열처리조건에 따른 숙지황의 품질변화

송대식,우관식,성낙술,김광엽,정헌상,이희봉,Song, Dae-Shik,Woo, Koan-Sik,Seong, Nak-Sull,Kim, Kwang-Yup,Jeong, Heon-Sang,Lee, Hee-Bong 한국식품영양과학회 2007 한국식품영양과학회지 Vol.36 No.6

숙지황을 간편하게 제조할 수 있는 새로운 방법을 개발하고자 고온고압처리방법을 적용시켜 처리조건에 따라 지표성분인 5-HMF의 함량과 몇 가지 품질특성의 변화를 조사하여 시판 숙지황과 비교분석하였다. 색도는 처리온도와 시간이 증가할수록 L, a, b값 모두 감소하였으며, $120^{\circ}C$, 4시간 처리와 $130^{\circ}C$, 2시간 처리 이후가 시판 숙지황의 색도와 유사하였다. Fructose는 $120^{\circ}C$에서 처리시간의 증가함에 따라 약간 증가하였고 그 후에는 큰 변화를 나타내지 않았으며, glucose는 $120^{\circ}C$, 3시간 처리까지 증가하였지만 그 후에는 변화가 적었다. Sucrose는 $130^{\circ}C$, 1시간 처리부터 검출되지 않았다. 아미노산은 모두 17종이 분석되었으며, 총 함량은 건지황에서 3,029 mg/100 g이었고 열처리온도가 증가할수 록 증가하여 $140^{\circ}C$, 2시간 처리에서 4,172 mg/100 g으로 가 장 높은 함량을 나타내었다. Catalpol 함량은 건지황에서 631.4 ppm이 검출되었으나 숙지황에서는 검출되지 않았고 고온고압처리에 의한 숙지황은 $130^{\circ}C$, 1시간 처리(275.9 ppm) 이후에 검출되지 않았다. 숙지황의 지표물질인 5-HMF는 건지황과 시판 숙지황에서 각각 0.12 및 4.04 mg/g으로 나타났다. 처리온도와 시간이 증가할수록 5-HMF 함량은 증가하였으며, $150^{\circ}C$, 5시간 처리구에서 24.95 mg/g으로 가장 높은 함량을 보였다. 5-HMF의 함량이 0.1% 이상일때 숙지황의 품질요건을 충족하므로 고온고압처리에 의한 숙지황 제조는 $130^{\circ}C$, 2시간에서 $140^{\circ}C$, 2시간 처리가 적합한 것으로 판단되었다. This study was performed to develop a more simple and convenient heat treatment process for increasing heating temperature than the traditional 9-times steaming process for Rehmanniae radix Preparata (R. radix P.). The R. radix was heated to various temperatures (110, 120, 130, 140 and $150^{\circ}C$) for different lengths of time (1, 2, 3, 4 and 5 hr). Chromaticity, free sugar, amino acid, catalpol and 5-HMF (5-hydroxy-methyl-2-furaldehyde) content of water extracts of R. radix P. were analysed. With increasing heating temperature and time, the L, a and b-value of samples gradually decreased. Fructose and glucose contents were increased to $120^{\circ}C$ for 5 hr (5.21 and 6.67%, respectively) with no changes afterward. Sucrose content was not detected after $130^{\circ}C$. Total amino acid was increased to $140^{\circ}C$ and decreased afterward. The maximum total amino acid content was 4,172 mg/100 g at $140^{\circ}C$ for 2 hr (R. radix L.: 3,029 mg/100 g). The catalpol was decreased to $130^{\circ}C$ for 1 hr and not detected afterward. The 5-HMF content increased with increasing heating temperature and time. The maximum content of 5.HMF was 2.5% in $150^{\circ}C$ for 5 hr. Hence, it can be suggested that the heat treatment at $130^{\circ}C$ for 2 hr or more is the most optimum processing conditions, instead of the traditional 9.times steaming process.

