-dimensional anatomical images with information about physiological signals and biochemical events.16 As a powerful diagnostic imaging tool in medicine, MRI can distinguish normal tissue from diseased tissue and lesions in a noninvasive manner,17–19 which avoids diagnostic thoracotomy or laparotomy surgery for medical diagnoses and greatly improves the diagnostic efficiency.Multiple MRI imaging parameters can provide a wealth of diagnostic information.In addition, the desired cross-section for acquiring multi-angle and multi-planar images of various parts of the entire body can be freely chosen by adjusting the MRI magnetic eld;this ability makes medical diagnostics and studies of the body's metabolism and function more and more effective and convenient.Contrast agents are often used in MRI examinations to improve the resolution and sensitivity;the image quality can be signicantly improved by applying contrast agents which enhance the MRI signal intensity by increasing the relaxation rates of the surrounding water protons.20 Due to the high magnetic moment(seven unpaired electrons)and slow electronic relaxation of the

paramagnetic gadolinium(III)ion, gadolinium(III)-based MRI contrast agents are commonly employed to increase the relaxation rate of the surrounding water protons.16,21 However, most of these contrast agents are nonspecific and provide only anatomical information.On the basis of Solomon–Bloembergen–Morgan theory,22–24 several parameters can be manipulated to alter the relaxivity of gadolinium(III)-based MRI contrast agents.These parameters include the number of coordinated water molecules(q), the rotational correlation time(sR)and the residence lifetime of coordinated water molecules bound to the paramagnetic Gd3+ center(sM).Adjusting any of these three factors provides the opportunity to design “smart” MRI contrast agents for specific biochemical events.25–27 In recent years, there have been many studies on the development of responsive gadolinium(III)-based MRI contrast agents;most of them have focused on the development of targeted, high relaxivity and bioactivated contrast agents.These responsive gadolinium(III)-based MRI contrast agents can be modulated by particular in vivo stimuli including pH,28–35 metal ion concentration36–43 and enzyme activity.44–50 Notably, a number of copper-responsive MRI contrast agents have been reported to detect uctuations of copper ions in vivo.51–58 These activated contrast agents exploit the modulation of the number of coordinated water molecules to generate distinct enhancements in longitudinal relaxivity in response to copper ions(Cu+ or Cu2+).In this study, we designed and synthesized a binuclear gadolinium-based MRI contrast agent, [Gd2(DO3A)2BMPNA], that is specically responsive to Cu2+ over other biologicallyrelevant metal ions.The new copper-responsive MRI contrast agent comprises two Gd-DO3A cores connected by a 2,6-bis(3-methyl-1H-pyrazol-1-yl)isonicotinic acid scaffold59,60(BMPNA), which functions as a receptor for copper-induced relaxivity switching.The synthetic strategy for [Gd2(DO3A)2BMPNA] is depicted in Scheme 1.Subsequently, the T1 relaxivity of [Gd2(DO3A)2BMPNA] was studied at 25 C and 60 MHz in the absence or presence of Cu2+.Experiments to determine the selectivity of [Gd2(DO3A)2BMPNA] towards Cu2+ over other biologically-relevant ions were carried out as well.Luminescence lifetime was measured to determine the number of coordinated water molecules(q)of [Gd2(DO3A)2BMPNA] in the absence or presence of Cu2+.In addition, T1-weighted phantom images were collected to visualize the relaxivity enhancement caused by Cu2+, suggesting potential in vivo applications.Experimental section

Materials and instruments

