Analysis of Compound 109 using 13C NMR Spectra

Analysis of Compound 109 using 13C NMR Spectra The 13C NMR spectrum of compound 109-114 is represented in Plate 40-45. Structural elucidation of 109 by 13C NMR spectrum has been described and it was confirmed from the two dimensional NMR reports of 109. Assignments for the other compounds 109-114 made by comparing with compound 109. Table 33 lists the chemical shift values of 109. A collection of signals resonated in the aliphatic region at 20.85, 26.60 and 27.98 ppm of the three signals in the aliphatic region, signals at 20.85, 26.60 and 27.98 ppm are assigned to C-7, C-6 and C-8, respectively. The C-5 signal is merged with solvent signal. In addition to this, the benzylic carbon signals C-2 and C-4 were resonated at 64.53 and 62.52 ppm respectively, whereas the bridgehead carbon C-1 was appeared at 45.69 ppm. Moreover, a collection of signals appeared in the region 102.69-131.40 ppm, which are unambiguously assigned to aryl carbon. A part from the assigned signals, two signals resonated in the downfield at 142.56 and 142.72 pp m is assigned to ipso carbons. Another four unassigned signals resonated in the down field region at 159.55 to 166.27 ppm and these signals belong to C=0, C=N, C-OH carbons respectively. 1H-13C COSY spectra Plate 46 and 47 represents the 1H-13C COSY spectrum of 105 and the correlations showed in Table 34. HMBC (Plate 40) and HSQC (Plate 41) correlations have been used to assign the benzylic carbons, ipso carbons of aryl group, and methylene carbons (C-6, C-7, and C-8). The benzylic protons observed at 4.30 (H-2a) and 4.25 ppm (H-4a) showed cross peak with 64.33 (C-2) and 62.52 ppm (C-4), which may be due to the C-2 and C-4 carbons of the piperidone heterocyclic of the ABN system. The bridgehead methine proton signals at 2.50 (H-1e) and 2.98 (H-5e) ppm was correlated with the carbon signals at 45.69 ppm (C-1) and 39.57 ppm (C-5). This indicates that the signals appeared at 45.69 and 39.57 ppm is unambigously assigned to C-1 and C-5 carbons. Cross peak with the protons resonated at 2.77 (H-7a) and 1.27 (H-7e) ppm was correlated with the carbon signal at 20.85 ppm and this confirms the signal at 20.85 ppm was solely specific to C-7 carbon. H-6a and H-6e protons appeared at 1.45 and 1.60 ppm showed cross peak with 26.60 ppm (C-6 carbon), which confirms that the signal at 26.60 ppm was due to C-6 carbon and the carbon signal at 20.85 ppm was attributed to the corresponding C-7 carbon. Similarly, the H-8e (1.63 ppm) and H-8a (1.55 pm) protons was correlated with the carbon signal at 27.98 ppm (C-8), which suppors that the signal at 27.98 ppm was ascribed to the cyclohexane ring carbon C-8. Analysis of spectra of 109-114 1H and 13C NMR spectral analysis of other compounds such as N-(2,4-bis(4-chlorophenyl)-3-azabicyclo[3.3.1]nonan-9-ylidene)-2,4-dihydro-xybenzohydrazide101, N-(2,4-bis(4-fluorophenyl)-3-azabi-cyclo-[3.3.1]nonan-9-ylidene)-2,4-dihydroxybenzohydrazide 102, N-(2,4-bi-s(4-bromophenyl)-3-azabicyclo[3.3.1]nonan-9-ylidene)-2,4-dihydroxy-benzohydrazide 103, N-(2,4-dip-tolyl-3-azabicyclo[3.3.1] nonan-9-ylidene)-2,4-dihydroxybenzohydrazide 104, N-(2,4-bis(2-chloro-phenyl)-3-azabicyclo[3.3.1]nonan-9-ylidene)-2,4-dihydroxy-benzohy-drazide 105 was analyzed in a similar way of 109. The chemical shift and splitting patterns observed using 1H and 13C NMR assignments for other compounds is presented in Tables 35 and 36 and their corresponding spectra are given in Plates 33-37 41-45, respectively. Tables 37-42 show the brief description of analytical and spectral data of compounds 109-114. Taken together, all the above observations substantiate the proposed structure and twin-chair (CC) conformation o f 2r,4c-diaryl-3-azabicyclo [3.3.1] nonan-9-one-4-methyl-1,2,3-thiadazole-5-carbonyl