20160428b BO Sapporo - 北海道大学触媒科学研究 ...pcat.cat.hokudai.ac.jp/class/me2016/20160428b_BO_Sapporo.pdf · Advanced Course in Molecular Environmental Science 4 format

2016/04/28—Advanced Course in Molecular Environmental Science 1

April 28, 2016

Advanced Course in Molecular Environmental Science 2

Advanced Course in Molecular Environmental Science I

Division of Environmental Material Science, Graduate School of Environmental ScienceThe first semester of Fiscal 201610:30─12:00, Thursday at Lecture Room D103

Bunsho OhtaniInstitute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan011-706-9132 (dial-in)/011-706-9133 (facsimile)

[email protected]://www.hucc.hokudai.ac.jp/~k15391/


objectives/goal/keywords

objectivesUnderstanding of scientific methods based on the studies onchemicals and environments. No transmission of knowledge inchemistry or environmental science is expected.

goalTo find a way of thinking and to understand fundamental scientificmethods for better interpretation of chemistry and environment

keywordsEnvironment and chemicals, Scientific methods, Fundamentals forchemical research

topicsfuel cell: mass communication and scientific articles/microwaveoven/identification of chemical substances/dioxin/climbing MountEverest/A map of European countries: taking laboratorynotebooks/triple crown in science/jamming up in buses: originality inscience/diet control products and methods: ethics/recycle


format

• Answer several questions in each classes. Any answers areevaluated if meaningful. Answers in null correspond justyour absence. <30%>

• A quiz, leading to and encouraging understanding chemistryand/or science, has to be submitted in the end of this course.<50%>

• Students have to submit "a question" with each nickname toProfessor Ohtani and impression/comments after each classand vote for "question and answer". <20%>


schedule

(1) Apr 14 introduction with introduction(2) Apr 21 mole and Avogadro constant(3) Apr 28 necessary and sufficient conditions/Mt. Everest(4) May 12 microwave oven/Internet(5) May 19 originality in science/fake(6) May 26 experimental notebook(7) Jun 16 blood type/chi-square (chi-squared) test(8) Jun 23 cell(9) Jun 30 triple crown(10) Jul 7 recycle and ecology(11) Jul 14 green-house effect/correlation(12) Jul 21 recognition/XXXed(13) Aug 4 presentation of quiz(14)(15)


Ｑ

What is the substance (shown in chemical formula), not a mixture of compounds, in largest amount in this room not including walls, ceiling and floor?

How much moles is it?

What is the element in largest number of atoms?How many is it?

substances (shown in chemical formula)


• inner volume of this room• air: ca. 80% of nitrogen (N2) and 20% of oxygen (O2)• 1 mol of gas: 22.4 L at 273 K/24.5 L at 298 K• wooden materials = cellulose (molecular weight?)• iron-made materials = density (ca. 8 g cm-3) and molar

mass (ca. 56 mol-1)・ human beings are made of chemical compounds• Approximately 60% of human body is water (80% in baby).• approximately 85% in a brain• Possibly, water is the largest in molar amount, but depends

on the number of students.• Hydrogen atoms may be the largest in number

calculation of molar amount


measurement of Avogadro's constant

• prepare a solid sample of pure substance• measure density (volume/mass) of the sample: V (m3 kg-1)• measure number of relative weight of atom in the sample,

atomic mass: u (kg mol-1)• measure number of atoms included in the sample: n (m-3)

Avogadro's constant, NA (mol-1) =

V × u × n


done!

• secondary-cut hair: 1.506 g• 24.8 g for 598 pieces/9.8 g for 218

pieces = 0.0432 g• total number:

ca. 35,000


requisites for a researcher

with basic facilities

• fundamental knowledge and skills• communication skills (not only in English)• just doing it, without looking for the reason for not doing


Photocatalysis

Q Do you know "photocatalysis"?Q Do you know examples of application of photocatalysis other than (1)

photocatalytic decomposition and/or (2) photoinduced superhydrophilicity?

regular PVC Teflon-coated titania-coated

after exposure outdoor for 5 months

air purifier

pipecolinic acid 12

redox-combined photocatalytic reaction

example: photocatalytic synthesis of pipecolinic acid (PCA) from L-lysine

L-lysine ($1/1 kg) → PCA ($500/1 g）

pipecolinic acid 13

photocatalytic synthesis

oxidation of amino group by h+

hydrolysis of imines to give aldehyde or ketone

Schiff base formation by dehydration

reduction by e-

-H2O

HN NH2

COOH

H2N NH

COOH

-H2O

H2N NH2

COOH

H2O -NH3 H2O -NH3

HOCNH2

COOH

H2N O

COOH

N COOHN COOH

NH

COOH NH

COOH

pipecolinicacid (PCA)

cyclic Schiffbase

L-lysine (Lys)

2e-, 2H+ (Pt)2e-, 2H+ (Pt)

2h+ -2H+

pipecolinic acid 14

N

HN

NH2

O

NH2

ONH

COOH

O COOH

NH

NPh

HOOC

H

N

NH

O

NH NH

HN HNCl

H

H

H

HCl

O

ON

NH PhO

inhibitor of protein kinase C

Perumattam, J.; Shearer, B. G.; Confer, W.; Mathew, R. M. Tetrahedron Lett. 1991, 32, 7183-7186.