Oxidation of 5-Hydroxymethyl-2-furaldehyde (HMF) using resin supported transition metals

( Huynh Thanh Thien Nhan ),조진구 한국공업화학회 2018 한국공업화학회 연구논문 초록집 Vol.2018 No.0

5-Hydroxymethyl-2-furaldehyde (HMF), a product formed by the dehydration of certain sugars, is a versatile bio-based building block. Its molecular structure contains both aldehyde and alcohol functional group, which allows for various structural reformations into toxin-free and biodegradable furan-monomers. In this research, we focused on the oxidation of 5-Hydroxymethyl-2-furaldehyde (HMF) using transition metals deposited on ion exchange resin. Several metal catalysts and solvents were screened for the reaction. Results show that oxidation was achieved and HMF was completely converted to products such as 2,5-Furandicarboxaldehyde (DFF), 5-Formyl-2-furancarboxylic acid (FFCA), and 2,5 Furandicarboxylic acid (FDCA).

Processing of agricultural apple fruit waste into sugar rich feedstocks for the catalytic production of 5-HMF over a Sn Amberlyst-15 resin catalyst

C.H.L. Tempelman,J.F. Jacobs,S. Ramkhelawan,A. Mok,W. van der Zalm,V. Degirmenci 한국공업화학회 2021 Journal of Industrial and Engineering Chemistry Vol.99 No.-

In this study we considered processes of treatment of agricultural apple waste which is normallydiscarded. We show the effect of various pre-treatment procedures on thefinal catalytic performance toproduce 5-HMF from this real world biomass waste. Our study of the various potential pre-treatmentsteps, and their effect on the catalytic performance, provides valuable new insights which can be used forthe development of new processes for the localised small scale valorization of agricultural fruit waste. The apple waste is aimed to be converted into a sugar rich feedstock stream for the catalytic conversion to5-hydroxymethyl furfural (5-HMF) at low temperatures ( 120 C). Filters with varying pore sizes werestudied for thefiltration of apple pomace after milling the rotten apples in order to reduce the solidscontent. The testedfilters varied in pore sizes of 0.2 mm, 2 mm and 54 mm. The effect of heating, acid orbase treatment of the apple slurry was evaluated for increasing the speed offiltration. The highestflowrate was obtained for thefilter with 54 mm pores. The sugar richfiltrates were investigated in thecatalytic conversion to 5-HMF over an easy-to-manufacture Sn exchanged resin (Amberlyst-15) catalyst. Results showed thatfiltrates obtained over a 2 mmfilter lead to the highest 5-HMF yields (18 %) withoutextra additives. Adjustment of the reaction mixtures to pH 7 resulted in a lower catalytic activity. 5-HMFis proposed to be extracted from the aqueous layer by using an organic liquid layer (methyl isobutylketone, MIBK). In order to increase the diffusion of 5-HMF to the MIBK layer the addition of salts to thereaction mixture was investigated. This leads to lower catalytic activity, possibly due to catalystdeactivation. Our results showed that a relatively wide porefilter (54 mm) provides the fastest appleprocessing method and afiltrate reacting to the highest 5-HMF yield in catalytic conversion of the sugarrich product stream obtained from agricultural waste apples.

Physicochemical effects of different processing temperatures on 5-hydroxymethyl-2-furaldehyde and the volatile flavor of domestic honey