All materials for synthesis were purchased from commercial suppliers and used without further purication.1H and 13C NMR spectra were taken on an AMX600 Bruker FT-NMR spectrometer with tetramethylsilane(TMS)as an internal standard.Luminescence measurements were performed on a Hitachi Fluorescence spectrophotometer-F-4600.The time-resolved luminescence emission spectra were recorded on a Perkin-Elmer LS-55 uorimeter with the following conditions: excitation wavelength, 295 nm;emission wavelength, 545 nm;dela time, 0.02 ms;gate time, 2.00 ms;cycle time, 20 ms;excitation slit, 5 nm;emission slit, 10 nm.The luminescence lifetime was measured on a Lecroy Wave Runner 6100 Digital Oscilloscope(1 GHz)using a tunable laser(pulse width ¼ 4 ns, gate ¼ 50 ns)as the excitation(Continuum Sunlite OPO).Mass spectra(MS)were obtained on an auto ex III TOF/TOF MALDI-MS and anIonSpec ESI-FTICR mass spectrometer.Elemental analyses were performed on a Vario EL Element Analyzer.Synthesis Synthesis of compound 3.Methyl 2,6-bis(3-(bromomethyl)-1H-pyrazol-1-yl)isonicotinate(Compound1)59,60 and 4,7,10-tris(2-(tert-butoxy)-2-oxoethyl)-4,7,10-triaza-azoniacyclododecan-1-ium bromide(Compound 2)61 were prepared following thereported methods.Compound 2(0.25 g, 0.296 mmol)was suspended in 2 ml anhydrous acetonitrile with 6 equivalents of NaHCO3(0.1492 g)and the mixture was stirred at room temperature for 0.5 h.Compound 1(0.0675 g, 0.148 mmol)was added, and the mixture was slowly heated to reflux(80 C)and stirred overnight.After the reaction was terminated, the mixture was cooled to room temperature, and the solution was ltered.The precipitate was washed several times with anhydrous acetonitrile, and the collected ltrate solution was evaporated under reduced pressure.The residue was puried using silicagel column chromatography eluted with CH2Cl2–n-hexane–CH3OH(10 : 3 : 1, v/v/v)to afford Compound 3(0.1038 g, 53%)as a pale yellow solid.1H NMR(600 MHz, DMSO): 8.22(s, 2H), 8.15(s, 2H), 6.62(s, 2H), 4.53(s, 4H), 3.82(s, 3H), 3.42(m, 4H), 2.98(m, 8H), 2.85(s, 8H), 2.71(m, 24H), 1.33(s, 54H)(Fig.S1†).13C NMR(151 MHz, CDCl3): d 173.21, 172.44, 163.99, 152.38, 150.11, 143.13, 128.07, 109.83, 108.36, 82.59, 57.84, 56.52, 56.06, 55.56, 52.98, 50.55, 48.91, 47.30, 27.96(Fig.S2†).HRMS(ESI): m/z calc.for C67H111N13O14 [M + 2H]2+ 661.92650, [M + H + Na]2+ 672.91747, [M + 2Na]2+ 683.90844, found [M + 2H]2+ 661.92584, [M+ H + Na]2+ 672.91690, [M + 2Na]2+ 683.90682(Fig.S3†).Synthesis of compound 4.Compound 3(0.1 g, 0.0756 mmol)was stirred with triuoroacetic acid in methylene chloride solution(2 ml)at room temperature for 24 h.The solvent was then evaporated under reduced pressure, and the residue was washed three times in CH3OH and CH2Cl2 to eliminate excess acid.The obtained residue was dissolved with a minimum volume of CH3OH and precipitated with cold Et2O.The precipitate was ltered to afford a brown yellow solid(0.1022 g).1H NMR(600 MHz, DMSO): 9.06(s, 2H), 8.17(s, 2H), 6.84(s, 2H), 4.33(s, 4H), 3.98(s, 3H), 3.56(b, 20H), 3.09(m, 24H)(Fig.S4†).13C NMR(151 MHz, D2O): d 174.11, 169.13, 164.64, 150.75, 148.85, 142.10, 129.88, 109.75, 107.99, 55.69, 54.01, 53.10, 52.43, 51.15, 49.59, 48.22, 47.69(Fig.S5†).MALDI-TOFMS spectrum(CH3OH): m/z calc.for C43H63N13O14 [M H] 984.46, found 984.7(Fig.S6†).Anal calc.for C43H63N13O14-$3CF3COOH$2H2O: C, 43.14;H, 5.17;N, 13.35;found C, 42.34;H, 4.999;N, 13.29%.Preparation of [Gd2(DO3A)2BMPNA] and [Tb2(DO3A)2-BMPNA].Compound 4(0.05 mmol)was dissolved in 2 ml of highly-puried water.GdCl3 or TbCl3(0.1 mmol)was added dropwise.The pH was maintained at 6.5–7.0 with NaOH during the whole process.The solution was then stirred at 75 C for 24 h.MALDI-MS(H2O): m/z calc.for C42H55N13O14Gd2 [M + H]+ 1281.46, found 1281.4(Fig.S7†).MALDI-MS(H2O): m/z calc.for C42H55N13O14Tb2 [M + H]+ 1284.3, found 1284.4(Fig.S8†).T1 measurements.The longitudinal relaxation times(T1)of aqueous solutions of [Gd2(DO3A)2BMPNA] were measured on an HT-MRSI60-25 spectrometer(Shanghai Shinning Globe Science and Education Equipment Co., Ltd)at 1.5 T.All of the tested samples were prepared in HEPES-buffered aqueous solutions at pH 7.4.All of the metal ions(Na+, K+, Ca2+, Mg2+, Cu2+, Zn2+, Fe3+, Fe2+)were used as chloride salts.Concentrations of Gd3+ were determined by ICP-OES.Relaxivities were determined from the slope of the plot of 1/T1 vs.[Gd].The data were tted to the following eqn(1),20

