STUDY ON THE HEMICELLULOSE OF FORMOSAN BAMBOO

了農休學報
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
STUDY ON THE HEMICELLULOSE
(159 )
OF FORMOSAN
BAMBOO (Sinocalanus Latiforus
hy
Hoang-Hwa Yang
ACKNOWLEDGMENT
Tbe writer is deeply indebted to profo5sor F. K. Ho for valuable suggestion and
吧。rdial
instruction and to Mr. C. H. Hschi , Mr.
J. c.
Su for helpful advice and assistance
throughout the experiment.
The writer wishes to express
bi~
sincere thanks to Mr. C. C.
Cha 時
f，o r
his kind
advice and help throughout the fermentation test.
Thanks are also due Mr. W. H. Chang for carrying out the paper p:>t ition chromato-
-g raph.
CONTENTS
1. Irrtroduction.
2. Fxperimenta l.
1,1. Definition and kinds of hemicellul-
2,2. Preparation and analysis of the
oses.
1,2. Propertics of hemice l! uloses.
1 丸 Sohem :1tic
cOncept of the possible
relationship between the hemice lI ulose
andα-ce l! ulose.
1,4. Structure of hemicellulose.
1月.
2,1. Cutting down of the bomboo.
Methcds of investigation of hemci •
llulose.
1 ,6. The substances resistant to hydrolysis of the hemice lI uloses.
1 ,7. Indu strial Importance of Hemicelluloses.
1 ,8. unse t tled problems.
sample.
2,3. Preparation of the hemice l! uloses.
2,4. General properties of the hemicelluloses.
2,5. The estimations of reducing powders
of the hemice Il uloses.
2,6. The examination
0
f the hYdrolysis
products.
2,7. Disussion of the experimentaI results.
Summary.
Li terature Cited.
Summary. (Chinese)
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
( lGJ)
是林學報
L INTRODUCTION
Bamboo is one of the most common plants in Formosa, China , Japan and 1ndia. It
is regarded in our island as an important item for various economical
end~ ，
making poles
for various uses , bucket hoops , cages or baskets and paper-pulp , etc. , and also as ornamentaI plant.
The bamboo sends Out shoots which consis t" of two parts, the culms or stems , and
the sheaths. The shoots, the young culms, are so tender that they can be eaten boiled , and
are greatly esteemed as delidous vegetables by C; hinese and Jap:mese both. The stalks
which are interrupted in their internal Communication by the nodes or joints , are enveloped in a sheath which rises from the lower and of each node. 1n China , Fo rmosa and in
some districts of Japan , paper is usual1y manufactued from the crude pulp prepared from
bamboos a year old. But nowadays papers manufactured from bamboo at Taichung and
1
Zuchia~ have no good quality. The color
Hwa Ii enkang by the magnesium su If ite mothod of
of the papeI is more or less ye Il ow after bleaching. The bad bleachability and black spots
formation after bleaching of bamboo pulp may due to the hemicellulose , lignin and pectinous substances because the kind of ash present was said have no influency on the qua Ii ty
of paper. And lignin , pentosan , pectin contents of bamboo are exceedingly large compare
1.2.
coniferous.~'-' However , recently it was reported that the
with ordinary woods such as
bamboo pulps Were m a. nufactured by Soda Process, have very good qua Ii ty both in 1ndi a.
3 .4 .5. _.. 6
and"'~'~' Chin a.-.
The study of the chemical compositions of the bamboos is , therefore , very important
from the point of view of industrial chemistry and also of biochemistry.
‘
T have !tudied the chemical constituents of the
However , K. Miyake and T. Tadokoro'
shoots
0
f
“ Sasa
painculata, Shibata and
Makino 九 grown
in Hokkaido anrl confirmed the
occurrence of xylan , araban cellulose , glucose , fructose and sucrose , but could not detect
any starch , galactan , and methyl pentosan.
8
Yasuo Sasaoka has investigated the ιarbohydrate of young shoot of bamboo Madake
(Phyllo staobys quiliol FM) by means of hydraulic press. From the yielded exdressed
juice, after treatment with diI ute sulphuric aCid , he suceeded to isolate 1 一(+)- xylose ,.
d-glucose , and glucuronic acid.
.9
\Vhile by same treatment Sitezo-ogrïJ has studied the pentosan of Gulms of M a. dake
and Mosochiku (Phyllostacbyl mìtis) and identified the presence of large quantities of
xylose with lit tI e amount of ar a. binose in thcse hyd.rolysates.
However , so far as writer has learncd , concerning the hemice Il ulose of bamboo onlv
has been investigated by Fritz Hoyer.
This literature , of coutse can not be found in our island. Consequen tI y , the results i s.
quite obscurc. (1n Jo urnal of Chemocal Adstract Vo I. 38, No. 9, 1944 only re ported a. s
fo lI ows:
Hemice Il ulose from wood. bamboo, straw , grass etc.. Fritz Hoyre (to Akt. Ges. fuer
HalbzelJstoff-Industrie , Ger. 714 , 937, Nov. 20. 1941,) (c. f. C. A. 35 8297 1941))
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
是棉墊報
(lGl )
Present study is a smalI attempt to clarify the chemical composition of the hemicellulose derived from culm of Formosan boomboo Mazu (Sinocalanus Latiferus Munre).
1,1. Definition and kinds of Hemicelluloses.
10
This term was applied by
Schulze~~
(1891) to a group of constituents of the ceU
membrane which un Ji ke ce lI ulose , Were soluble in dilute alkali and were readily hvdrolized
to pentoses and hexoses.
Modern work on the hemice Jl uloses has shown that in m05t cases the crude product
obtained by alkali extraction can be resolved into several fractions distinguished by their
extraction solubilities and hydrolytic products , that many to these fractions contain uron ic.
aciòs rather than pentosan , constitutes the dominan t. Such hemicellulose has been proposed
to describe as polyuronides, Ieaving the oIder term hemice lJ uloses for those which yield n()
uronÎc acids on hydrolysis.
Table 1.
The differentiation of the hemice lJ uloes.
|Hemicellul~I
圓4tFBE
E.-oFne
-
圓
圓
圖
l
•
;l
JB.M.
可
I Jr onic
-&LE
••
-l
FZ而言而|
“-
圓、-nu
mcrE
I.M. ,
EE- -An-的 cτBEE-
cellulose fraction
Extractcd by dilute alka Ji
Hydrolysed by hot dilute acid
E恥 u
-qw&心
I~…odcted wi古
arid
Not contaíni ng
uro r. ic acid
Polyoses
Hexosans
Pentosans
Hexoprntosans
Reserves
Ma芷 nan Araban
xylan
IJolyuronides
Cvt9-uroni des
Encrusting
Substance
Pentose+uronic acid
Hoxose 十 uronic add
Pentose+hexose+uro nic acid
|
α叫岫
凹
11I
Ccllulosic Framework
Substance
Xylan Mannan
Glucosan
Hemice l! uloses from variety of plant materials have nOw been isolated and examined
but few general con cI usions can be drawn , the hemice Il ose of woody tissues is almost
always of xylan glucuronide type which has a high ratio of xy!os-e to uronic acid. The
hemice lI ulose fractions from mesquite wood , for example , contain 6 to 12 xylose units to
.,
One of gI ucuronic acid 12
-~， the bark of trees , on the other hand , yield s a hemicellulose of
13 (Frax inus excelsior)
another type , a galactangalacturonide , thus the bark of Ash"'''
gives
20 p~r cent of hemice Il ulose , tbe hydrolysis products of which are mainly galactose (with
Ii ttle mannose an c1 arabinose) and galacturonic acid.