최석호,남명수 충남대학교 농업과학연구소 2021 Korean Journal of Agricultural Science Vol.48 No.4

This study was performed to suggest concentration methods leading to the production ofhoney with an excellent flavor by examining the effects of the concentration temperature and method on changes in 5-hydroxymethyl-2-furaldehyde (5-HMF) levels and the flavor components of honey. The 5-HMF contents of honey samples concentrated in a tray concentrator at 45, 50, 60, and 70℃ were 2.1, 2.3, 2.5, and 3.1 mg·kg-1, respectively, demonstrating that the 5-HMF contents increased as the concentration temperatures were increased. The honey vacuum-concentrated at 70℃ showed a higher 5-HMF content than that at 60℃, similar to the tray-concentrated honey at different temperatures. The main and other minor flavor components of the honey were volatilized and significantly reduced after vacuum concentration. In the tray concentration, all of the honey samples concentrated at 40, 50, 60, and 70℃ showed flavor component patterns similar to each other, and most of the main and other minor flavor components in the honey were volatilized and significantly reduced after tray concentration. As such, most of the main and other minor flavor components of the honey were mostly removed at 70℃ after both the vacuum concentration and tray concentration processes. The effects of the concentration method and temperature on the viscosity, 5-HMF level, and flavor components of the honey were found to be significant in this study. Given that the components of honey were shown to undergo significant physicochemical changes depending on the concentration method used and temperature during laboratory-scale production, the concentration methods devised in this study can be applied industrially.

Basic anion-exchange resin (AER)-supported Au-Pd alloy nanoparticles for the oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furan dicarboxylic acid (FDCA)

Antonyraj, Churchil A.,Huynh, Nhan Thanh Thien,Park, Seok-Kyu,Shin, Seunghan,Kim, Yong Jin,Kim, Sangyong,Lee, Kwan-Young,Cho, Jin Ku Elsevier 2017 Applied Catalysis A Vol.547 No.-

<P><B>Abstract</B></P> <P>Au-Pd alloy nanoparticles supported on basic anion-exchange resin (AER) have exceptional catalytic activity for the oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furan dicarboxylic acid (FDCA) with an equimolar amount of base. SEM-EDX and TEM analyses show that 5–20nm Au-Pd alloy nanoparticles are well dispersed both on the resin surface and inside resin spheres by a simple procedure without any assistance of additives. XPS analysis reveals that Au- and Pd metals exist in an alloy form on the AER support, which is confirmed by a comparison study with a mixture of AER-supported monometallic nanoparticles (AER-supported Au and AER-supported Pd). In the presence of a 1:1 ratio of Au-Pd alloy nanoparticles over Amberlite IRA-743 resin with O<SUB>2</SUB> (10bar) at 373K in an equimolar Na<SUB>2</SUB>CO<SUB>3</SUB> aqueous solution, HMF is oxidized to FDCA with a 93.2% yield. On the other hand, mixture of AER-supported Au and AER-supported Pd affords only a 52% FDCA yield under identical conditions. This catalyst can be used 6 times without any significant loss of activity. FDCA is also obtained from HMF with an 82.9% yield in air (40bar).</P> <P><B>Highlights</B></P> <P> <UL> <LI> Au-Pd alloy nanoparticles were simply supported on basic anion-exchange resin. </LI> <LI> The nanoparticles were dispersed both on the resin surface and inside resin sphere. </LI> <LI> HMF was oxidized to FDCA with 93.2% yield using this catalyst. </LI> <LI> This catalyst could be used 6 times without any significant loss of activity. </LI> <LI> With this catalyst, FDCA was obtained from HMF with an 82.9% in air. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Basic anion-exchange resin (AER)-supported Au-Pd alloy nanoparticles were readily prepared and successfully applied to the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furan dicarboxylic acid (FDCA).</P> <P>[DISPLAY OMISSION]</P>

Activation of formyl CH and hydroxyl OH bonds in HMF by the CuO(1 1 1) and Co₃O₄(1 1 0) surfaces: A DFT study

Ren, Jun,Song, Kai-he,Li, Zhenhuan,Wang, Qiang,Li, Jun,Wang, Yingxiong,Li, Debao,Kim, Chan Kyung Elsevier 2018 APPLIED SURFACE SCIENCE - Vol.456 No.-

