Method of producing n,s-containing, chitosan-based polymer
SUBSTANCE: present invention relates to a method of producing a N,S-cyclo-containing chitosan derivative. Described is a method of producing a chitosan-based N,S-cyclo-containing polymer (I) which contains in the macrochain 1-oxa-6-thia-4,8-diazocycloundecane fragments: I, by reacting chitosan with formaldehyde and a S-containing compound, characterised by that the S-containing compound used is hydrogen sulphide, the formaldehyde solution is pre-saturated with H2S and the reaction is carried out with molar ratio chitosan: formaldehyde: hydrogen sulphide of 1:2:1, at temperature of 0-60°C in a chloride medium for 24 hours.
EFFECT: obtaining modified chitosan which exhibits properties of a highly efficient heavy metal sorbent for waste water treatment, an extractant for separating rare, noble and precious metals and a complexing agent for biological molecules.
1 tbl, 3 ex
The present invention relates to organic chemistry, in particular to a method for producing N,S-cicloturismo derivative of chitosan (I)having the structural formula:
where n=50-70%, m=30-50%.
Currently, chitosan and its derivatives are considered as soil builders: company Ecogel produces patented chitosan containing drug "anti-Stress", designed to accelerate engraftment and acclimatization imported or transplanted plants http://www.ecogel.ru).
Like N,S-cyclododecane biopolymers having glucopyranose 1-oxa-6-thia-4,8-diazocyclopentadiene heterocycles are of interest as highly effective sorbents of heavy metals to wastewater treatment, extractants for the separation of rare, precious and precious metals, as well as selective complexing agents of biological molecules (T.Becker, .Schlaak, .Strasdeit // Reactive and Functional Polymers, 2000, 44, p.289-298. Z. Cao, H. Ge, S. Lai // European Polymer Journal, 2001, 37, p.2141-2143).
It is known that chitosan and its derivatives are promising polysaccharide materials to create ion-exchange membranes used in ultrafiltration and dialysis, and their complexing ability can be used for selective extraction of some metals from seawater (Evert, Antiseptci// USP, 2001, CH, No. 1, p.72-87). Chitosan and its phosphate derivatives, in particular phosphate chitosan can be used as biocompatible materials (Wang X., Ma J., Wang Y., He, B. // Biomaterials, 2001, v.22, no.16, p.2247), sorbents for the extraction of uranium (Sakaguchi T., Hirokoshi T., Nakajima A. // Agric. Biol. Chem., 1981, v.45, no.10, p.2191), chiral matrices to create a metal-complex catalysts (E. Guibal // Prog. Polym. Sci., 2005, v.30, no.1, p.71).
According to literature data, the chemical modification of chitosan can be carried out for all functional groups. Thus, a method of obtaining N,O-carboxymethyl-N,O-sulfotransferase chitosan (Zhao Xia, LV Zhihua, XU Jiamin, YU Guangli // Journal of Ocean University of Qingdao, 2003, v.2, no.1, p.69-74)with inhibitory activity against platelet blood:
There are examples of modifications of chitosan solely by the primary amino group of the polysaccharide. A method of obtaining N-alkyl derivatives of chitosan, which is based on the interaction of chitosan with aliphatic aldehydes by introduction of alkyl substituents on the amino group of the original polymer via Schiff's base (Keisuke Kurita, Satoko Mori, Yasuhiro Nishiyama, Manabu Harata // Polymer Bulletin, 2002, 48, p.159-166). It was shown that with increasing alkyl radical increases antibacterial activity of derivatives of chitosan (Chun But Kim, Jang Won Choi, Heung Jae Chun, Suk Kyu Choi // Polymer Bulletin, 1997, v.38, no.4, p.387-393).
The closest prototype of the method is based on the interaction of chitosan with formaldehyde and a thiol with obtaining sulfur-containing derivative, having grafted linear N-alkylthiomethyl group (Tanja Becker, Michael Schlaak, Henry Strasdeit // Reactive and Functional Polymers, 2000, 44, p.289-298), which selectively absorbs cadmium in the presence of salts of Nickel and zinc.
Thus, in the literature there are no data on the modification of chitosan on the amino group with obtaining N,S-containing cyclic derivative of chitosan.
The authors faced the problem of obtaining cyclic N,S-containing derivative of chitosan interaction timetreasure reagent "CH2O-H2S ' (A Wohl. Berichte, 1886, 19, 2344) with the primary amino groups of the original biopolymer. Information about how to obtain the above cyclic derivative such method in the literature are missing.
This goal is achieved by the interaction of saturated hydrogen sulfide aqueous 37%solution of formaldehyde with hydrochloric acid solution of chitosan taken in a molar ratio of the initial reagents chitosan:formaldehyde:hydrogen of 1:2:1 at a temperature of 0-60°C and stirring for 24 hours. The reaction mixture is neutralized with a weak solution of NaOH, the modified polymer is precipitated by 70%ethanol and centrifuged. When this clause is to obtain N,S-cyclododecane derivative of chitosan (I), in macrocopy which along with 2-amino-D-pyranose fragments are 1-oxa-6-thia-4,8-diazacyclooctadecane fragments. The reaction proceeds according to the scheme:
where n=50-70%, m=30-50%.
