英语专业论文开场白

第一篇：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：英语专业答辩开场白

英语专业答辩开场白

篇一：3分钟英语专业毕业论文论文答辩开场白

Good morning, professors and everyone.I come from JMU College.I am XXX and my supervisor is prof XXX.With her sincere and intellectual guidance, I have finished my paper.The title of my paper is An Analysis of Ahab’s Personality Tragedy in Moby Dick.I choose this title as my topic due to the following reasons.Firstly, I am fond of literature works , especially gothic literature works.Secondly, I am quite familiar with this work as this is one of the texts in our American literature course.Last but not least , Moby-Dick is widely recognized as the summit not only of Melville’s art but of American nineteenth-centry fiction.The purpose of this essay is to study Captain Ahab,the role in Moby-Dick, whose leg was bitten by the white whale in his process of the whaling.After losing his leg, he determined to revenge Moby Dick and tried to kill it.In order to revenge, Ahab ultimately dooms the crew of the Pequod(save for Ishmael)to death by his obsession with Moby Dick.By taking the comprehensive analysis perspective of Moby-Dick, this thesis will point out that the main characteristics of Ahab.This paper consists of three parts.Part one presents an introduction to the Social Background and the life of the Author Herman Melvillehe ,Part two presents The Main Characteristics of Ahab.there are three aspects have been divided to analyze his characters: his monomania , his selfishness, and his individualism.Part three presents The Consequences of Ahab's Personality Tragedy.OK, that's all.Thank you!Questions : 1.怎样运用理论去分析的

2.针对你论文中的某个商标翻译而考你噢，所以要熟悉你论文中作为例子的翻译 3.什么是monomania（偏执狂）？

4.白鲸记的象征意义有哪些

5.亚哈船长为何复仇选择我们，选择成功！

如需备注，请自行写在下面： 篇二：英文论文答辩开场白

英文论文答辩开场白

Opening Speech

（一）Good morning, Distinguished professors and teachers, ladies and gentlemen, thank you for attending the oral defense.(或Welcome to attend the oral defense.)：

I am Zhao Jing.Firstly, I would like to express my sincere gratitude to my supervisor Zhong Ming, for his intellectual guidance, invaluable instructions and comments on my thesis.It is with his valuable assistance that I have finally accomplished this thesis.The title of my paper is The Masculine Spirit of The Old Man and the Sea The whole thesis consists of 3 parts.The first part will give brief introductions on the background which contains the social and cultural aspects and the introduction to the author of the masterpiece.In The second part is going to have a brief introduction of the old man and the sea and analyze the masculine spirits in the old man and the sea such as the faith optimistic and the wisdom of the hero.In the third part, it is the natural conclusion and the deep consideration.I choose this as my topic due to the following reasons.Firstly, I am fond of literature works.Secondly, I am quite familiar with this novel as this is one of the texts in our intensive teaching course and I have taught this text for more than 3 times.Last but not the least, I’m deeply appreciated to the masculine spirit and hope I can get and practice it in my future.For the above facts, I select the subject of The Masculine Spirit of The Old Man and the Sea as the title of my paper.I hope by studying this novel we can know more about the author Hemingway and his honorable masculine spirit.“A man can be destroyed but not be defeated.” Such kind of spirit can help us raise our independence and confidence and show more concern for our mental health.That’s all.Thank you!

2、主要陈述内容（）：

（1）自己选择这个题目的原因；

（2）设计和实施的简单过程（如，商务方向：采用什么方法来搜集信息、资料等）；search the information from library and then internet（3）自己论文的主要内容（不要念论文，最好用4、5句话简单介绍论文内容，如，商务方向：做了哪些调查，得出什么结论，计划如何实施项目）；

（4）仍然存在的问题（如，商务：在实施项目中可能会遇到的风险以及如何解决）；the aspect which I have quoted may be not perfect and have many deficiencies

3、最好准备相关文字并熟记（答辩时要脱稿陈述，但是可以看PPT文件）。

4、语言最好简单清楚，不要直接用论文中内容，应该用解释性的句式，如：When I was designing the lessons, I found that….二、回答老师问题（老师用英语提问，学生用英语回答）：

1、大约有4－6个问题，时间将持续10－15分钟。

2、首先要听清楚问题，如果没有听清，可以要求老师重复问题（可以说pardon之类的话）。

3、回答时首先要态度好，要切题，而且不要保持沉默，不会时可以表示抱歉。

4、常见问题：

（1）Will you please give us a self-introduction? 有些学生可能由于紧张没听清问题便开始背诵论文的内容，结果造成答非所问。

（2）Give us a presentation of your thesis.有些学生一听到thesis便详细而又不理解地背诵其论文内容, 在被打断之后便不知该说什么。其实, 考官只是想知道你对论文的总体了解, 让你简单阐明自己论文的内容与观点。

（3）Why do you choose such a theme?/ What do you want the reader get from your thesis? 对于这个问题，你可以谈谈你的喜好，你想要读者从中得到什么。

（4）What is the uniqueness of your point of view? 对于这个问题，你可以谈谈你的观点与他人不同之处及原因。这就要求你有相关知识。

之后便是针对你的论文的问题了。

（5）关于选题：如Why did you choose this topic for your paper?或Why were you interested in this project？

（6）关于具体部分：

商务方向：SWOT，COSTING，FLOWCHART，RISK，STAKEHOLDER，如Do you think is this a necessary activity for the project?（7）关于背景知识及理论知识：如What does SWOT stand for?（商务）（8）关于论文存在的问题：如In the last sentence on page … there are some grammatical errors.（9）关于项目或论文将来的发展：如：商务方向：If possible, will you ca 篇三：最新英语专业毕业论文答辩开场白结束语精品范文

最新英语专业毕业论文

开场白结束语优秀范文

尊敬的各位老师：

早上好！

我叫××，是英语专业××班的学生，我的论文题目是×××(这里改成英语专业论文题目)。首先，感谢您们在百忙之中抽出宝贵时间倾听我的英语专业毕业论文答辩。我英语专业论文导师是××(改成英语论文导师名字)教授，无论从确定选题、拟定提纲、完成初稿，还是到最后定稿，我都得到了××(改成英语论文导师名字)教授的精心细致指导。借此机会，我要向我的导师表示深深的谢意，同时对任教我的各位英语专业相关老师表示由衷的敬意。下面我将英语专业论文设计的主要内容向各位老师作一汇报，恳请各位老师批评指导：

首选，允许我介绍一下我的英语专业毕业论文的选题背景和研究意义。随着时代和社会发展，英语领域相关理论和技术研究日新月异……（简单阐述本论文在英语领域的背景和研究意义）。因此，×××(这里改成英语专业论文研究内容)在英语研究领域和社会上有着广泛的应用前景。

其次，我想介绍一下×××(这里改成英语专业论文题目)这篇论文的主要结构和内容。论文结构包括摘要与关键词、目录、正文、附录、参考文献等五个部分。×××(这里改成英语专业论文题目)正文主要内容包括论文综述、研究过程和方法、研究结果和结论分析。(这

第四篇：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 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