KR20030050685A - Compound of calcium-nucleic acid and manufacturing method of the same - Google Patents
Compound of calcium-nucleic acid and manufacturing method of the same Download PDFInfo
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- KR20030050685A KR20030050685A KR1020010081190A KR20010081190A KR20030050685A KR 20030050685 A KR20030050685 A KR 20030050685A KR 1020010081190 A KR1020010081190 A KR 1020010081190A KR 20010081190 A KR20010081190 A KR 20010081190A KR 20030050685 A KR20030050685 A KR 20030050685A
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Abstract
Description
칼슘은 인체에 가장 많이 존재하는 무기질 원소로서, 일반 성인의 경우 체중의 약 2%인 1,200g정도를 체내에 보유하고 있다. 체내 칼슘의 99%는 골격과 치아를 형성하고 있으며, 나머지 1% 정도만이 근육의 수축과 이완, 규칙적 심장 박동, 혈액응고, 효소의 활성화, 세포 내 자극과 흥분의 전달과 같은 생리활성 조정 기능을담당하고 있다.Calcium is the most abundant mineral in the body, and the average adult has about 1,200g of body weight, about 2% of body weight. 99% of the body's calcium forms bones and teeth, and only 1% of the body's calcium regulates physiological activities such as muscle contraction and relaxation, regular heartbeat, blood coagulation, enzyme activation, and intracellular stimulation and excitation delivery. I am in charge.
체내 칼슘 농도는 항상 일정한 농도(약 10mg/100㎖)로 유지되어야 하며, 칼슘의 공급이 장기간 결핍되어 체내 칼슘 농도가 낮아지면 골다공증(dsteoporosis), 구루병(rickets), 테타니(tetany)와 같은 골격과 관련된 질환 이외에도 순환기 계통 질환, 대장 질환, 고혈압 등의 각종 성인병과 관련되는 문제점이 있다. 따라서, 이와 같은 문제점의 해결을 위하여 적당한 칼슘의 섭취와 적절한 소장 내 칼슘 흡수량의 증가가 중요하다.The body's calcium concentration should be maintained at a constant concentration (about 10mg / 100ml) at all times, and if the calcium supply in the body is low due to long-term deficiency of calcium supply, skeletons such as osteoporosis, rickets, and tetany In addition to related diseases, there are problems associated with various adult diseases such as circulatory system diseases, colon diseases, hypertension and the like. Therefore, in order to solve this problem, proper calcium intake and proper increase of calcium absorption in the small intestine are important.
칼슘의 섭취는 적절한 칼슘 공급원을 통해서 일어나는데, 식품 중 칼슘 공급원의 가치는 칼슘 함량뿐만 아니라 체내 이용성에 의해서 평가된다. 이러한 체내 이용성은 칼슘염의 형태, 신체의 생리적 상태, 나이 및 식이 인자에 의해 결정된다. 최근 여러 나라에서 소뼈 회분(bone ash), 패각분말(shell powder), CCM(calcium citrate malate)와 같은 칼슘 공급원 및 칼슘 보충제가 개발되어 보급되고 있다. 칼슘의 이용성을 증진시키기 위해 단백질을 특정 효소로 분해하여 얻은 칼슘 흡수 펩타이드와 특정 단백질이나 펩타이드를 화학적으로 수식한 인산화 단백질 혹은 펩타이드가 널리 이용되고 있으며, 이중 가장 널리 알려진 것이 우유에 들어있는 카제인 단백질을 트립신으로 분해시켜 만든 CPP(casein phosphopeptide)로 카제인의 serine 잔기가 인산화 되어 있어 소장 내 가용성 칼슘과 결합하여 체내 흡수를 용이하게 해주는 물질로 알려져 있다.Calcium intake occurs through appropriate calcium sources. The value of calcium sources in food is assessed not only by the calcium content but also by the body's availability. This availability to the body is determined by the type of calcium salt, the physiological state of the body, age and dietary factors. Recently, calcium sources such as bone ash, shell powder, calcium citrate malate (CCM) and calcium supplements have been developed and spread in many countries. In order to enhance the availability of calcium, calcium absorption peptides obtained by breaking down proteins with specific enzymes and phosphorylated proteins or peptides chemically modified with specific proteins or peptides are widely used. Among them, the most widely known casein protein is milk CPP (casein phosphopeptide) made by trypsin is known to be phosphorylated with serine residues of casein, which is combined with soluble calcium in the small intestine to facilitate absorption in the body.