1n addit Ï') n, however , the extr阿 t contaÎns a contribution from the ctllulosic fabric
itself , con;isting of shorter chain poJysaccharides which in situ are oriented aud included
in the ceIJulose mice lJ es or reticulate structure , and kllown as" ce~lulosa r. s均 uronic groups
are believed to be largely absent from ceIlulosam.
(162 )
STUOV ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
是林學報
1久 Properties of hemicelluloses.
Hemice Il ulose preparafions are usually non-redudng, and often more or less soluble or
dispersible in water, though not originally extractab!e by water to any appreciable exten t.
Some may be precipitated from alkaline solution by simple acidification , others only floc-c ulate out on the addition of alcohoJ , acetone, or some similar solvents. They are optically
active , more frequently laevo-rotatory than dextro-rotatory. Stable methoxyl groups , presumably in other linkage , appear to be a characteristic of many polyuronide hemicelluloses
It seems likely that some of the acetyl groups in wood are associated with the hemice lJ uloses. These , of course, cannot be found in preparations obtained by alkaline extractio
ùut are present in fracti ons removed by water from holocelluloses.
1,3. Schematic concept of the possidle relatíonshíp botween the hemicellulose
and α-cellulose 13
~
。
1
on
. 。-
戶吼叫
芥
d
lnmFM 叫
，‘』月
moH
kuusr'
hn-
Fu-- ••
Iy 叩門
ebaz
•• 11sreupb-m
nusIdo-
HO 叫『
pm 一
Increasing chain lenglh
L IGNIN
Shorter choin G
con!oining
Xylose uni!s
Monnoss uni!s
Uronic ocid
un i! s
Me!hoxyl groups
Ccntoining tlle
nonccrbohydrote
ma'eria! of the
c811 ....011 .
Acelyl groups
。 nd
golactose
ond arobinose units.)
(pos~ibly
Borderzonebetween !he hemicellulose ond !rue cellulos Cl
The above figure is the scheme derived by Rouis , E. 、Nïse which indicates that
threshold detween cellulose and hemice lIulose. To obviate schematic difficulties, the designationα-cellulose. ， deserves amplification. It is defined in analytical terms. It is the
alkali-insoluble fibr ous resìdue obtained under carefuly contro lI ed condition fro m mixture
of polysac~harides， such as those of found ìn wood "Cross and Bevan cellulose" or “holoce lIulose". Thus , it is largely“ true cellulose" (with its long glucopyranose chains). However ,
it retains some mannose and or xylose and uronic acid unit as wei l. This “ tru巴 celI ulose"
nlay be defined acadamically in term of a homopolymer i. e. the alkaliresistant glucose
chain in wood.
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocal在 nus Latfiorus Munre)
農林學散
It is obvious then that
αceIIulose
(Hì3 )
and ce Il ulose itself are elusive terms that need
cI ear definition. Either method of definition has its weaknesses. The analytical definition
is dependent on a rigid set of arbitrary definition assu m:es that only glucose
units are present in the resistant ceIIulose chains that there is nO possibility that occasioofα-ce Ilulose
naly mannose , xylose, or glucuronic acid uníts can occur in such chains. The later assumption is entir eI y speculative and may be quite unjustiiied. Ther are no reliable data either
for or againist such a hypothesis.
1,4. Structure of hernicellulose.
s. J.
14 have investigated the structllre
of hemicelluose of Phormium tenax
Mclory~"
(N. Z. Flax) by means of methylation and proposed fo lI owing formula for it.
Hemicellulose of P. tenax.
Xn 1:4 X 1:4 Xn
where: n=9 or 10
2
X = xylopyranose.
I
G= D-glucuronic acid.
X:
4
1
G
The calculated equivalent of the hemice lIulose (2816-3080) in the formula is in good
agreement with equivalent of 3 ,000 actuaIl y found.
1,5. Methods of investigation of hernicellulose.
],5 , 1.
Methods of isolation of hemice Il ulose.
._
. 15
a. O'Dwyer's procedure
Wood is repeatedly extracted with cold 4 per cent NaOH f oIIowing treatment with
water, 0.5 per cent ammonium oxalate and sold 0.2 per cent HaOH, the two former to
remove pectic
substanc 白，
and the later to remove protein , and expendient later found to
be unnecessary sence the nitrogen content of most wood is excedingly low.
b.
Norris and preece's procedure.
Prior to extraction employ a pretreatnetment with hOiling alcohoJic soda (1 per cent
16 with intention
NaOH in 50 per cent eth:mol) a device introduced ' by Norris and Pr巴 ece~~
17 to have
of reducing the polysaccharides in alkaline extract. Süch treatment later shown....'
a serious degradative effect on some
18 preece Jater re cognized
this to be so
hemicellulose-~ ，
and concurred in its abandonment.
c.
Chl orination procedure (Sand and Nutter)
19
The moist sawdust is treated with excess chiorine gas , and extracted with cold 10 per
ce 司t. NH4 0H solution which removes excess chlorine and halogen acids as we Il as the
lignin rendered of the hemice Il uloses is extracted with cold 10 per cent NaOH. The
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
(lG4 )
農村學報
chlorim.tiJn and extraction are repeated fOUl times beiore delignification. and presum 3. bly
hemice lI ulose extraction , are complete.
Extraction of hemice lI ulose from holoce lI ulose.
d.
procedures have noW
b 巴εn
dev己 Ioped
for the complete de Ii gnification of ce I! ulosic
materials , the residue then containing all or nearly all , the polysaccdarides of the ce lI waI I.
...., c 0.... 1- ___:...]..20 ..._....l J.l:.~ "t. _l~..._'1..1......~.' .....c TI!+ ,,__
....7'"____...1- 21
The “ Skelettsubstanzen"" of
Schmidt-~ and the “ holoce lI uJose" of Ritter and Kurth~~ are
___-1
representa扎 ng
the cellulose , ceIIulosans , and polyuronide hemice lI uloses, and which providc
good starting matcriaIs for the study of the hemice Il uloses of hard
woods~
Since their
extraction from such residues can be accomplished by miI d mct Íl ods.
i)
Schmidt's proccdure.
By chlorine dioxide suceeding treatnent to remove Ii gnin he got "Skelettsnbstanzcn H •
ii) Ritter and Kurth procedure.
Sincc Sehmit's procedure required approximately one month for completion(17-26 days).
it was the
d 巴 sire
of Ritter and Kurth to device a rapid method suitablc for routine purp-
Qses. This. ai!ll was achieved by repeated alternate trealments of extractîve free wood with
ch!orine and alcohoI-pyridine soIution , entire operation requiring only the hours for a Il
but a sma lI fraction of
th~
Iignin. The
r巴拉lue
!ater removed by a 30-minute treatment
with calcum hypochlorite solution (PH 7.0-7.5). Thc procedure h o. s a further advant o. ge
()ver th o. t of Schmidt in that the chemicals employed do not offer any serious h J.Z ards.
Haegglund and Sande Ii n's procedure.
iii)
1n
sep巴 ating
in combination
iv)
the work of Ritter o. nd Kurth , substituted acetOne for the ethanoI used
v; ith
pyridine for extraction of the chlorinated sample.