2 steps 8 steps

local anesthetic (Astra, Sweden)

Federsel, H. J.; Jaksch, P.; Sandberg, R. Acta Chem. Scand.

Ser. B 1987, B41, 757-761.

antitumor antibiotic DKP593A

Gitterman, C. O.; Rickes, E. L.; Wolf, D. E.; Madas, J.; Zimmerman, S. B.; Stoudt, T. H.;

Demmy, T. C. J. Antibiot. 1970, 23, 305.

several steps

mycotoxic alkaloidVerruculotoxin

Martens, J.; Scheunemann, M. Tetrahedron Lett. 1991, 32, 1417-1418.

3 steps

angiotensin conversion enzymeinhibitor

Flynn, G. A.; Giroux, E. L.; Dage, R. C. J. Am. Chem. Soc. 1987, 109, 7914-7915.

L-pipecolinic acid

fine chemicals from pipecolinic acidRopivacaine


identification: molecular mass

Ｑ

What the molecular mass of, e.g., 160.05 for a certain compound means?

Ｑ

Why figures after the decimal point appears?


basic requirements for identification

in the field of organic synthesis

• elemental analysis data matching within 0.3% = giving formula like C10H8O2

• NMR spectrum reasonable for a given structure or coincidence with that of an authentic sample

• milli-mass data


milli-mass spectroscopy

• any atoms except for 12C has after-decimal-point atomic mass• distribution of isotopes

C10H8O2 = 160.052430C9H8ON2 = 160.063663

atom atomic mass abundance atom atomic mass abundance


photocatalytic reaction of naphthalene by titania

no reports on elemental analysis: gas chromatographic data onlyrequired matching of elemental analysis within 0.3%

problem in photocatalytic organic synthesis

OH OHCHO

CHO

both of them are of C10H8O2 = 160.05

in original report in revised report


gas chromatography

impossible to IDENTIFY substances by chromatography


necessary and sufficient conditions

• no sufficient conditions for identification• only necessary conditions/we don't know how many necessary

conditions

if this is the object compoundmolecular weight should be ...elemental analysis should be ...NMR spectrum should be ...infrared absorption spectrum should be ...

(ONLY) probability is HIGH = no proof

A

B

CD

E

必要条件

十分条件《真理》

nc

sctruth


Mount Everest

Party of Nihon University 1995http://www.everest.co.jp/everest95/nu-ev95.html

ridgethree climbing routes

summit


Japanese climber arriving the summit 3 times

Mr. Yasuo Kato

(1) 38th in the world/October 26, 19734th for Japanese/first time in autumn season/due to bad weather 13 fingers lost

(2) 105th in the world/May 3, 1980climbing with a VTR camera

(3) 135th in the world/December 27, 1982died on the way back


Mount Everest

ＱWho was the first summiteer(s) of Mount Everest?


the first SUMMITEER

English party: May 29, 1953Edmund Hillary (New Zealand) and Tenzing Norgay (Nepalese Sherpa )

Definition of SUMMITEERarriving the summit and coming backIf this is limited to only "arriving the summit", it is impossible to decide who is the first summiteer, since

Mr. George Mallory, who said "Because it is there", tried to summit in 1924 with Mr. Andrew Irvine, butfailed. In 1999 the Mallory and Irvine Research Expedition, sponsored in part by the TV show Nova andthe BBC, and organized and led by Eric Simonson, arrived at Everest to search for the lost pair. Guidedby the research of Jochen Hemmleb, within hours of beginning the search on 1 May, a frozen body wasfound by Conrad Anker at 26,760 feet (8,160 m/at 180 m down to the summit) on the north face of themountain. As the body was below where Irvine's axe was found in 1933, the team expected the body tobe Irvine's, and were hoping to recover the camera that he had reportedly carried with him. They weresurprised to find that name tags on the body's clothing bore the name of "G. Mallory." The body wasremarkably well preserved, due to the mountain's climate. The team could not locate the camera. Expertsfrom Kodak have said that if a camera is ever found, there is some chance that its film could be developedto produce printable images, if extraordinary measures are taken.

http://www.nepal.co.jp/rne/news/MIURAHI/miura2.htm


summiting

ＱHow can you prove the summiting?


fake in movie

Capricorn One (UK, 1977)

First trial to reach Mars with fake of NASA ...


requisites for a researcher

with basic facilities

• fundamental knowledge and skills• communication skills (not only in English)• just doing it, without looking for the reason for not doing• double check: humility (modesty) for one's work


climbing route

• three routes (ridges) to the summit

• no way for traverse• passing A followed by passing B

proves summiting

A

B

C

summit


comments on this lecture and question

Please send email in Japanese or English within 48 hours

to: [email protected]: me20160428-XXXXXXXX(your id number)

[email protected]<full name><nickname><comments on today's lecture><question(s): at least one>


sample mail

to: [email protected]

subject: me20160428-12345678

me20160428-12345678

[email protected]

大谷文章

某教授

今日の講義ではなぜ講義名が「分子環境学特論I」なのかはわかりませんでしたが，これからの講義がすこし楽しみです．

先生はなんでそんなに男前なんですか．

Documents

20160428b BO Sapporo - 北海道大学触媒科学研究 ...pcat.cat.hokudai.ac.jp/class/me2016/20160428b_BO_Sapporo.pdf · Advanced Course in Molecular Environmental Science 4 format