종래기술로서 대한민국 특허공보 제91-10045호(1991.12.12. 공고)의 킬레이트화 된 칼슘이온 제조방법과, 특허출원 제10-1999-0010337호(1999.3.25. 출원)의동물 등의 뼈를 고온, 고압 처리하여 연화시키는 기술, 공개번호 제1997-0061268 호 (1996.2.21. 출원)의 글루텐 펩타이드를 유효성분으로 하는 미네랄 흡수 촉진제 등이 보고되고 있으나, 이는 뼈 자체의 물리적 가공 기술이나, 단백질에서 유래되는 칼슘 흡수 촉진소재로서, 핵산물질을 이용하는 본 발명과는 차이가 있다.As a conventional technique, bones of chelated calcium ions of Korean Patent Publication No. 91-10045 (December 19, 1991) and animals of Patent Application No. 10-1999-0010337 (filed March 25, 1999) A technique for softening by high temperature and high pressure treatment, and mineral absorption accelerators using gluten peptides of Korean Patent No. 1997-0061268 (filed Feb. 1, 1996) have been reported. As a calcium absorption promoting material derived from, there is a difference from the present invention using a nucleic acid material.
또한, 지금까지 이용되고 있는 칼슘소재는 다양하나 이들 모두는 흡수되기 어려운 상태의 칼슘 화합물이며, 섭취되더라도 극 미량만이 흡수될 수 있다는 결론이 많은 학자들에 의해 밝혀지고 있다.In addition, many scientists have been found to conclude that the calcium materials used so far, but all of them are calcium compounds in a difficult state to be absorbed, and only a very small amount can be absorbed even if ingested.
한편, 핵산물질은 모든 생물의 세포에 함유되어 있는 생체 고분자 물질로 nucleotide라는 단위물질이 중합된 polynucleotide 형태로 존재하며, 핵산 염기, 5탄당, 인산으로 구성되어 있다. 즉 분자 구조 특성상 칼슘과 결합할 수 있는 인산기가 많이 존재하며, 열이나 pH에 비교적 안정하기 때문에 식품에 적용할 경우, 가공적성도 유리할 것으로 기대 된다.On the other hand, the nucleic acid material is a biopolymer material contained in the cells of all organisms and exists in the form of a polynucleotide in which a unit substance called nucleotide is polymerized, and is composed of nucleic acid base, pentose sugar, and phosphoric acid. In other words, due to the molecular structure, there are many phosphate groups capable of binding to calcium, and because it is relatively stable to heat or pH, it is expected to be advantageous when applied to food.
이에 본 발명은 상기와 같은 상황을 감안하여 발명한 것으로, 모든 생물의 세포에 함유되어 있는 핵산물질 중 분자량이 1,000 - 1,000,000인 고분자 핵산물질이 칼슘과 결합하여 칼슘 침전을 억제하는 기능이 있음을 확인하였으며, 이에 따라 고분자 핵산물질과 칼슘을 결합시켜 체내 소화 환경에서 침전되지 않고 흡수가 용이하도록 한 칼슘-핵산물질 복합체 및 그 제조방법을 제공하고자 함에 그 목적이 있다.Accordingly, the present invention has been invented in view of the above situation, and it is confirmed that a polymer nucleic acid material having a molecular weight of 1,000-1,000,000 in the nucleic acid material contained in the cells of all living organisms has a function of inhibiting calcium precipitation by combining with calcium. Accordingly, an object of the present invention is to provide a calcium-nucleic acid complex and a method for preparing the same, wherein the polymer-nucleic acid and calcium are combined to facilitate absorption without precipitation in the digestive environment of the body.