22
Monoethanolamine procedure
Approximltely 2 gr o. ms of extractive free sawdust (GO-80 mesh). whose moisture
conlent 1s known are chIJrinated f or three minutes by passing chlorine gas through a
funneI inverted over the crusible held in position on a suction flask and kept cool with
iccd water. The sawdust is thcn stirred throughly and rechlorinated for two minutes.
The excess chlorine and hyolrochloric acid p lO duced by the treatment are removed by
passing aIc ohol through s o. mple. The chlorine free sample is a Il owed to stalld in contact
with hot alcohol-monoethanol- o. rriine mixture for 2 minutes. Then removed with suction. At
tbis stage the hard woods become deep red the soft-wooùs brown.
The soIvent treatment is then repe o. ted. After thc second solvent treatment , the sample
1S washed with 95 per cent ethanol , fo lI owed by distilled water. The chlorination a nd extraction trratments repea ted until the residue becomc white following chlorinatio n and is
not colored by the addition of hot alcohoI-monoethanol-amine.
The author claimed that by this prced \l re dup Ii cate .holoce Il ulose determin o. t ions can
b 巴 made
On extractive free wood sa.吋 ust in approximatcly three hours. As furthe r advan-
t o. ges , it is stated that the chemlcaIs used emit no offensive odors" and the distinct color
end poinl is obtained , changing from a Ii ght pink or Iight brown to white on removaI of
the. Iast trace oÍ Ii gnin.
STUDY ON THE HEMICELLUIOSE OF FOR.MOSAN
BAMBOO (Sinocalanus Lo~iforus Munrc)
-是林學服
( 105)
有1 尺
v)
Modification of monoethano lJmine procedurc--.
孔10difying
the S. S. Forest Fab. technique Slorch and
Mucll 巴 r
introduced C1 ,: inlO
moist beech wood shaving under reducing pressure. The temperaturc rise was slight , and
the improvement in chlorine absorption marked.
Each chlorination is followed by washing witb
soIvent (Ca
H~O
and treatment with a mildlY
b且已 ic
(OH 站， NH.!_O 日 or
Na!) C0 3 ) fo Il owcd by washing and rechlorination. Subsequently material is again washcd , blcached with NaC [Q (0.5% active C1) for an hour
followed by washing.
Each chlorination required about 30 min. with 20 g wood. The holocellulose content
calculated on a Ii gnill free basis was 76-77% when
NH~OH
Or Ca (OH\2 was used. Holo-
-c ellulose when treated with 0.2% NaOH lost only about 10% of its original weight , but
when such treatment was fo lJ owed by extn. with 4.% NaOH approx. 25% of holceilulose
was removed. A loss of 34% of holoce lJ uiose was notecl when 17.5% NaOH was used.
This inàicates
vi)
anα-cellulose
Sodium
cOntent (free from pentosans) of about
24
43.5克.
chlorit 巴 procedure
The advantages of the shortened chlorite-holoceIlulose procedure are 1) the ease of
manipulation. 2) It s reptoducibility. 3) The relatively slight degr 3. dation of the polysaccharides. 4)
Th 巴 possibi Il ty
of obtaining Iarge scale laboratory preparations. 5) The fact
that it pemits the quantitative separation and the sludy of both the hemice Il ulose and
ccllulose
fractions ，且nd
6) that it
exp~dites
the iso!ation of sma lI amounts of pectic
material found in wood.
Ten-gram sample of air dried unextracted wood prepared by passing through a Wieley
mi lI, arc heated to CooC with a solution containing 50 ml. of water , 50 m I. of acetic acid
and 50 g. of sodiumchlorite. After the initial hcating the de Ii gnification is allowed to
proceed at about 30 0 C for 24 hrs. , the mixture being stirred at intervals. At lhe end of
this period the nearly white , which retained its wood structure was filtered by suction and
washed with ice water. The hemice Jl llloses are removed in any desirable number of fraction
by successive extractions with aqueous potassium hydroxide in an atmosphere of nitrogen.
It was found in this study to begin with 4 to 5% and to end with 24% potassium hydro25
xide. This proc 巴 dure is afterward modified by wise. Murphy and Addieco , A. A"'~; so that
the total chloriting
vii)
p巴 riod
could be shortened to 3 to 4 hrs.
procedure for isolation of hemice Jl ulose direc tI y from wood.
Hemicellulose can be prepared within a singlc working èay and the procrdurc gives
bigher yield s than do the direct mothod previo叫}' described.
By trea ting 525 g. air-dried sugar maple sawdust at 65-75 0 C. with
for 2 hr3. t hen adding 5900 m l.
H~O
88晶 ml ，
205'(]' KOH
and heating the stirred suspensi on for another 2 hrs.
an apreciable fraction of the hemice Il ulose (1) was extracted. The alk. soln. of Hemice Ilulose was filtere cI and 1 was pptd. with an excess of MeOH and bleached with
NaC10立且 nd
AcOH. Hemicellulose obtained in 14.6.% yie ld containcd no lignin , 7.1% ash , 2.0% MeO ,
可6.6%
pentosans and 16.67% uronic anhydride. The remaining wood resiàue , when treat ed
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
(166 )
with AcOH.and
NaCl 。這 anò
是林學報
then extd. with hot aq. KOH by the above method , yield
3.5% 2nd hemicellulose fraction which remained 5.2% lignin , 3.033~ MeO. 77.7% pentosans
and 9.8% uronicanhydride.
1,5,2. Methods of identification of hcmicelluiose.
Id 己 ntification
of component sugars and sugar acids is effected after hydrolysis. usually
by boiling with dilute acid or sOmetimes by pressure treatmen t. Qualitative methods that
ha ve been uscd in the identification of the sugars ordinarily occuring in hemicelluloses
involve mainly thc preparation of osazones or sOme other characteristic derivatives. The
benzimidazole cOm'pds and paper partition chromatography, sbould prove particularly valuable for this purpose. procedures applkable in the characterization of the uronic acid has
been summarized by Norman.
a.
Methods of identification of xylose.
i) prepalation of the osazone.
ii) preparation of xylonic acid-cadmium bromide double salt.
iii)
detection of small amonnts of arabinose in xylose preparations.
After removing the bulk of the xylose by crystallization the syrup (0.5 g.) in 75%
alcohol (6 m l.) is treated with
α-benzy.
phenylhydrazine (0.5 g.). After 12 hrs. arab Ìl:ose
172. 。
benzyl-phenyl hydra í'.:O ne is precipitated and is crysta Ili ged from qcoho I. M. P.
iv)
A simple microbiological method has been developed which pcrmits the determ-
ination of 12 to 50 mg. of xylose in the presence of gIucose , mannose , arabinose , and
glucuronic aciã , with an accuracy of 96 to 104%. It depends on the use of Hansenula
suaveolens (N. R. R. L. No. 838) which ferments xylose quantitatively but not arabinose ,
rhamnose , and glucuronic acid. lnasmuch as N. R. R. L. No. 838 aIso ferments glucose , the
hexoses must be fermentcd prior to its use. Such fcrmentation is effected by Saccharomyces
carlsbergensis (N. R. R. L. No. 379) , which has only a very slight action on
xylo 鈍，
an
error for which due correction may be made27
b.
Tbe
Identification by preparation of benzimidazole compounds.
28，~9，30
procedure-~'-v， vv.
is based on the combination of 1) a potassium hypoiodate
methanol oxidation and 2) the use of O-phenylendiamine as reactant for the characterization of the resulting aldonic acids as benzimidazole de Ii vatives according to the fo Il owing
equatíon.