<P><B>Abstract</B></P> <P>The first principle calculations with on-site Coulomb repulsion U terms were carried out to investigate the 5-hydroxymethylfurfural (HMF) adsorption on the CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces, two widely used oxidation catalysts. The adsorption of HMF molecule is energetically favoured in both cases, and HMF is more inclined to bridge adsorption via hydroxyl and formyl groups binding with surface O and metal sites. Moreover, the adsorption energy relies on both the coordination type of surface lattice oxygen to which the H atom binds and the formation of H-bond involving hydroxyl and formyl groups on the adsorbed HMF. Also, the hydroxyl OH bond breaking is very easy and is likely to be the first step in HMF oxidation, and then the OH insertion reaction to produce 2,5-furandicarboxylic acid (FDCA). The corresponding experimental results also show that the CuO and Co<SUB>3</SUB>O<SUB>4</SUB> surfaces are promising candidate catalysts.</P> <P><B>Highlights</B></P> <P> <UL> <LI> CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces catalyze the oxidation of 5-hydroxymethylfurfural (HMF). </LI> <LI> Initial binding was formed through bridged-adsorption with O atoms in HMF. </LI> <LI> Oxidation reaction proceeds through the OH bond breaking pathway. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Schematic potential energy diagram for the formyl CH and hydroxyl OH bonds of HMF dissociation on CuO(1 1 1) and Co<SUB>3</SUB>O<SUB>4</SUB>(1 1 0) surfaces. Obviously, the hydroxyl OH bond breaking is easier than that of the formyl CH bond on the two surfaces, which indicates the first step of oxidation of HMF to FDCA should be hydroxyl OH bond breaking.</P> <P>[DISPLAY OMISSION]</P>

침지용매에 따른 숙지황의 품질특성

우관식(Koan Sik Woo),송대식(Dae Sik Song),이준수(Junsoo Lee),이희봉(Bee-Bong Lee),정헌상(Heon-Sang Jeong) 한국식품과학회 2007 한국식품과학회지 Vol.39 No.3

숙지황의 제조에 미치는 침지용매의 영향을 살펴보기 위하여 건지황을 막걸리와 증류수에 24시간 침지한 후 구증구포하여 숙지황을 제조하면서 증수에 따른 catalpol, 5-HMF, polyphenol, flavonoid, 항산화활성 및 ACE 저해활성 등을 분석하였다. Catalpol 함량은 건지황에서 631.4 ppm으로 나타났으며, 증수가 증가할수록 급격히 감소하였고 막걸리 침지는 8증(75.84 ppm)까지, 증류수 침지 처리구는 9증(61.27 ppm)까지만 검출되었다. 5-HMF, 총 폴리페놀, 총 플라보노이드 함량은 증수가 증가할수록 증가하였으며, 5-HMF는 막걸리 침지는 13증(0.40%) 이후에, 증류수 침지 처리구는 11증(0.40%) 이후에 시판 숙지황의 함량과 비슷하였고 총 폴리페놀 함량과 총 플라보노이드 함량은 막걸리와 증류수침지 처리구 모두 14증에서 가장 높은 함량을 나타내었다. 전자공여능은 건지황과 시판 숙지황 모두 1 ㎎/㎖의 농도에서 각각 19.44 및 52.49%이었으며, 막걸리와 증류수침지 시료 모두 14증에서 각각 66.80 및 75.60%로 증가하였다. 총 항산화력도 처리증수가 증가할수록 증가하였다. ACE 저해활성은 건지황과 시판 숙지황 모두 1 ㎎/㎖의 농도에서 각각 28.70 및 49.37%로 이었으며, 처리 증수가 증가할수록 증가하여 막걸리와 증류수침지 시료 모두 10증에서 각각 93.23 및 94.78%로 가장 높은 활성을 나타내었다. This study was performed to investigate the effects of pre-soaking methods on the preparation of Rehmannia radix Preparata (R.P). The R. radix L (R.L) was soaked in distilled water and traditional Korean wine for 24 hr, then the soaked R.L was treated with a traditional nine-time steaming process. Next, catalpol, 5-hydroxymethyl-2-furaldehyde (5-HMF), polyphenols, flavonoids, antioxidant activities, and ACE inhibition activity were analyzed for the R.P produced by the different methods. The catalpol content of the R.L was 631.4 ppm, but the content decreased as steaming increased to 8-9 times. The 5-HMF, polyphenol, and flavonoid contents of the RL were 0.12 ㎎/g, 5.09 ㎎/g, and 0.83 ㎎/g, respectively, and these increased gradually with increasing steaming times. As the steaming times of the distilled soaking water increased, the antioxidant activities of 1 ㎎/㎖ increased from 19.44% to 75.60% at 14 times of steaming. The ACE inhibition activities of 1 ㎎/㎖ of the distilled soaking water increased from 28.70% to 94.78% at 10 times of steaming, but decreased afterward.