도 1 및 도 2 - 종래의 칼슘흡수촉진제 및 본 발명의 칼슘-핵산물질 복합체의 칼슘 가용화 능력을 비교 도시한 그래프1 and 2-a graph comparing the calcium solubilization ability of the conventional calcium absorption promoter and the calcium-nucleic acid complex of the present invention
도 3 - 종래의 칼슘흡수촉진제 및 본 발명의 칼슘-핵산물질 복합체의 시간경과에 따른 칼슘 가용화 능력변화를 도시한 그래프Figure 3-Graph showing the change in calcium solubilization capacity with time of the conventional calcium absorption promoter and calcium-nucleic acid complex of the present invention
도 4 및 도 5 - 본 발명의 pH 및 열처리온도변화에 따른 칼슘 가용화 능력을 도시한 그래프4 and 5-graph showing the solubility of calcium according to the pH and heat treatment temperature change of the present invention
상기 목적을 달성하기 위한 본 발명의 칼슘-핵산물질 복합체의 제조방법은, 칼슘 원료를 적당한 용매에 용해시키는 용해단계, 이 용해단계에서 제조된 칼슘 용액에 핵산물질을 첨가하여 결합시키는 반응단계, 이 반응단계에서 제조된 칼슘-핵산물질 복합체 용액의 pH를 조절하는 pH 조절단계, 가용성 칼슘-핵산물질 복합체를 분리하기 위한 여과단계, 여과단계에서 분리된 가용성 칼슘-핵산복합체를 건조하기 위한 건조단계가 순차적으로 진행되어 달성되며, 최종적으로 마쇄단계를 거치게 되는 것을 특징으로 한다.Method for producing a calcium-nucleic acid composite of the present invention for achieving the above object, the dissolving step of dissolving the calcium raw material in a suitable solvent, the reaction step of adding a nucleic acid material to the calcium solution prepared in this dissolving step, this PH adjustment step of adjusting the pH of the calcium-nucleic acid complex solution prepared in the reaction step, filtration step for separating the soluble calcium-nucleic acid complex, drying step for drying the soluble calcium-nucleic acid complex separated in the filtration step It is achieved by proceeding sequentially, characterized in that the final grinding step.
즉, 상기 제조방법에 의해 칼슘-핵산물질 복합체를 제조하였으며, 칼슘의 생체내 침전을 방지하여 체내 흡수율이 높일 수 있음을 확인할 수 있었다.That is, the calcium-nucleic acid composite was prepared by the above method, and it was confirmed that the absorption rate in the body can be increased by preventing the precipitation of calcium in vivo.
본 발명의 제조방법을 단계별로 상세히 설명하면 다음과 같다.Referring to the manufacturing method of the present invention in detail step by step as follows.
먼저 본 발명의 칼슘 원료를 용해시키는 용해단계는 칼슘 원료에 따라 2가지 방법으로 나눌 수 있다.First, the dissolving step of dissolving the calcium raw material of the present invention can be divided into two methods depending on the calcium raw material.
칼슘 원료로 물에 대한 용해도가 높은 염화칼슘, 탄산칼슘, 젖산칼슘 등을 사용할 경우는 상기 칼슘 원료를 물에 용해시켜 5% ∼ 20% 용액으로 만든다.When calcium chloride, calcium carbonate, calcium lactate, or the like having high solubility in water is used as the calcium raw material, the calcium raw material is dissolved in water to make a 5% to 20% solution.
반면, 칼슘 원료로 물에 대한 용해도가 높지 않은 우골 회화분, 어골 회화분, 패각 회화분, 난각 회화분 등을 사용할 경우, 상기 칼슘 원료를 0.1N ∼ 2N의 구연산, 젖산, 초산 등의 유기산에 용해시켜, 2% ∼ 15% 용액을 만든다.On the other hand, when using calcium raw materials such as right bone ash powder, bone bone ash powder, shell ash powder, egg shell ash powder, etc., which are not highly soluble in water, the calcium raw material may be applied to organic acids such as citric acid, lactic acid, acetic acid and the like. Dissolve to form a 2% to 15% solution.
본 발명의 반응단계는 상기 용해단계에서 제조된 칼슘 용액을 천천히 교반하면서 칼슘 양에 대해 20%∼ 150% 비율로 핵산물질을 투입하고 20 ℃∼40℃에서 1시간∼3시간 동안 교반하면서 반응시킨다. 이 반응단계에서 칼슘과 핵산물질이 결합하여 칼슘 - 핵산물질 복합체가 생성된다.In the reaction step of the present invention, while slowly stirring the calcium solution prepared in the dissolution step, the nucleic acid material is added at a rate of 20% to 150% based on the amount of calcium and reacted with stirring at 20 ° C. to 40 ° C. for 1 hour to 3 hours. . In this reaction step, calcium and nucleic acid material combine to form calcium-nucleic acid complex.