(1/T1)obs ¼(1/T1)d + r1[M](1)

where(1/T1)obs and(1/T1)d are the observed values in the presence and absence of the paramagnetic species, respectively, and [M] is the concentration of paramagnetic [Gd].Luminescence measurements.Luminescence emission spectra were collected on a Hitachi uorescence spectrophotometer-F-4600.The luminescence lifetime was measured on a Lecroy Wave Runner 6100 Digital Oscilloscope(1 GHz)using a tunable laser(pulse width ¼ 4 ns, gate ¼ 50 ns)as the excitation(Continuum Sunlite OPO).Samples were excited at 290 nm, and the emission maximum(545 nm)was used to determine luminescence lifetimes.The Tb(III)-based emission spectra were measured using 0.1 mM solutions of Tb complex analog in 100 mM HEPES buffer at pH 7.4 in H2O and D2O in the absence and presence of Cu2+.The number of coordinated water molecules(q)was calculated according to eqn(2):62,63 q= ¼ 5(sH2O1 sD2O1 0.06)(2)T1-weighted MRI phantom images.Phantom images were collected on a 1.5 T HT-MRSI60-25 spectrometer(Shanghai Shinning Globe Science and Education Equipment Co., Ltd).Instrument parameter settings were as follows: 1.5 T magnet;matrix =256 256;slice thickness =1 mm;TE= 13 ms;TR= 100 ms;and number of acquisitions =1.Results and discussion Longitudinal relaxivity of [Gd2(DO3A)2BMPNA] in response to copper(II)ion To investigate the inuence of Cu2+ on the relaxivity of [Gd2(DO3A)2BMPNA], the longitudinal relaxivity r1 for the [Gd2(DO3A)2BMPNA] contrast agent was determined using T1 measurements in the absence or presence of Cu2+ at 60 MHz and 25 C using a 0.2mMGd3+ solution of [Gd2(DO3A)2BMPNA] in 100 mM HEPES buffer(pH 7.4)under simulated physiological conditions.The concentrations of Gd3+ were determined by ICP-OES.The relaxivity r1 was calculated from eqn(1).In the absence of Cu2+, the relaxivity of [Gd2(DO3A)2BMPNA] was 6.40 mM1 s1, which was higher than that of [Gd(DOTA)(H2O)](4.2 mM1 s1, 20 MHz, 25 C)and Gd(DO3A)(H2O)2(4.8 mM1 s1, 20 MHz, 40 C).64 Upon addition of up to 1 equiv.of Cu2+, the relaxivity of [Gd2(DO3A)2BMPNA] increased to 11.28 mM1 s1(76% relaxivity enhancement).As shown in Fig.1, the relaxivity gradually increased with the copper ion concentration, reaching a maximum value of approximately 1.2 equivalents of Cu2+.Due to the use of triuoroacetic acid in the synthesis of Compound 4, triuoroacetic acid residues produced CF3COO in the [Gd2(DO3A)2BMPNA] solution, allowing CF3COO to partially coordinate with Cu2+ to form “Chinese lantern” type structure complexes.65 When the amount of added copper ions was further increased to above 1.2 equiv., the relaxivity was maintained at the same level.The observed difference in Cu2+-triggered relaxivity enhancement demonstrated the ability of this contrast agent to sense Cu2+ in vivo by means of MRI.Our designed contrast agent not only exhibited a higher relaxivity, but also displayed a Cu2+-responsive relaxivity enhancement.Selectivity studies The relaxivity response of [Gd2(DO3A)2BMPNA] exhibited excellent selectivity for Cu2+ over a variety of other competing, biologically-relevant metal ions at physiological levels.As depicted in Fig.2(white bars), the addition of alkali metal cations(10 mM Na+, 2 mM K+)and alkaline earth metal cations(2 mM Mg2+, 2 mM Ca2+)did not generate an increase in relaxivity compared to the copper ion turn-on response;even the introduction of d-block metal cations(0.2 mM Fe2+, 0.2 mM Fe3+, 0.2 mM or 2 mM Zn2+)did not trigger relaxivity enhancements.We noted that Zn2+ is also