Heterogeneous selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-diformylfuran (DFF) using O₂

( Churchil Angel Antony Rajjeganathan ),조진구 한국공업화학회 2014 한국공업화학회 연구논문 초록집 Vol.2014 No.1

5-Hydroxymethylfurfural (HMF) is a versatile building block chemical obtained from biomass-derived carbohydrates which can be converted to a wide range of chemicals and fuels. The selective oxidation of HMF leads to 1,2-diforomylfuran (DFF), which finds application in furan based polymers, pharmaceutical intermediates and fine chemicals. The heterogeneous catalysed selective conversion of HMF to DFF is still remains a challenge due to multiple side reactions and separation/ purification of DFF from high boiling solvents. Among the low boiling solvents we studied toluene showed maximum HMF conversion of 95% with 95% DFF selectivity MIBK afford >95% HMF conversion with >95% DFF selectivity.

Evaluation of process performance on biohydrogen production in continuous fixed bed reactor (C-FBR) using acid algae hydrolysate (AAH) as feedstock

Anburajan, Parthiban,Yoon, Jeong-Jun,Kumar, Gopalakrishnan,Park, Jong-Hun,Kim, Sang-Hyoun Elsevier 2019 INTERNATIONAL JOURNAL OF HYDROGEN ENERGY - Vol.44 No.4

<P><B>Abstract</B></P> <P>In this study, a novel inoculation method to mitigate the inhibition of 5-hydroxymethylfurfural (5-HMF) is proposed. Acid algae hydrolysate containing 1.5 g 5-HMF/L and 15 g hexose/L hexose was fed to a continuous fixed bed reactor (C-FBR) partially packed with hybrid-immobilized beads. The inoculation method enabled a high rate of H<SUB>2</SUB> production, due to the reduction of 5-HMF inhibition and enhanced biofilm formation. Maximum hydrogen production was achieved at a hydraulic retention time of 6 h with a hydrogen production rate (HPR) of 20.0 ± 3.3 L H<SUB>2</SUB>/L-d and a hydrogen yield (HY) of 2.3 ± 0.4 mol H<SUB>2</SUB>/mol hexose <SUB>added</SUB>. Butyrate and acetate were the major soluble metabolic products released during fermentation. Quantitative real-time polymerase chain reaction analysis revealed that <I>Clostridium butyricum</I> comprised 94.3% of the total bacteria, which was attributed to the high rate of biohydrogen production.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Pore of support material was packed with hybrid immobilized beads. </LI> <LI> The new inoculation method mitigated the inhibition of 5-HMF on bio-H<SUB>2</SUB>. </LI> <LI> H<SUB>2</SUB> production of 20.0 L/L-d was achieved with 1.5 g 5-HMF/L. </LI> </UL> </P>

시판품 숙지황중의 5-hydroxymethyl-2-furaldehyde (5-HMF) 함량분석

김호경,전원경,김영아,고병섭,Kim, Ho-Kyoung,Jeon, Won-Kyung,Kim, Young-A,Ko, Byoung-Seob 한국한의학연구원 2003 한국한의학연구원논문집 Vol.9 No.1

Rehmanniae Radix Preparata attributes good blood circulation and it has been used for the treatment of dizziness, men's sterility, excessive loss of blood and weakness. On the quality control of commercial Rehmanniae Radix Preparata, quantitative determination of 5-hydroxymethyl (5-HMF) using HPLC method has been conducted. Quantitative analysis of S-hydroxymethyl-2-furaldehyde (5-HMF) in commercial Rehmanniae Radix Preparata showed average of $0.136{\pm}0.057%$ in 14 samples collected throughout the regions of Korea.