본 발명의 pH 조절단계는 칼슘 원료로 물에 대한 용해도가 높은 염화칼슘, 탄산칼슘, 젖산칼슘 등을 사용할 경우는 생략 가능한 공정이나, 칼슘 원료로 물에 대한 용해도가 높지 않은 우골 회화분, 어골 회화분, 패각 회화분, 난각 회화분등을 사용할 경우는 유기산에 용해시키므로 알카리 용액을 이용하여 pH를 4.0 ∼ 7.5로 조절한다. 이때 pH 상승으로 인해 칼슘의 용해도가 떨어져 침전물이 발생하기 때문에 후속공정으로 여과단계가 필요하게 된다.The pH adjustment step of the present invention is a step that can be omitted when using calcium chloride, calcium carbonate, calcium lactate, etc., which have high solubility in water as a calcium raw material, but the bone ash powder and fish bone ash powder which does not have high solubility in water as calcium raw material. , Shell shell ash powder, egg shell ash powder, etc. are dissolved in organic acid, so the pH is adjusted to 4.0-7.5 using an alkaline solution. In this case, since the solubility of calcium is lowered due to the increase in pH, a precipitate is generated, and thus, a filtration step is required in a subsequent process.
본 발명의 여과단계는 pH 상승으로 인한 불용성 칼슘-핵산물질 복합체를 제거하기 위한 공정이며, 필터프레스를 이용하거나 원심분리 할 수 있으며, 여과 시 여과보조제를 사용하는 것 바람직하다. 이때 여과액에는 칼슘-핵산복합 물질이 가용화 된 상태로 용해되어 있으며 후속의 건조단계에서 건조를 진행하여, 분말상의 칼슘-핵산복합체를 얻는다.The filtration step of the present invention is a process for removing the insoluble calcium-nucleic acid complex due to the rise in pH, it is possible to use a filter press or centrifugal separation, it is preferable to use a filtration aid. At this time, the calcium-nucleic acid composite material is dissolved in the filtrate in a solubilized state and dried in a subsequent drying step to obtain a powdered calcium-nucleic acid complex.
본 발명의 건조 및 마쇄단계는 동결건조나 분무건조 혹은 열풍건조를 실시하여 칼슘-핵산물질 복합체를 분말화 하는 과정이며 마쇄하여 최종 제품을 얻는 공정이다.The drying and grinding step of the present invention is a process of pulverizing the calcium-nucleic acid composite by performing lyophilization, spray drying or hot air drying, and grinding to obtain a final product.
이상과 같은 제조방법으로 얻어진 칼슘-핵산물질 복합체는 가용성이며, 체내 소화 환경에서 칼슘의 침전을 억제하여 칼슘의 체내 흡수성을 향상시킨다.The calcium-nucleic acid complex obtained by the above production method is soluble and inhibits the precipitation of calcium in the digestive environment of the body, thereby improving the absorption of calcium in the body.
이하 본 발명을 실시예 및 비교예에 의해 설명하고자 한다. 그러나 이들에 의해 본 발명의 기술적 범위가 제한되는 것은 아니다.Hereinafter, the present invention will be described by way of examples and comparative examples. However, these are not intended to limit the technical scope of the present invention.
(실시예 1)(Example 1)
염화칼슘 5g을 100 ㎖ 증류수에 용해시키고, 참치 정소에서 추출한 핵산물질(핵산함량:84.5%, M.W. 98,500 정도) 5g을 투입하여 37℃에서 1시간 교반하면서 칼슘-핵산물질 복합체를 형성시켰다.5 g of calcium chloride was dissolved in 100 ml of distilled water, and 5 g of nucleic acid material (nucleic acid content: 84.5%, M.W. 98,500) extracted from tuna testicles was added to form a calcium-nucleic acid complex while stirring at 37 ° C for 1 hour.
반응종료 후 여과하여 여과 액을 얻은 후, 반응종료 후 잔존할지 모르는 유리 염화칼슘을 제거하기 위해, 한외 여과 장치(Membrane : M.W. cutoff 10,000)를 이용하여 유리 상태로 존재하는 염화칼슘을 제거하였다.After completion of the reaction to obtain a filtrate by filtration, in order to remove the free calcium chloride that may remain after the completion of the reaction, using an ultrafiltration device (Membrane: M.W. cutoff 10,000) to remove the calcium chloride present in the free state.