hydrazones 102-108. Biological study Free radical scavenging activity Intensity of the free radical scavenging potential strongly depends upon its chemical structure. Several studies have demonstrated that the free radical scavenging effects is noticeably influenced by the number and position of hydroxyl groups on the D ring and by the extent of conjugation between the D ring amide carbonyl group [1-4]. The dihydroxy structure in the D ring confers high stability to the hydrazones phenoxyl radical via hydrogen bonding or by electron delocalization. The amide carbonyl group double bond (Conjugation with the amide oxo group) determines the coplanarity of the phenyl ring and participates in radical stabilization via electron delocalization over all ring system [4]. Initial studies on analysis of free radical scavenging potential of diaryl 3-azabicyclononanones revealed a concentration dependent weak anti-radical activity resulting from reduction of DPPH†¢, ABTS†¢+, O†¢Ã¢Ë†â€™, OH†¢, and nitric oxide radicals to their non-radical forms. In order to bring the dihydroxy structure in the D ring and the amide carbonyl group double bond (Conjugation with the amide oxo group) into diaryl 3-azabicyclononanones to enhance the free radical potential (figure 14), We therefore synthesized N-(2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)-2,4-dihydroxybenzohydrazide (109-114) by the reaction of 95,96,98-101 with 2,4-dihydroxybenzoic acid hydrazide (94) in the presence of acetic acid. All the tested compounds showed a concentration dependent anti-radical activity against various free radicals. IC50 values for the free radical scavenging effects of ascorbic acid and various synthetic compounds (109-114) are shown in Table 43.This may be due to the hydrogen atom donation mechanism and the electron donation mechanism. In the hydrogen atom transfer mechanism, hydroxyl groups donate hydrogen to a radical stabilizing it and giving rise to a relatively stable hydrazones phenoxyl radical. Figure 15 illustrates the probable mechanism of hydrogen atom donating ability of compounds 109-114. The electron donation mechanism involves through the strong hydrogen bond of -OH moiety with the oxygen atom of amide carbonyl group that may prevent efficient deprotonation and enhance their radical scavenging action by means of hydrogen atom donation. Figure 16 illustrates the probable mechanism of free radical scavenging effects of compounds 109-114 through electron donating mechanism. Structure A is the parent neutral molecule of compounds 109-114. Structure B is the initial radical ions and structure C is its more stable tautomeric form. The tautomeric form C of the radical ions results from the initial radical ions B and proton transfer from C-2Ê º -OH to carbonyl groups. We found required structural features to scavenge free radical in our tested compounds (109-144). However, we have noticed a diverse range of effects against various free radicals. This may be due the different substitution at the C-2 and C-6 positions of the azabicyclononan-9-one moiety. Compound 8 devoid of any substituents at the para position of the phenyl groups at the C-2 and C-6 positions of the azabicyclononan-9-one moiety and phenyl rings with electron-donor methyl groups at the para position of compounds 113 showed excellent free radical scavenging effects compared to standard antioxidant ascorbic acid, a known antioxidant used as a positive control. This may be due to incorporation of methyl groups at para position phenyl ring. Several studies have demonstrated that organic molecules incorporating a methyl groups can act as free radical trapping agents and are capable of opposing oxidative challenges [5,6]. Compounds possessing electron-withdrawing chloro (110/114), bromo (111), and fluoro (112), substitutions at the para position of the piperidine moiety showed admirable in vitro free radical scavenging effects against various free radicals. This admirable or less free radical scavenging effects of compounds with bromo, choloro and fluoro substitutions may be due to the electron-withdrawing inductive effect of halogens. The results obtained in the present study are in line with other findings [7,8]. Taken together, the current research suggests that azabicyclononane ring ensuring hydroxyl groups on the D ring and by the extent of conjugation between the D ring amide carbonyl group with strong free scavenging effects (111) may conceivably contribute to its protective effects against free radical-induced oxidative stress and carcinogenesis. Antibacterial and antifungal activity Synthesized compounds 109-114 were examined for their antibacterial and antifungal potencies. In vitro studies by twofold serial dilution method was adopted. Streptomycin/ streptomycin/ fluconazole were used as a positive control. Table 44 shows the MICs of test compounds 109-114. Analysis of in vitro antimicrobial effects of all the N-(2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)-2,4-dihydroxybenzohydrazide 109-114 revealed a diverse range of (1.56-200  µg/mL) against the various bacterias and fungus. The compounds deprived of any substituents at the aryl rings in 109 hinder the growth of all bacteria and fungus at a MIC value of 100-200 ÃŽ ¼g/mL. However, compounds 110, 111 and 112 possessing para halo (electron withdrawing substitutents chloro, fluoro and bromo) substituted aryl groups in azabicyclononane moiety accounts for the enhanced inhibitory effects against B. subtilis, K. pneumonia, P. aeruginosa, S. aureus, A. flavus, A. Niger, C. albicans, and Candida6 at MIC value s of 1.56-25  µg/mL when compared to the standard antibiotic streptomycin/ fluconazole. Several studies have also documented that electron-withdrawing groups (fluoro, bromo and chloro) substituted azabicyclononan-9-one derivatives exhibited outstanding antibacterial and antifungal activities [9,10]. Compound 114 with ortho chloro substituent in the phenyl moiety displays good antibacterial activity against all pathogens. Other compounds displayed reduced inhibitory effects against various bacterial strains compared to the standard streptomycin/ fluconazole. The results of the present study demonstrates that electron withdrawing groups at the para position of the aromatic ring in azabicyclononan-9-one moiety exert superior inhibitory effect against various tested microbes compared to the other test compounds and standard drug. The SARs based on IC50 values (table 44) showed that variations in substitution of the aryl groups at C-2 and C-4 position of the azabicyclononane ring may have significant impact on the anti-microbial activity against various microbes. Conclusion The chemical condensation of diversely substituted diaryl 3-azabicyclononan-9-ones with 2,4-dihydroxybenzoic acid hydrazide in the presence of acetic acid provide corresponding hydrazones 109-114 with increased antioxidant potential and anti-microbial effects. Although various hydrazones exerted the free radical scavenging effets in a good dose-dependent manner, compound 109 and 113 were more active in scavenging free radicals than their parent hydrazones and ascorbic acid. In addition, the results of the antimicrobial activities of hydrazones revealed that compounds 110, 111 and 112 possessing para halo (electron withdrawing substitutents chloro, fluoro and bromo) display promising activities against all tested microorganisms. The results of the present study provide a further insight into the structural requirements to develop potential new antioxidants and anti-microbial agents.