known to replace Gd3+ in transmetalation experiments;however, studies with analogous Gd3+-DO3A complexes demonstrated that this ligand is more kinetically inert to metal-ion exchange.66 To ensure the kinetic stability of the complex, we used MS to monitor [Gd2(DO3A)2BMPNA] in the presence of 1 equiv.of Zn2+.No metal-ion exchange was observed at room temperature after 7 days(Fig.S13†).Relaxivity interference experiments for [Gd2(DO3A)2BMPNA] in the presence of both Cu2+(0.2 mM)and other biologically-relevant metal ions were also conducted;the results are shown as black bars in Fig.2, indicating that these biologically-relevant metal ions(Na+, K+, Mg2+, Ca2+, Fe2+, Fe3+, Zn2+)had no interference on the Cu2+-triggered relaxivity enhancement.In addition, we also tested the Cu2+ response for [Gd2(DO3A)2BMPNA] in the presence of physiologically-relevant concentrations of common biological anions to determine whether the Cu2+-triggered relaxivity enhancement was affected by biological anions at physiological levels.As previously mentioned, Cu2+ binding induced an enhancement in relaxivity from 6.40 mM1 s1 to 11.28 mM1 s1(a 76% increase).As shown in Fig.3, in the presence of citrate(0.13 mM), lactate(0.9 mM), H2PO4(0.9 mM), or HCO3(10 mM), the Cu2+-triggered relaxivity enhancement was approximately 61%(from 6.01 mM1 s1 to 9.66mM1 s1), 66%(from 6.13mM1 s1 to 10.16 mM1 s1), 20%(from 5.88 mM1 s1 to 7.02 mM1 s1), or 55%(from 6.15 mM1 s1 to 9.55 mM1 s1), respectively.Additionally, 100 mM NaCl had almost no effect(an approximately 75% increase), and a simulated extracellular anion solution(EAS, contain 30 mM NaHCO3, 100 mM NaCl, 0.9 mM KH2PO4, 2.3 mM sodium lactate, and 0.13 mM sodium citrate, pH =7),67 resulted in a Cu2+-triggered relaxivity enhancement of approximately 26%(from 6.02 mM1 s1 to 7.56 mM1 s1).Generally, the results revealed that lactate, citrate, and HCO3 had slight impacts on the Cu2+-triggered relaxivity enhancement, while H2PO4 and EAS influenced the enhancement to a greater degree.As shown in Scheme 2, [Gd2(DO3A)2BMPNA] possessed two water molecules after the addition of 1 equiv.Of Cu2+.According to the work of Dickins and coworkers, in lanthanide complexes with two water molecules, the waters can be partially displaced by phosphate, carbonate, acetate, carboxylate, lactate and citrate at different levels.68–70 The influence of these anions on the Cu2+-triggered relaxivity enhancement may be attributed to the partial replacement of coordinated water molecules by these anions.The relatively high concentration of phosphate could likely replace coordinated water molecules to reduce the increased number of water molecules surrounding the paramagnetic Gd3+ centre induced by Cu2+.As shown in Table 1, we measured the number of water molecules in the rst coordination sphere of Tb3+ in the presence of phosphate;the number of coordinated water molecules(q)decreased from 1.5 to 0.8.Coordination features Luminescence lifetime experiments were performed to explore the mechanism of the Cu2+-triggered relaxivity enhancement.Luminescence lifetime measurements of lanthanide complexes have been widely used to quantify the number of inner-sphere water molecules.71 In particular, Tb3+ and Eu3+ have commonly been applied for lifetime measurements because their emission spectra are in the visible region when their 4f electrons are relaxed from higher energy levels to the lowest energy multiplets.72,73 Therefore, the Tb3+ analogue of [Gd2(DO3A)2BMPNA], [Tb2(DO3A)2BMPNA], was prepared according to a similar method, and the luminescence lifetimes of the Tb3+ analogue in HEPES-buffered H2O and D2O in the absence and presence of Cu2+ were measured.As shown in Fig.S9,† the luminescence decay curve of [Tb2(DO3A)2BMPNA] was tted to obtain the luminescence lifetimes74(Table 1), and the number of coordinated water molecules(q)was calculated by