/1'1
hO
A笠，EINA
(
、 l? 月大_~卅V
門、/
(H 己叫忱→ c H10H(CHO仇久 ~i~~_ 、仆→叫山吼叫 (ì 叫 σ
已可;:扎
泣三
L
心 jG 心叫
M
川O叫叫叫…恤
ι
A州d州枷
ld品.山伽
仕()-叫-
〉
b
σ←…~刊心〈
叫
μ
ι叫叫叭: 一 ο
枷;拉〉〉〉ι 一(例
ι叫叫叫叫吋恥圳叫川。州川州刊川州
)~半一〈吋;
klex怕也叫
4~
O
sμ~(ÅYo- d..;be."t~叫呵。!已
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocaliinus Lαtiforus Munre)
農林學報
c.
Paper partition chromatography
(167 )
31
Louis, E. Wise recently reported , paper plrtion chomatography was applied to the
separation of simple sugars obtained by partiaI hydrolysis of holoce Il ulose , cellulose , and
various pulps.
Arabinose in sma lI amount was found in the hydrolyzates of sugar pine , western white
pine, and Vilginia pine , obtained by heating
0.01 日 !!SO.!.. It s
tographica lI y and by formation of diphenYl hydrszone. M. P.
presence was shown chroma197-200 。
1.6. The substences resistant to hydrolysis of the hemiceiluloses (body X.
aldobíonic acid , and oxy cellulose).
The hemice Iluloses of mesquite wood have been extensively studied by Sand and
12
according modi fed procedure of O'Dwer's method. AII components were accounted
'Gary~-
for armo!!t completely in terms of xylose , hexuronic acid , and ether-linked mGthoxy groups,
together with sma Il but variable amounts of an insoluble residu5 remaining after hydrolysis.
lhis residue , which they described as “ body X" was almost certainly lignin.
The development of method for the preparati on and examination of the hemicelluloses
from wood may we Il be fo lI owed through the sequence of papers by
over the past twenty
y月 ars.
15 extending
O'Dwyer~V
In her earlier work , the hemice lI ulose of American white oak
was investigated. The extraction was fo lI owed just writer has mentioned in the methods
.of extraction of hemice Il ulose. She divibed the hemice Il ulose in two fractions. Fractlon A
(hemlcellulose A) was ohtained by' precipitation with acetic acid , and Fraction B (hemicellulose B) by subsequent addition of 2 volumes of alcoho l. On hydrolysis with 1% sulfuric
acid for 3 hrs , xylose was Ii berated and after neutra Ii zation with barium carbonate, the
barium salt of an acid was precipitated by alcoho 1. The analysis of this salt agrced the
harium salt of an aldobion ic acid composed of xylose and methoxy hexouronic acld.
32
Camp~llV-
has reported Ihat he isolated from the
Sá.p
wO <l d of oak and walnut slarch
that contained acidic groups and was composed of approximately 90 %, anhydroglucose unit
linked to an aldobionic anhydride (probably glucose-glucuronie acid) wbich may be partly
methvlated.
19
However , sand and Nutter
have investinated the hemicellulosc of mcsquite wood by
4
-
the chrolination procedure and found the substance
resj~tant
to hydro!ysis was oxy-ccllulose.
1 久 Industrial Importance of Hemicelluloses.
1,7,1. In t he pulp and paper industry.
There is an increasing realization that this group may be more valuable than hitherto
suppo~cd.
The proccss of isobtion of cc lI ulose from wood , usualIy centers round the
removaI o f lignin. Virtually all industrial delignification p l' ocesses , howevcr, effect at
the same time the removal of hemicc Iluloses to different degrees , according to the
conditions of the treatment and the natu re of wood. It may somelimes be lhe case
that delignification is less complete than the removal of thcse acompanying polysaccharides.
Because the chemistry of the hemice Il uloses is ~till obsc,ure and t "'le determination difficut ,
(lG8 )
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Snoctlanus Litiforus Munre)
是林學報
very few technical studies of their fate in pulping processes have been rnade. (but hem icvú
eI! ulose in sulfite waste liquor had been inve~tigated by Japanese wood chemist , Uchida ).
.、.、
In practice , an apprcciable fraction of the wood rnay rernain unaccounted for , or
unnecessarily discarded. There are rnany purposes for which a higherα-cellulose is not
3壘，35 ，36)37 ，38 ，39
，.，~， vv. on thc
essentia l. It is forshadowed by a number of interesting papers~~'~~'VV)~'
properties and utillization of holoce !l uloses prepared from woo.d, preliminary studies On
the paper rnaking quillities of holocellulose preparations have:given encouraging rewlt. sheet
of good rnechan i<:al prQperHes have been obtained despite the relativelY high content of
non-ce l1 ulosic rnateria i. Holoce Il ulose obtained frorn spruce was processed in a labortûry
beater , its physicaJ characteristice sludied at intervals.
The Jess resistant carbohydrates , which include both polyuronide hemicelluloses and
cellulosanes , have an irnportant influence on the developrnent of a gelatinous hydrate. The
product has good fiber bonding and developed e lC ceptional strength characte rÍ stics. On the
basis of these resu It s , Hontz and Kurth40 suggested that the cooking process in production
of pulps to be use d. for highly hydrated papers should be conducted , in such a rnanner thal
f the hernice lI ulo sic rn'aterials i s retained.
41
1,7,2. Hernicellulose nitrate
as rnuch as possible
0
Atternpt has been rnade to prepare the nitrate of herniceIl ulose. The nitrates obtaineð
by treating hernicellulose with AcOH and HN0 3 and also with H!;!SO-!_
and HN03
containing srnall arnount of H 2 S0 4 arc stable , and no sign of decornposion was seern in S
rnonths.
1,7,3. Films from hernicellulose acetates.
42
Chales L , Smart and Royl. Whisher~" frorn hernicellulose A (1) (A higher rnol . polysaccharide prepared by neutra Ii zigg alk. concob hernice lI ulose upon acetylation with A. c 呵。
in the presence of 0 , 25% HN0 3 produces a w hite fibrous acetate containing 86.6% Ac
groups , when cast frorn dioxane, CsHsN, or CHCls-MeO 日
showing a tens iI e strength of 7.2 Kg/s. g. rnrn.
(9.11λ cI ear
Iil rns are
produ~ed
1.8. unsettled problems.
(1) The structure of hernice lI ulose must be established in rnore sure basis.
(2) Is the conbination between hemicellulose and ligniD entir eI y physical or chemical
!
If it is chernical corn可 ination in what linkage they are combined 1
(3) 1n what rnan ner herniccl1ulose combined with ce lI ulose
1 What is the clear disti-
nction betwecn Cc Il lllosan and hcrnico lI ulese?
(4) rn h~micellu lose rnolecu峙， !\cetyl and methoxyl groups are in what linkage.s combine with othcr groups '1
(5) The structure oí lignin
43 .
must bc established in rnOre sure basis. In Hl 7 , O.
Mueller ~~ in Gaettingen Univcrsity investigating the hernicellulose of beech wood and
advanced the hypotnesis that lignin fragrnent rcrnaining in holocellnlos t! is polysaccharide
in nature and ma y be an aldose condensation product and that the assumption that carbo-
STUDY ON THE HEM1CELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
農林學報
( 169)
hydrates of cell can be determined quantitatively by difference after making a single
lignin determination is erroneous. What may be the fate of this hypothesis?