Ready to Quit Smoking? Essay

Tobacco is the most preventable cause of death in the United States. An estimated 443,000 people prematurely die from smoking cigarettes. It also causes serious illnesses, such as Coronary heart disease, lung cancer, and oral cancer. 46.6 million Americans continue to smoke despite their knowledge of these risks (CDC). How hard is it to quit smoking? Nicotine is in fact one of the most addicting substances in society. Some people say it is extremely difficult. There are many different ways to quit smoking. The most effect yet, most difficult way is complete abstinence from smoking. Other alternatives include, nicotine gum or patches, medication and e-cigarettes. In order to quit smoking one must understand addiction of nicotine and how it affects the body. The human brain has tiny neurotransmitters called dopamine. â€Å"Dopamine is the brain’s primary motivation neurotransmitter (Polito). â€Å" For example, when you are hungry or thirsty and you finally find time to eat or quench your thirst, that overwhelming, satisfactory sensation is caused by the flow of dopamine released from the brain. Nicotine is an external chemical that passes through the blood/brain barrier that stimulates dopamine. Once there is that chemical dependency on nicotine in order for your brain to release dopamine, it becomes and addiction. There are 4 steps in this addiction cycle. First, a person’s blood nicotine level falls. Second, the brain generates a craving by building up and restricting the flow of dopamine. Third, one inhales new nicotine. Fourth, the brain releases dopamine and the cycle continues. Now that one can fully understand the effec ts of nicotine, the next step can be taken. â€Å"Cold Turkey,† the common term used by smokers, means complete abstinence from smoking. To start the quitting process one must first set a date to quit. One should remove all tobacco products from their persona, house, and vehicle. Then they should tell their friends and family that they are  quitting. Also, it is wise to inform their smoking buddies to not smoke around them or offer them any cigarettes. This completes the start process. In the first five days of not smoking, the number of cravings can reach up to 8 cravings. It is tough to power through. However, there is hope. There is something called, â€Å"The 5 D’s to Quitting Smoking.† The first is â€Å"Delay (CoxHealth).† Cravings only last to a maximum number of three minutes per craving. If the smoker can set a timer and wait three minutes the craving will, in fact, go away. However, it will probably feel like the longest three minutes of their life. The second is ,â€Å"Distract yoursel f (CoxHealth).† If the smoker can direct their attention to something else during their craving, they will have a greater chance of fighting their withdrawals. Perhaps playing a sport, running, or watching television can help distract them from their mental obsession. The third â€Å"D† is, â€Å"Drink water (CoxHealth).† Staying hydrated is essential to fight cravings. Water is good for the body and helps ease the physical withdrawals. The fourth is, â€Å"Deep breathes (CoxHealth).† This refers to meditation and breathing exercises, such as circular breathing. Circular breathing is where one inhales for three seconds, holds their breath for 3 seconds, exhales for three seconds, and then holding that for 3 seconds before inhaling again. The last â€Å"D† is, â€Å" Discuss your feelings (CoxHealth).† These are the fundamental principles to quitting smoking cold turkey. However, there are other ways to quit smoking. Nicotine gum and nicotine patches seem to work just as well as cold turkey. It is a substitute, but it does help stop the habit of inhaling harmful smoke into the lungs. When prescribed these, â€Å"Crutches,† there is a set of instructions that the smoker should follow. They start at a high milligram dosage, then every week the doses become smaller and smaller. It is effective but extremely expensive. Medication can also be prescribed buy doctors. Scientists have come up with a special pill that makes a person sick from smoking a cigarette. It’s a form of negative reinforcement that makes a person not want to smoke because it makes them sick. This is probably not the best way to quit because is extremely expensive. Quitting this way does not yield a long-term effect. It  is only a temporary means to completely quit smoking. Electronic cigarettes are not as expensive but it is still a substitute. These e-cigarettes do tend to break easily and the cartridges need to be replaced every so often, which may become expensive over a long period of time. There is an atomizer in their products the shoot liquid nicotine into the lungs via water vapor. This is not very harmful yet the nicotine addiction remains. When smoking these e-cigarettes there is no real plan to quit. Instead it is just to maintain a healthier lifestyle. Smoking is by far the worst and hardest habit to stop. It is expensive and creates harmful repercussions. Cold turkey is probably the best way to quit due to the fact that it is natural and inexpensive. However, it is not the only way to stop smoking. Alternatives like nicotine gum and patches, medication, and electronic cigarettes effectively stop the habit of smoking. In retrospect these seem to be temporary unless following a solid plan to completely stop. There can be no definite way to stop smoking. The choice is still always up to the person who wants to quit smoking, where will power plays an important role to smashing this horrible habit completely. Work Cited CDC. â€Å"Tobacco Use.† Centers for Disease Control and Prevention. Centers for Disease Control and Prevention, 16 Nov. 2012. Web. 22 Feb. 2014. CoxHealth. â€Å"The 5 Ds to Quitting Smoking.† CoxHealth. CoxHealth, n.d. Web. Polito, John R. â€Å"Tobacco Company Deception Aboutchemical Addiction to Nicotine.†Nicotine Addiction 101. Nicotine Cessation Educator, n.d. Web. 18 Feb. 2014. â€Å"Using the Nicotine Patch, Nicotine Gum, Nicotine Nasal Spray or Nicotine Inhaler.† – American Family Physician. N.p., 1 June 2001. Web. 24 Feb. 2014. Nordqvist, Christian. â€Å"Electronic Cigarettes Can Harm The Lungs.† Medical News Today. MediLexicon International, 3 Sept. 2012. Web. 23 Feb. 2014.