eqn(2).The analysis results(Table 1)for [Tb2(DO3A)2BMPNA] in HEPES-bufferedH2OandD2O in the absence and presence of Cu2+ indicated that q increased from 0.6 to 1.5 upon the addition of 1 equiv.of Cu2+;this result indicated that the Cu2+-triggered relaxivity enhancement for [Gd2(DO3A)2BMPNA] was most likely due to the increased number of coordinated water molecules around the Gd3+ ion upon Cu2+ binding to the pyrazole centre(Scheme 2).Aer the addition of Cu2+, Cu2+ removed the pyrazole centre N atom from the paramagnetic Gd3+ ion to generate an open coordination site available for a water molecule.Luminescence emission titrations of [Tb2(DO3A)2BMPNA] towards Cu2+ were also performed to investigate the binding properties of the contrast agent towards Cu2+.Upon addition of 1 equiv.Cu2+, the luminescence of [Tb2(DO3A)2BMPNA] at 545 nm decreased gradually and reached a minimum due to the quenching nature of the paramagnetic Cu2+(Fig.S10†).The titration data indicated a 1 : 1 binding stoichiometry(Scheme 2)Copper-responsive T1-weighted phantom MRI in vitro To demonstrate the potential feasibility of this Cu2+-responsive [Gd2(DO3A)2BMPNA] for copper-imaging applications, T1-weighted phantom images of [Gd2(DO3A)2BMPNA] were acquired in the absence and presence of copper ions.The phantom images depicted in Fig.4 displayed distinct increases in image intensity in the presence of 1 equiv.Cu2+ compared with those without Cu2+(Fig.4D).Moreover, some of the other competing metal ions were also tested to further verify the selectivity of [Gd2(DO3A)2BMPNA] towards Cu2+.Discernible differences were not observed upon the addition of Mg2+(Fig.4C), Zn2+(Fig.4E), or Ca2+(Fig.4F).In addition, we also tested the clinical contrast agent Magnevist(Fig.4G);the image intensity was a bit darker than that of our contrast agent.Conclusions

In conclusion, we designed and synthesized a novel bismacrocyclic DO3A-type Cu2+-responsive MRI contrast agent, [Gd2(DO3A)2BMPNA].The new Cu2+-responsive MRI contrast agent comprised two Gd-DO3A cores connected by a 2,6-bis(3-methyl-1H-pyrazol-1-yl)isonicotinic acid scaffold(BMPNA)that functioned as a Cu2+ receptor switch to induce a distinct relaxivity enhancement in response to Cu2+;the relaxivity was increased up to 76%.Importantly, the complex exhibited high selectivity for Cu2+ over a range of other biologically-relevant metal ions at physiological levels.Luminescence lifetime experiment results showed that the number of inner-sphere water molecules(q)increased from 0.6 to 1.5 upon the addition of 1 equiv.Cu2+.When Cu2+ was coordinated in the central part of the complex, the donor N atom of the pyrazole centre was removed from the paramagnetic Gd3+ ion and replaced by a water molecule(Scheme 2).Consequently, the Cu2+-triggered relaxivity enhancement could be ascribed to the increase in the number of inner-sphere water molecules.The designed contrast agent had a longitudinal relaxivity of 6.40 mM1 s1, which was higher than that of [Gd(DOTA)(H2O)](4.2 mM1 s1, 20 MHz, 25 C)and Gd(DO3A)(H2O)2(4.8 mM1 s1, 20 MHz, 40 C).In addition, the visual change associated with the signicantly enhanced relaxivity from the addition of Cu2+ was observed in T1-weighted phantom images.Acknowledgements We are grateful to the State Key Laboratory of Electroanalytical Chemistry for nancial support.Notes and references 1 S.Puig and D.J.Thiele, Curr.Opin.Chem.Biol., 2002, 6, 171.2 S.C.Leary, D.R.Winge and P.A.Cobine, Biochim.Biophys.Acta, Gen.Subj., 2009, 146, 1793.3 D.D.Agranoff and S.Krishna, Mol.Microbiol., 1998, 28, 403.4 H.Kozlowski, A.Janicka-Klos, J.Brasun, E.Gaggelli, D.Valensin and G.Valensin, Coord.Chem.Rev., 2009, 253, 2665.5 K.J.Barnham, C.L.Masters and A.I.Bush, Nat.Rev.Drug Discovery, 2004, 3, 205.6 D.J.Waggoner, T.B.Bartnikas and J.D.Gitlin, Neurobiol.Dis., 1999, 6, 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