44
(6) 1s protopectinase and hemice lI ulase identical or not
(7) What is clear relation ship between hemiceIIuloses and cellulosans?
(8) Is the structure of hemicellulose one of relativeI y simple chain molecules or is one
of large chain molecules varying numbers of recurrent?
(9) Hemice lI uloses are presumably derivéd from' starch presumably by oxidation and
32 ,
decarboxylation , or from pectin , but is it reaIly to be so""'?
2: EXPERIMENTAL
2 ,1. Cutting down of the Bainboo.
The spe ci.mens were grown in Zusan near Taichung, and were secured through the
courtesy of Mr. S. Lin.
One year öld (total length 20.7 m. , largest diameter 14.5 cm.) and few years oId (total
length 16.5 m., largest dia meter, 12.0 cm .) of culms of bamboos were cutted down on August
24 th. 1950; from Lamboo jungle. (In each hectre of jungle there are average 1200 stumps of
bamboo). The nodes and sheaths were removed. Each other nodes were collected and weighed.
The s3. mple has total weight of 56.4 Kg. and contain about 85% of water. The sampIe
transported to the laboratory and started. the experiment after 3 days.
2 ,2. Preparation and analysis of the sample.
Sample was cutted longitudinally in sma Il pieces, chipped by scissors in proper sizes.
and passed through a Wiley mi11. From 56.4 Kg. of cI ums, about 10 Kg. of Wood powders
we-r e obtained.
That passe <il 20-48 mesh (mesh to inch) were used for general analysis of the bamboo
and the powder has
48一100
mesh sizes were used for the extraction of the hemiceIJuloses.
The results of generaI analysis of the bamboo are indicated at T AELE 2. Analytical
Results of Sinocalauus Lt iforus Munre.
air dried
basis
water-free
basis
mOlsture
crude
protein
15. 凹%
1.50.%'
1.88%
S 丸 n.c.
cruQe
fat
crude
fiber
crude
ashes
pcntosan
s.n.n.
c.
1.70%
42.26%
2.63.:'-<>'
1-6.27%
20.01%
2.3 %,
. 50.U%,
3.12%
19.32%
23.4 4%
= soluble
non-niterogenous 'com'pd
From above resu It s it may be safely to say that almost all of soluble-non-nitrogeneous
compound s may regard as Ji gnin and the contents of pentosans of the ba,mboo are relatively
1,2. ; i. e. Phylostachys.
sma lI co mpare with other spacies or. varieties of the bamb-oos~'-'
reticulatac. Koh., Bambasa. slenostacya. Hack., phyIIostachys. eawtis.
Th~
sample was further subjected to brief generaI analysis of wood. The results are
indicated at T a. b!e 3.
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
(170 )
ture
crude
ashes
other
extract
15.69,%'
3.12,%'
2.13,%'
mOls 呵
Cross Beyan
ce lI uJosc
54.9;:;,%'
pentosan
TotaI
nitrogen
19.32%
0.30%,
是本「學報
Ii gnin
24.44%
The contents of Ii gnins and pentosans were determined accordlng to the method of
45...
•
...，，~_
"46
Japan~~， and thc procedure of U. S. Forest~~ Products Laboratory,
standard wood analysis of
respectively. The estimaiion of Cross and Bevan's ceIlulose was carried out after the
.壘7
procedure described in the mannual
. 2 ,3. Preparation of the hemicellulose.
Under the circumstance, because
IfO
sodium chlorite were available , choiced the Proc-
edure of Norris and preece.
2 ,3,1. The removal of pectins.
a.
hot water treatment.
1n a flask containg 500 g. of the sample added 3.5 L. of water and heated on a water
80-90。‘ C fQr 15 hrs. The rnixture was allowed to cool , filtered through muslin.
To the transparent filtrate being acidified with glacial acetic acid , was poured with equal
bath at
,
volume of 96,%' eth mo) , a white precipitate was recovered. The residue was further subj•
ded to the same treatment for 1 hrs. , but cou)d not obtain any precipìtate. Yield of crude
pectin obtained fro :n 6.5 Kg. sarnple was 80.2 g..
This crude pectin has been studied sO that not anaJ ", lized.
b.
0.5% ammonium oxaJafe treatment.
The removal of pectin from the residue is completed by repeating extraction with 0.5.%
ammonium oxalatc solution. To the residuea after above treatment add 3.5 L. of 0.5,%'
ammonium oX 3. late solution and were slood for 7 hrs on a water bath at 80-90 0 C.. To the
filtrate 0f the above mixture poured into 10.% cupper sulfate , observed blue precipHates
are forming , but not recovered.
2 ，持久
The removal of lignin.
The removal of lignin of the. above residues was carried out two extractions with
3.4 L. 0 f NaoH, each extraction being carried out under reflux for 4 hrs.. After second
extractio !l, the filtered tissue was further filtered through muslin , excess liquid was again
removed at the press.
2 丸 4.
a.
Tue isolation of the hemicelluloses.
The extraction with 4% NaOH solution.
From 1000 g. of the above resiuethe first extraction of t. he hemicdluloses was carried
()ut with G L. 0 f 4% NaOH so lution. The mixtures were allowed to sl 3. nd for 4. 8 hrs. at
room-temperature with occasionally stirring. The fiJtered extract left standing in the
refriginerator ovei One night at 5 0C. was graclualI y added with constant stirring rather more
glacial acetic acid t. h:lD is necessary to neutralize i t. Observed the hemicellulose correspO!l ding to ' th~ A fraction in O'Dwayer's procedure was precipitating but not separat by
the ce !1 trifuge. Eq 'l ûl volume of 90% a)coh?l is then gradu:dly added with constant stirr Ì:1 g,
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
噩林學報
( 171)
namely , corresponding tO A and B fractions of O'Dwyer's procedure are precipitated toge.ther. The precipitat is then treated with graduaIl y increasing strengths of alcohoI , in the
usual ,way for obtaining a dry product. Drying is completed in vacuo , because no phosphorus pentoxide waS ava iI abie,. drying was carried Out over calcium chloride.
b.
The extraction with 10% NaOH soIution.
The above residue was further extracted with 10%, NaOH soIution , namely , to 2000 g.
of the rcsidue was added 7 L. of 70% NaOH sOlution , and the mixture was aIl owed to
stand für 48 hrs. at room-temperature. At this stage because the viscosity of the soIulion
was very high, so that the stirring was very difficu It. The exfracted solution was fi It ered
through mus Ii n, the filtered extract lct stand over one night in refrigenerator and treat
as before (as in case of the hemice Il ulose A) , the yields of crude hemjcellulose obtained
from 6.5 Kg. of the sample calculated on dry weight 230 g..
The stud y" of the above residue and purification of the hemice I! ulosts were not carried
out , because u nder the circumistance it was quite difficu It to accomp Ii sh.
2,4. General properties of the hemicelluloses.
• The product obtained by this method consists a fine greyish white amorphous rnass.
and more or Iess soiuble or dispersible in cold' water. It is soluble in boi Ii ng water, forming a gelatinous mlSS on coo Ii ng. It is easily soluble in cold 4% HaOH solution. It does
reduce Fehling solution and Is laevo-rotatory, it form gelatinout insoluble copper componnd
ón addition of excess Fehlirig soIution , and the filt I' ate Qbtained is quite transparen t. The
results of the estimations of ash content , specific lotation , pentosans, body x. are indicated
at Table S.
general propertles of the hemicelluloses.
Table 4.