한외 여과 장치에서 농축된 칼슘-핵산물질 복합체를 동결건조하고 마쇄하여 칼슘-핵산물질 복합체를 얻었다.The concentrated calcium-nucleic acid complex was lyophilized and ground in an ultrafiltration device to obtain a calcium-nucleic acid complex.
(실시예 2)(Example 2)
염화칼슘 5g을 100 ㎖ 증류수에 용해시키고, 연어 정소에서 추출한 핵산물질(핵산함량:94%, M.W. 120,000 정도) 5g을 투입하여 37℃에서 1시간 교반 하면서 칼슘-핵산물질 복합체를 형성시켰다.5 g of calcium chloride was dissolved in 100 ml of distilled water, and 5 g of the nucleic acid material (nucleic acid content: 94%, M.W. about 120,000) extracted from salmon testus was added to form a calcium-nucleic acid complex while stirring at 37 ° C for 1 hour.
반응종료 후 여과하여 여과 액을 얻은 후, 반응종료 후 잔존할지 모르는 유리 염화칼슘을 제거하기 위해, 한외 여과 장치(Membrane : M.W. cutoff 10,000)를 이용하여 유리 상태로 존재하는 염화칼슘을 제거하였다.After completion of the reaction to obtain a filtrate by filtration, in order to remove the free calcium chloride that may remain after the completion of the reaction, using an ultrafiltration device (Membrane: M.W. cutoff 10,000) to remove the calcium chloride present in the free state.
한외 여과 장치에서 농축된 칼슘-핵산물질 복합체를 동결건조하고 마쇄하여 칼슘-핵산물질 복합체를 얻었다.The concentrated calcium-nucleic acid complex was lyophilized and ground in an ultrafiltration device to obtain a calcium-nucleic acid complex.
(실시예 3)(Example 3)
염화칼슘 5g을 100 ㎖ 증류수에 용해시키고, Whole DNA(from salmon testes, Sigma 사) 5g을 투입하여 37℃에서 1시간 교반 하면서 칼슘 - 핵산물질 복합체를 형성시켰다.5 g of calcium chloride was dissolved in 100 ml of distilled water, and 5 g of Whole DNA (from salmon testes, Sigma) was added thereto, followed by stirring at 37 ° C. for 1 hour to form a calcium-nucleic acid complex.
반응종료 후 여과하여 여과 액을 얻은 후, 반응종료 후 잔존할지 모르는 유리 염화칼슘을 제거하기 위해, 한외 여과 장치(Membrane : M.W. cutoff 10,000)를 이용하여 유리 상태로 존재하는 염화칼슘을 제거하였다.After completion of the reaction to obtain a filtrate by filtration, in order to remove the free calcium chloride that may remain after the completion of the reaction, using an ultrafiltration device (Membrane: M.W. cutoff 10,000) to remove the calcium chloride present in the free state.
한외 여과 장치에서 농축된 칼슘-핵산물질 복합체를 동결 건조하고 마쇄하여 칼슘-핵산물질 복합체를 얻었다.The concentrated calcium-nucleic acid complex was lyophilized and ground in an ultrafiltration device to obtain a calcium-nucleic acid complex.
(비교예 1)(Comparative Example 1)
상기 실시예 1∼3에서 제조된 칼슘-핵산물질 복합체와 칼슘 흡수 촉진제로 시판 사용 중인 CPP2(casein phosphopeptide Ⅱtype, 명치제과, 일본)를 대상으로 칼슘 가용화 능력을 실험한 결과, 칼슘-핵산물질 복합체 형태의 칼슘 소재가 칼슘 가용화 능력이 우수한 것으로 나타났으며, CPP 2보다 낮은 농도에서도 효과적으로 칼슘을 가용화 시킬 수 있었다. 상기 실험 결과는 도 1 및 도 2에 나타내었다.As a result of experiments on calcium solubilization ability of the calcium-nucleic acid complex prepared in Examples 1 to 3 and CPP2 (casein phosphopeptide II type, Meiji Confectionery, Japan) which is commercially available as a calcium absorption promoter, calcium-nucleic acid complex form The calcium material of was found to have excellent calcium solubilization ability, and was able to effectively solubilize calcium even at lower concentrations than CPP 2. The experimental results are shown in FIGS. 1 and 2.