The Secret to Ivy League Common App Essay Samples

The Secret to Ivy League Common App Essay Samples How to Choose Ivy League Common App Essay Samples Schedule your time accordingly in order for your application reflects your very best effort. No crashes and bugs ought to be detected. The Common App offers you 650 words to explain anything you haven't had the space or opportunity to communicate in the remainder of your application. The Debate Over Ivy League Common App Essay Samples You just need to modify your app. If your app was rejected as a result of a metadata issue, you can resolve the matter and resubmit the same build. The Common App is just useful if people may find and utilize it. Completing the Common App is hard. To help you further, look at our set of Common App examples to observe how a great essay is structured. Picking the story is simply the very first step. Or you can find with three other ideas that offer a skeleton. Brainstorm thoughts and see what arises. The level of your ingredients also crea tes a huge difference. The internet application lets you create unique versions of the application for unique schools, and the site will also keep an eye on the different application requirements for the various schools to which you're applying. The good thing is that it's possible to take immediate action to accomplish improved outcomes within the constraints of present rules and regulations. After a fair amount of time, return to the application and attempt to continue to the signature page. Choosing Ivy League Common App Essay Samples To explore system requirements, users want to leave the homepage and locate a link provided at the base of either the registration page or among the various log-in pages. Normally every time a user clicks a hyperlink to a site, the site opens in an internet browser. With the addition of a BROWSABLE intent filter, you're saying your app can be started by means of a user clicking on a web site url. Before your app can be published, you are in need of an assortment of information to finish the procedure. What the In-Crowd Won't Tell You About Ivy League Common App Essay Samples Identifying your pre-professional interest on the application will make it possible for your advisors to supply you with a large array of support to see your objectives. Below, you will discover the top ten common web application design mistakes and the way to prevent them from hurting your customer overall engagement. The genuine application procedure and the time period for university has to be well organized. Obviously, among the most important elements of the application procedure to review and prioritize is deadlines. What You Must Know About Ivy League Common App Essay Samples Thus, do not procrastinate and get the most out of your time before school starts! If you don't have sufficient current knowledge in the region of your Spike, then it is not Spikey, and you need to strike it off the list. Even when you had to receive a job to he lp pay bills or stayed at home to deal with your younger siblings or sick relatives, make certain you communicate your commitments. If it is not aligned, then it is not Spikey so either find a means to receive it aligned or strike it off the list. See if there's a specified homeschool admissions counselor at every school. It's important to choose the perfect colleges. Try to remember, admissions committees might not even consider incomplete applications. So so as to open the door to many institutions in the nation, the Common Application now allows schools that don't have holistic admissions to become members. The essay is a significant portion of the college application process, made only more so by the growing number of students applying to college in america each year. Application essays are utilized to learn why it is you're enrolling for your preferred course. Where your private essay goes out to all the schools you apply to, supplements are targeted and just visit a single school. Understanding what the essay is and the way it fits into the college application procedure can help students understand the things that they have to do to be able to compose an essay that's an asset to their application. Starting early will enable you to perfect your essays, and earn a statement about you. Two new essay options are added, and a number of the previous