何Aad
的 DX
L
i -t1.
azB
jrLVd(
1Jny
Hemicellulose A
5.07%
,
Hernice I! ulose B
3.98%
78.2。
89.2。
75.67%
6.17%
86. 明%
8. 的%
The hemicelfulosos when dist iII ate with HC1 (sP. gr. 1.06) yield furfural and it may
be regarded as derived from xylan as inèicate in Iater ,. so th'ü lt calculated as xylan.
Because some color tubslances, perphaps Iignin , are lìti lI lemain in the herniceIIulose preparation , the observation of rotation of the hemice I! uloses were very dlfficult.
2 ,5. T he estimations of reducing powders of the
hemicellulose弓.
- In order to ascertain the relation betwcen the concentratio n of di l. acid and the
amount of r~ducing sugars present, each 0.5 g. of the products were subjected t0 hydroIysis with 500 cc. of 0.1, 0.2 , 0.3, 0,4, 0.5, 1% su Ifuric acid in aut oclave , wilhin 20 rnin.
tempe rature of outoclave was rised from 100 0 C to 1500 C and maintained this temperature
(about 4 atmosp:ieres) for 30 min ..
After neutralilltion and removaI of humin substances (Body X) diluled to 200 cc
and took 20 cc for
Betrand's method.
ascertaini 且g
the reducing power of the hydrolysed soIuions in each by
STUDY ON THE HEM1CELLULOSE OF FORMOSAN
BAMBOO (SJßocalanus Latiforus Munre)
(172 )
農林學報
It wer巴 found that:
H 2 SO <t%
reducing power %,
EI!!SO~%'
reducing power%
。f
0.1
86.4
1n case of hemÍc ellulose A,
.0.3
0.4
0.5
88.3
02.5
94 ,4
88.2
1
78.0
0.1
89.2
1n case of hemice Il ulosé B,
0.2
0.3
0.4
0.5
91.0
91.6
94.1
87.3
1
87.8
。.2
reducing sugar reckoned as xylose were obtained.
the relation of lhe concentration di I.
Figure 1.
H~SO"，
and reducing sugar pre.en t .
100
上。
于
,' ,
.
、， r' ‘付。可
101
‘~‘'，〔扎扎，<ß\I ....\O .,
~ ~O
。
0.1
O. l.
o.~
o.~
川、.......____.于diJd3
of i也SCUZ • 1
.-
ω恥的&品n.
2丸 The examination of the hydrolysis products.
Res t. on the basis of above re5u It s to 3() g. of the hemice Il ulose A in autoclave were
hydroyzed with 2000 cc. of O.4_%" H!!S04, solution. Within 20 min. the temperature of
auto c1 ave was rised for 100 0 to 150 0 C. and maintained this temperature (about atmosph-
,
eres) for 30 min.. The hYdrolysed soIution at the end of this time st iII contained a sma Il.
proportion of insoluble matter and has Ii ght ye lI ow color. After sufficient quantity of
barium hydroxide wa 5 added exaqly to neutra !i ze the solution. The solution was further
neutralized with barium
carbonate over
methyl-red-methylene blue.
CPH 5.4) and
fi ltered.
The sohtio ÏJ. being decolorized with charcoal , wa! concentrated under reduced pressure
below 45 0 C. to 5ma)! bulk (50 cc.) and further subjected to the
decolorization.
也 times
volume5 of 95% alcohol was added to it to get rid of. any barium su)f ate remaining, and after
the decolorization and iiltering , a( end of this stage the solution was already in sirupy
ιondition.
The sirup has a light ye lI ow color.
Toe hemicellulose B 27.4 g. Were subjected to same treatment just as before stated ,
the syrup also has. a light yeIl ow color.
A little more alc ohol was then added and the syrups were a l1 0wed to evaporate slowly
1)
ver sulfuric acid in the desicator. Then , the desicator let it stand in . a refrigenerator at
50 C. for
formed.
壘。 hu.
wi th occ 3. síona lIy stirring of the syrups , a white crystalline ma5S slowly
是林躍報
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus La ti[ orus Munre)
(173 )
Tbe proccdure is iIl ustrated at Cbart 1.
hydrolysis
p~oduct
neutralized with Ba (0日 )3 and BaCO J Over
metbyl-red-methylen e blue , allowed to stand
for a while a :1 d filtered off BaSO-!
-
,
A?L
vA
戶LV
-zl at
ryA
BOdy X Or humin
"S ubstance and pp t.
After decolorizalÌon cOncentrated to small
bulk (50 cc.) below 45 0 C. under reducing
pressure: Added 4 times vol~mes of 96X
alcohol and Ul tered off ppt. fOrmed.
of BaSO .•
llla
-4.-
'.A
a'
.•
AV-VA
ρLV
'Pp t. 1.
{fine particle)
Aftcr concentration , a l1 0wed to stand in a
refrigenerator Over One night. Small amounts
咽。 f ppt. formed was [\Itered of f.
Il-
.-'',
....
QA
,
-a
- '"
•••
ave-
抱
，且
叭
P
&ELW
'LV
After concentration and decelorization ,
neutralized i t.
eaVJVA-U nr
•••••••••••
Concentrated unde r: vaccum OVer H:)S0 1.
crysta Il ine mass.
一一-Chart. 1.-一一
'2, 6,1. ppt. 1.
lt consists of fine white particles. 、iVheo it was suùjected to naphthoresorcinOl test
thc result was negative. pp t. 1 when heated in a crusible no chared phenomena was
obs ~ rved.
2,6,2. ppt. ~.
When pp t, .2. was subjected to chl\ r , the white color not turns t o black. On furtber
heating ppt . 2 not disappear and still has a whfte color. ppt. 2 COnsis t of SOme inorgan1c
sait s i s apparen t.
:2,6,3. Tbe exa:n ination of reducing sugars.
The syrups deirved from the hernicellulose A and B have the sweetish tastes and have
light ye Il ow colors.
The syrups were suöjected to general qualitati ve tests of rnonosacchari de , the resu lts
(
STUDY ON THE HEMICELLULO SE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
17基〉
最科學報
are indicated as follow.
a.
quálitative tests of pentoses.
1)
color test of pentose.
i)
Wheeler and .To lI en's tes t.
Hemicellulose A (+ +), Hemice Jl ulose B (+ +).
ii)
Schj ff' 5 tes t.
Hemicellulose A (+ +), Hemice lI ulose B (+ +).
Bual's test.
i ii)
Hemicellulose A (+ +;, Hemicellulose B (+ +).
Rosenthaler's test.
iv)
Hemicellulose A (+ +), Hemicellulose B (+ +).
Van der
v)
test.
Haar'~
Hemice lI ulos t! A (+ +), Hernice lI ulose B (+ +).
2)
color tests , of methyl pentose.
i)
Widtsoo and Tollcn's test.
Hemice]]úlose A (一)
?,
Hemice lI ulose B (一)1.
Oshima and Tollen's tes t.
(一)， Hemice lI ulose B
i i)
Hemicellulose A
(一).
Maquenn's test.
iii)
Hemice lI ulose A
(一)，
Hemicellulose B
(一).
AIl the color tests of pentose were predominately posi tive for its presences, while
in cases of methyI pentose were negative.
It will be safely to say that becaus~ of the simultaneou's presence of large amounts
of p t" ntose , those of meth yl pentose were greatèiy inhibited.
b.
qualitative tests of hexoses.
1) fcrmentation tes~.