(비교예 2)(Comparative Example 2)
상기 실시예 1∼3에서 제조된 칼슘-핵산물질 복합체와 칼슘 흡수 촉진제로 시판 사용 중인 CPP2(casein phosphopeptide Ⅱtype, 명치제약, 일본)를 대상으로시간 경과에 따른 칼슘 가용화 능력의 변화를 비교 실험한 결과, 시판 사용중인 CPP2는 4시간 이후부터는 칼슘 가용화 능력을 상실하는 것으로 측정되었으나, 칼슘-핵산물질 복합체 형태의 칼슘 소재는 오랜 시간 동안 칼슘 가용화 능력을 유지하는 것으로 나타났다. 상기 실험결과는 도 3에 나타내었다.The results of comparative experiments of changes in calcium solubilization ability over time with the calcium-nucleic acid complex prepared in Examples 1 to 3 and CPP2 (casein phosphopeptide II type, Myung-Jin Pharm., Japan) in use as a calcium absorption promoter The commercially available CPP2 was found to lose calcium solubilization ability after 4 hours, but the calcium material in the form of calcium-nucleic acid complex retained calcium solubilization ability for a long time. The experimental results are shown in FIG. 3.
(비교예 3)(Comparative Example 3)
상기 실시예 1에서 제조된 본 발명의 칼슘-핵산물질 복합체에 대해서 여러 pH (2,3,4,5,6) 및 열처리(100℃, 121℃)조건에서 칼슘 가용화 능력의 유지 정도를 실험한 결과, pH 및 열처리에 대해 비교적 안정하였고, pH가 낮을수록, 열처리 온도가 높을수록 가용화 능력이 다소 감소하였다. 상기 실험 결과는 도 4(100℃ 열처리 조건) 및 도 5(121℃ 열처리 조건)에 나타내었다.For the calcium-nucleic acid composite of the present invention prepared in Example 1 was tested the degree of maintenance of calcium solubilization capacity at various pH (2,3,4,5,6) and heat treatment (100 ℃, 121 ℃) conditions The results were relatively stable with respect to pH and heat treatment, and the lower the pH, the higher the heat treatment temperature, slightly decreased the solubilization capacity. The experimental results are shown in Figure 4 (100 ℃ heat treatment conditions) and Figure 5 (121 ℃ heat treatment conditions).
이상 설명한 바와 같이, 본 발명은 칼슘-핵산물질 복합체 형태의 칼슘소재로서, 칼슘과 고분자 핵산물질(M.W.1,000 - 1,000,000)을 결합시킴에 따라, 이 고분자 핵산물질이 칼슘의 생체내 침전을 억제하며, 이에 따라 체내의 가용화 칼슘의 양을 증가시켜 칼슘의 흡수를 용이하도록 함을 확인하였다.As described above, the present invention is a calcium material in the form of a calcium-nucleic acid complex, and combines calcium and a polymer nucleic acid material (MW1,000-1,000,000), thereby inhibiting the precipitation of calcium in vivo. Accordingly, it was confirmed that the absorption of calcium was facilitated by increasing the amount of solubilized calcium in the body.
또한, 칼슘-핵산물질 복합체의 칼슘소재는 여러 pH나 열처리 조건에서도 비교적 안정하기 때문에 의약품, 건강 보조식품, 특수 영양식품 형태의 칼슘 보조제 뿐만 아니라 일반 가공 식품의 칼슘 공급원으로도 폭넓게 이용될 수 있는 효과가 있다.In addition, the calcium material of the calcium-nucleic acid complex is relatively stable under various pH or heat treatment conditions, so it can be widely used as a calcium source for general processed foods as well as calcium supplements in the form of medicines, health supplements and special nutritional foods. There is.
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| KR20160049631A (en) * | 2014-10-28 | 2016-05-10 | 조향현 | Preparation method for milk protein with high content of organic mineral using nucleotide as an catalyst |
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| WO2016060411A1 (en) * | 2014-10-13 | 2016-04-21 | 조향현 | Method for producing organic mineral and nucleic acid composite |
| KR20160049631A (en) * | 2014-10-28 | 2016-05-10 | 조향현 | Preparation method for milk protein with high content of organic mineral using nucleotide as an catalyst |
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