questions are revised. Share an essay on any subject of your pick. Be aware that a few schools need supplemental essays as well as the typical essays in the app. Some colleges or universities supply you with a list of essay questions but in many instances, you are going to be given the chance to think up a fantastic essay question and topic all on your own and then write about doing it. Many students fall in the trap of attempting to compose a full autobiography in 650 words. The Nuiances of Ivy League Common App Essay Samples Utilizing the Common Application website, figure out which forms you'll require. Students also have the choice to select, I don't know which Visa I'll hold. When you must submit your Common Application will be contingent on whether you're making an Early Action, Early Decision or Regular Decision application. The Common Application, also called the Common App, will be your very best friend during the college application procedure. If you wind up making major modifications to your academic course schedule, be certain t o notify the colleges you applied to. College applications can be intimidating, but with a couple of basic measures it's possible to locate the proper attack. Describe your educational rise and development via your school years. Use this down-time to acquire in addition to your college admissions game program.

Atomic Bomb Essay example - 1218 Words

The Manhattan Project nbsp;nbsp;nbsp;nbsp;nbsp;The Manhattan Project was and is still one of the most secretive projects ever created in United States history. The purpose of the Manhattan Project was simple: to build; test; and unleash its power if necessary. Robert Oppenheimer and General Leslie Groves were the two men put in charge of this mission. These two men along with the top scientists from around the country were brought together to construct the most deadliest thing known to man. nbsp;nbsp;nbsp;nbsp;nbsp;The project originated in the Pentagon in 1942 when General Groves was told, by the White House, he was to lead the Manhattan Project. World War II had already been raged for three years when the Nazis, after being†¦show more content†¦One thing that was not found inside these borders though was women, not even wives of the scientists. No scientist was allowed to talk to anyone outside the camp about what they see, hear, taste, or even smell. Everything they knew belonged to the army now. Everything they knew from here on was highly confidential. There job was to create the atomic bomb and to do nothing else but that. They were to refer to bomb as the gadget or devise for security reasons. The scientists were given 19 months to complete their mission. Most of them complained that it could not be done, that it was not enough time. nbsp;nbsp;nbsp;nbsp;nbsp;Under the leadership of Oppenheimer the work and research began. After several days, their work got them no where. They were faced with the problems such as weight, velocity, and detonation. To make such a bomb they needed materials heaving enough to weight tip the biggest cranes in the world. Late one night, while eating an orange and talking to another scientist, Seth Neddermeyer (a scientist) thought of an idea called implosion. He got the idea from the orange he was eating. This was probably the one idea that the atomic bomb is centered around. Without implosion, the atomic bomb could not be created. When he squeezed the orange, juice squirted out or an outwards explosion. If you can reverse this process, then the explosion goes in creating a even bigger force. This theory applies to Plutonium.Show MoreRelatedThe Atomic Bomb1214 Words   |  5 Pagessurviving an atomic bomb is a perfect example of surviving.. A man with a miracle on his side. His story b ecame famous throughout the world. This man had the courage to tell his story to the world. Surviving the two atomic bombs is not a small thing to comprehend. Therefore, it would take a man who had the courage and integrity to survive it all. On August 9, 1945, the B-29 bomber wedged through the clouds in a Japanese city of Nagasaki that unleashed a 22-kiloton plutonium bomb known as â€Å"FatRead More The Atomic Bomb1719 Words   |  7 PagesThe Atomic Bomb Albert Einstein predicted that mass could be converted into energy. This was the basis for the atomic bomb. 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