，~ _,_'^ __.t..^.l _48
The syrups were diluted and subjected to Lindner's micto methode~V by means of the
fernientative power, of “ Press-hefe Rasse 12".
Both syrups derived from hemicellulose A anb B were stronly fermented. Consequently.
the presences of zymohexoses in the syrup are apparent.
2)
the color
t 巳sts 0
f ketose.
The diluted syrups further were s1bjeced to the color tests of ketose. The results is
as follow.
i)
ii)
Pinoff's teS t.
Hem~ce Il ulos e
A
Seliwano 日 '5
test.
(一)，
Hemicellulose A (-),
iii)
Hemicellulose B (-).
B
(一).
Hemicellulose' B
(一).
Hemicellulos~
Ihla-Pechmann ,s test.
Hemice lI ulose A
(一)，
是本嗶報
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
( 175)
'The results indicated nO ketose is present i n the syrups.
3) the oxidation of the syrups by HNO s .
D-galact o肘， l-galactose , and d-galacturon;c acid , when are oxidized , produce music
.acid. The syrups were 5ubjected to music acid test, but the results were negative.
c.
quaLitative test of utonic acid.
The syrups were further subjected to naphthoresorcinol test , but the results were
-nega tlvc.
舍， 6， 4.
the .solapiöns Jf d-xylo$e.
As illustrating in Chart 1. the syrups derlved from hemiceIlulose A and B 1n desicoator wHh occationally sti rring, the whi te crystalline masses were sIowly fOrmed.
Yields of crystaUine masses from hemicellulose A 35 g. and hemice Il ulo切 B 27.4 g.
were 18.2 g. and 15.2 g. respecti vely.
The crystalline mass d;ssoIved if 95% alcohoI and a lI owed to stand in a refrigcnerator
-w ith occasfona Il y st; rring, graduaIly pr!sm;c crysta Il s formed.
25
They melted at 1 品145 0 and [α] î)= +30.4 0 Cafter 20 mi n.), +28.?0 (after 37 min.) ,
+25.2 0 Carter 40 min.) , +24.3 0 (after 50 min.) , +22.6 0 (after 60 min.) , +19.6 0 (70 min.) ,
+19.6 0 (80 min. ),
_ ~20
r
. _.
49
According to Brown~v xylose has [α] D == +85.9 (after 5 min.) , and this value gra.dua lI y decrease with time. After 2 hrs. it showsa consUint vaJue +18.6. 。
~2~
,
. ,
50 .,.
However , Schulze and To Jl en~~ indicated for xylose [α]D= 十 19.248 (p=10.0829) .
VA
51
was carri 芒 d out. Each 1 g:
As a !lil'ans of further fdentification , Bertra口 d's reaction
of the white crystalline masses derived from the hemicellulose A and B , were mixed with
r
-2 .5 g. of cadmi um carbonate and gradually with cooling mix f' d wi th 2 g. of bromine. The
mixtures were sl] owed to stand for 20 hr 鼠， then bro~ght to boi lI ng point and the 心 residue
washed with bOiling water. The fi It rates- were mixed 'w ith alcohoI and the salts-came out
in chara cterlstic boot-shaped crystals. ( (C S H 9 0 G)!!Cd-CdBr:!-2H 2 0).
By the properti es of melting
po 泣，
specific rotation and formation of the double
.cadmium salt of xylose as ind Î' cated above , the crystals were identified as xylose.
2月 .5.
a.
the examination Of other sugars.
the pr<!paration of the osazOnes.
Each Of 1.5 g. of the sylupy crystaIline masses derived from hemice lI l,ilose A and B,
were mixed with 3.5 g. of phenyl hydrazine, 3 cc. of glacial acetic acid , and 25 日. of
watér. Af te r ha If an
h孔，
no precipitation takes pJace , so that no t race of mannOse is
present. The mixtures were then heated On the water bath for 1-1/2 hrs.. A little turbid
phenomena was observed. so thqt trace of glucose may present. As mentÎJncd a bove , by
fermentati on test had alreday identifi 巴 d the presence of zymohexose in the syrup, whi le
the ketose and music acid test were all negative. 3nd nOW indicat~ nO trace of mannose
i 5 present Î' n the syrups. CO !l sequently , gJucose must a compo且 ent 0 f both hemi cellulo se A
and B. This fact was further
(onf~rmed
as below by paper chrom "l tography.
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocali\nus Latiforus Munre)
(176 )
農林學報
On cooling large amount of xylose osazOne came out in ye lI ow crystáls.
b.
the preparation of arabinose-diphenyl-h ydrazone.
After removing the bulk of xylose by the crystallization on the syrups in 75% alcohoT
dipheny~ hydrazìn whichhave been dissolved in ethanol , and let allowed to'
Were treated with
stand in the refrigenerater for 24
hr 丸，
the whi te crysta Is were appeared. Under microscope ,
they have needle shapes.
,
c. the analysi S by paper patition chromatograph.
The syrup derived from hernice l1 ulose A and B after removing the
subjected to one dimensionol
pap~r
bu 此-
of xylose ,.
patition chromatograph (ascendirig rnethode).
The relults are indicated as fo l1 ow.
substance idenified
BuOH-AcOH-H20 (4: 叫|戶…01 satd. wfth H20
color
Rf
glucose
Rf
a. bright brown
b_ dark brown
c. brownish ye lI ow
0 .1 5
xylose
‘
VA
0.4壘
M山 d
FLPM
盟國
O.a.
nuρv
EAu
、‘'，白，
。一oh利
arabinose
mm聊
{l
do-n
a.b.c~
rcny
Eh--
0.37
wn
LUVA nv
color
a. bright brown
b_ da rk brown
c. browni sh yeIl ow
a. red
b. chocoIa te brown
c. pink red
a. red
b. chocoIate brown
c pink red
a. color develOped with anilin hydrogen phtha.late.
b. color developed with benzidine.
c. color devdoped withα-naphthyl amine .
By the above results , the prcsenccs of small- amounts of arabinose and glucose in the
hemicellulos 巴 A and B were con fÏ rmed.
syrups derived from
2久 Disussion of the experimental results.
52
K.Ono~-
has investigated the components of the hemicellulöse of bagasse and found
the chief product of hydrolysis was xylose. He reported the hmicclluloses Were very rese53
. mble to Esparto-Xylan (accordi l} g tO Haworth~v.
Esparto-Xylan has a structure, arabofuranose- (xylos e)lf_' 7 xylos ~ ).
54
\V hile H. kurr.sawa ~~ has stud ied the same subject and concluded the sma lI amounts
of
arabinos~
were present i,n the hemiceIlulose. Except xylose and arabinose, he also
insisted that sma lI amounts of dextran (gIucosan) may be simultanously p.rcsent.
However , the he m icellulos~ A and B of the Formosan bamboo , cOntain 75%. and
85%. oí pentosans , respectively and those chi ~f compOnents are apparently xylo se. Except
xylans. writer has co nfirmed the s~multaneous presence of small amount of arabinose.. and'
dextr l\!l. (glucosan) in the hemicelluloses.
The above resuIts is very interesting and found out that the hemi'C elluloses of
th~
農林華報
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Lat Îf orus Munre)
( 177)
bamboo are very resemble that of the b a:gasse.
Furthermore , this results coincided with the results of the study of pentosan of the
.9
culms of Madake by S. Ogri~， except the fact th 1\t in the components Of the hem~ce lIulose
of the culms of the bamboo , there is a glucose unit.
As mentioned above, although the hemice Il uloses contain A and B fraction correspondtng the hemice Il ulose A and B of O'Dwyer's
prosedu 時，
COnsequent旬，
but not separated.
it ilì 'quite difficult to cOnclude nOw that whether the glucosans in the hemiceI1 ulose were
derived from ce lIulosan origin or not ,
The hydrolysis of the hemice I1 uIO$es were carried out under pressure treatment ,
Sl)
that whether the uronic acid in the hemicellul o"ses wcre decompOsed during the processes
or not is quite in question. but $t iJl it is interesting that the uronic acid iS not present
in the hemicelluloses of the culms of the FOrmosan bamboo.
As for the chemical reaction which Occurs in tlie hexose in the pla:l t thissues it was
assumed that first the CH 208 groúp of thé inolecule was attacked to convert the carboxyl
,
tran~formed
group by partial oxidaqon ln forming Iycuronic acid which was secondarily
H
OH
O
可
08
J
。
H
,
lE
竄
1
H
pt-E O
一-
1 r
OH ß
‘
0
,
IC
F』
1
H
r
Hlι!u
J
CHO-C一 C-C -C-C誼'lOH'- →
干!侃
r
OH 08
mi
08 H
IB
侃{」
into 1 (+) xylóse by the spIitting-off of CO 2 from the molecule.
CHO-;-Ld-cnqOH+CO2
H
OH
H
Thus, 1 (+) xylose in the plant resulted from. d-glucose, and glycuronic ácid stands
as an intermediate state in this transformation.
The fact which has been mentioned by many chemists that d-giuco 耳 e and galactose
háve almoSt always been found in nature with 1 (+) xylose and 1 (+) árabinose s40uld
account for the formatioa of the pentoses by the metabolic changelì of the hxoses in
plants ,
'
. uu
Moreover , it is a notoworthy fact that glycuronic acid.55
which was described as an
intermecli ate produ~ct of glucose metabolism in nature , was isolated from the expressed
juice of the shoots-. Confirmation of this substance was made by determining the rotary
power of its lactone , m, p , 166-90 [α]0 = 18,64-1 , 60 and aIso by transformation into the
barium salt of phynyI hydrazone , m, p , 192 0 and hydrazone , m, p, 1 81 。
Consequen tI y, the results aIso conf ifmed the view that although the relatively Iarge
amO ü. nts of h凹的嗨， gIucuronic add , are present in the shoots of bamboo , the contents are
gradua Il y reduce in accordance with its growth and in the culms of the hamboo , only
pentoses are predominantly presen t.
STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latforus Munre)
(178 )
農林學報
SUMMARY
Aecoràing to the procedure of Norris and Preece , after removaI of' crude pectins by
hot water， υ.5% ammonium oxalate treatment , the hemice Il ulose A of Formosan bamboo
(Sinocalonu s Latiforus. Munre) was extracted by 4% NaOH soIution. The a.bove residue
was further extracted with 1O,%' NaOH soIution and obtained the ~emice lI ulose B.
1. Thè hemice Il ulose A has ash contents 5.07%[α] 25::::: -78.20 'wh iI e the hemicellulose
B has ash contents 3.98% [α ]2 5=-89.2。
2. The hemice Il uloses compOse of two fract ions corresponding to O'Dwer's hemiceIlulose A a. nd B.
From the hydrolyzates of hem icc Il ulose A and B. d-xylose was isolated by crystallization. The pr~smic crysta lI s melted at 142-145。﹒ [α]26 = +19.6 0 (after 70 min.).
3.
Cajmiumbromoxylonates were prepared.
Furthermore in the hydrolyzates of the hemice lI uIse A a. nd B, except d-xylose. a rabinose a !l d gIucose Seem to be presen t. This fact was furth f!r. confirmed by paper patition
chromatography.
However. tbe ketose tests (Se Ii wano 丘， Pinoff etc.) were negative , and could not find
of any other pentoses Or hexoses in the hydrolyz a. tes.
presences
the
4. Tbe hemicellulos~s A and B may compose of either compound 0'1' mixture of 85%
-x ylan with smal J' amounts of araban and dextran. To darify the structure of the hcmicellu!ose of the Formosàn :bamboo. further study i 5 necessary.
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Bl向gard.
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~
universi 旬，
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939 (1 931)
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(1 892 )
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STUDY ON THE HEMICELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
農林學報
12. L. Sand and W. Y. Gary. J. Bio l.
Chem. 些.!:
(179 )
573 (1933)
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ibid.
20 656 (1926)
ibid.
~
381 (1928)
16. Norris. F. W. aud Preece. 1. A. B iOchem. J. 24 59 (1930)
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18. Preece I. A. B iochem. J. 34 251 (1940)
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S 啪叫 b t.
E.
B 侃 D.
Cbem. Ges. 54 1861
(1 凶 1)
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22. Mitchel l. R. L. and Ritter G. ]. J. Am. Chcm. Soc. 62 1958 (1940)
23. VOnk. Storch , und O. Mue Il er. Papier-Fabr.
(1939)
24 LOuis E. Wise. Inð. Eng. Cbem. Anal.
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Add 耽 0，
~
Tech. Wiss. II. Heft 26. Juni 213-220
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~
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27. Louis. E.
Wi 鈍，
and JObn W. Appling. Ind. and Eng. Cbem. 17 3 182 (1945)
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Jcbida J.
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( 180)
STUOY ON THE HEMfCELLULOSE OF FORMOSAN
BAMBOO (Sinocalanus Latiforus Munre)
41. Sadayosbi Watanabe J. 50c. Cbem. lnd ,
農林學報
Japan. 笠油6-7咕。 944)
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三浦伊八郎、西目眩二.木材化學 p.
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:農林學報
STUDY ON THE HEMTCELLULOSE OF FORMOSAN
BAMBOO (Siuocalanus Latiforns Munro)
(181 )
(中文摘妥)
關於臺灣之麻汁半纖維素之研究
楊
晃
爭
攘挪力斯 (Norris) 及普力斯 (preece) 二民實驗手潰，將台灣產麻竹(採集地為台中縣竹
w 區鹿谷鄉秀辜村，國立台灣大學實驗林管理處清水溝營林區)
，以熱水 0.5% 草酸欽除去粗植
物膠後，以 4~ 苛性的溶液浸出牟轍素 A ，再將;其建渣用 10% 苛性說，溶液浸出 d~n 侮到'*纖
維素 B 。
25
1.
牟纖維素A 含有灰分5.02% ，其 [α]D 為 -78.20 0 ，半織維素 B 之灰分含量為 3.98%'r巾
2民
共 [α] 白卸為 -8~.20 。
2.
此半織推素，即相當於歐姐阿女士所講的半纖雄素 A 及 B 二部分所組成。
8.
此牟纖維素水解後，可得右旅木憫之結晶分離。此菱形結晶之融點為
142-145 0 ，其
2民
[α] 口為 +19.6 0 (70 分鐘後)。此牟纖維素 A 及 B 水解時，除得右旋木牆之外，可得阿刺
伯糟。此事實以游紙界面層析法證明乏。關槍試驗 (seliwanoff，
pinoff etc) 結果無反應，同時
於水解物中並未發見其他五碳搪或六碳惜。
4.
此學纖韓素 A 及 B 自 85% 木聚醋與少量阿刺社糖膠及菌葡萄聚醋芝化合物哉混合物
所組成的。
若研究台灣車廠竹之牟纖維素之構造，領更進一步之研究。

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