We studied the effect of modified chitosan (I) and its salts based on oxalic (C2H2About4) and ascorbic (C6H8About6) acids on the growth of seedlings and the development of root rot on wheat plants. The objects of the study were treated with aqueous solutions of sample (I) and its salts with a concentration of 1%, 0.1% and 0.01 percent. The results are shown in table 1. The value of the parameter characterizing the ratio of the length of the sheet to the length of the root.
|The effect of the product (I) and its salts on the growth and development of root rot on wheat plants|
|Rate/concentration||Control||The sample I||I·C2H2O4||I·C6H8O6|
|The strength of growth/1%||1,05||0,79||0,68||1,19|
|The development of root rot/|
It is shown that the product of (I) at a concentration of 0.01% will influence the growth of seedlings of wheat, and on the suppression of root rot affects both itself and its salts in concentrations of from 1.0% to 0.01%. Adduct with ascorbic acid in a concentration of 0.1% inhibits the development of root rot completely. As a result of the studies revealed that the product timestribune chitosan exhibits good fungicidal activity is, he absolutely environmentally safe and commercially available.
Significant differences of the proposed method
In the proposed method is the interaction of saturated hydrogen sulfide formaldehyde - dielectrophoresis reagent capable of simultaneously interact with two amino groups of chitosan - (1-4)-2-amino-2-deoxy-D-glycolysation. As a result, this method allows to obtain a cyclic N,S-containing derivative of chitosan (I) with 1-oxa-6-thia-4,8-diazacyclooctadecane fragments in macrocopy, details of which in the literature are missing.
Unlike the prototype (Tanja Becker, Michael Schlaak, Henry Strasdeit // Reactive and Functional Polymers, 2000, 44, p.289-298) the reaction takes place with the formation of S,N-heterocycles on chitosan matrix.
The advantages of the proposed method
The method allows to obtain N,S-cyclododecane derivative of chitosan (I), which forms a stable hydrogel, the synthesis of which is not described in literature, and is easy to experiment.
The method is illustrated by example
Example 1. In a three-neck flask equipped with stirrer, reflux condenser and bubbler temperature-controlled at a predetermined temperature, loaded with 3.3 ml of 37% (10 mmol) of formalin, 30 min was barbotirovany hydrogen (derived from the estimated number of Na2S and HCl) with the formation of a mixture of CH2O and H2S is a rate of 2:1. Then the reaction mass was added dropwise 0.8 g (5 mmol) of chitosan dissolved in 100 ml of 2%HCl. The mixture was stirred at 0°C for 24 hours. The reaction mass was neutralized with NaOH solution to pH=7, the modified chitosan was besieged by 70%ethanol in the ratio by volume of 1:3 by adding dropwise concentrated solution of NaCI. The precipitated polymer was centrifuged and washed three times with 70%alcohol, dried in the air. The result was obtained 1.04 g of N,S-cicloturismo derivative of chitosan (I) with 30%functionalization.
Example 2. In a three-neck flask equipped with stirrer, reflux condenser and bubbler temperature-controlled at a predetermined temperature, downloaded the calculated amount of 37%formalin, 30 min was barbotirovany hydrogen (derived from the estimated number of Na2S and HCl) with the formation of a mixture of CH2O and H2S in the ratio 2:1. Then the reaction mass was added dropwise estimated number of mole of chitosan (0.8 g)dissolved in 100 ml of 2%HCl. The mixture was stirred at 20°C for 24 hours. The reaction mass was neutralized with NaOH solution to pH 7, the modified chitosan was besieged by 70%ethanol in the ratio by volume of 1:3 by adding dropwise concentrated solution of NaCI. The precipitated polymer was centrifuged and washed three times with 70%alcohol, dried in the air. In financial p is Tata obtained 1.20 g of N,S-cicloturismo derivative of chitosan (I) 35%functionalization.
Example 3. In a three-neck flask equipped with stirrer, reflux condenser and bubbler temperature-controlled at a predetermined temperature, downloaded the calculated amount of 37%formalin, 30 min was barbotirovany hydrogen (derived from the estimated number of Na2S and HCl) with the formation of a mixture of CH2O and H2S in the ratio 2:1. Then the reaction mass was added dropwise estimated number of mole of chitosan (0.8 g)dissolved in 100 ml of 2%HCl. The mixture was stirred at 60°C for 24 hours. The reaction mass was neutralized with NaOH solution to pH 7, the modified chitosan was besieged by 70%ethanol in the ratio by volume of 1:3 by adding dropwise concentrated solution of NaCI. The precipitated polymer was centrifuged and washed three times with 70%alcohol. The result was obtained 1.04 g of N,S-cicloturismo derivative of chitosan (I) 50%functionalization.
The spectral characteristics of the1(1IR spectra were obtained on a spectrophotometer "Specord 75IR" in suspension in vaseline oil. One-dimensional NMR spectra1H,13C-and two-dimensional spectra (HSQC, COSY) of compound I registered on a “Bruker Avance 400”, internal standard TMS, solvent DMSO-d6.)
N,S-cicloturismo derivative of chitosan (I):
The connection I
The IR spectrum v cm-1: 750, 1050, 1170, 1620, 2900, 3200.
An NMR spectrum1N, D22).
An NMR spectrum13With, ppm, δ: 55.9 d, (C-2); 57.8 t (C-7); 57.9 t (C-6); 71.8 (C-3), 75.9 (C-5), 77.7 (C-4), 97.5 (C-1).
where n=50-70%, m=30-50%.
The method of obtaining the N,S-cicloturismo polymer (I) based on chitosan containing macrocopy 1-oxa-6-thia-4,8-diazacyclooctadecane fragments
the interaction of chitosan with formaldehyde and S-containing compound, characterized in that as S-containing compounds using hydrogen sulfide, formaldehyde solution is pre-saturated with H2S and the reaction is carried out at a molar ratio of chitosan - formaldehyde - hydrogen of 1:2:1, at a temperature 0÷60°C in hydrochloric acid environment within 24 hours
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention refers to biochemistry. What is presented is a conjugate of hyaluronic acid and novocaine of a structure as defined in the patent claim containing 20-50% residues of novocaine.
EFFECT: conjugate is water-soluble; it possess the amphoteric properties and contains no side O-acylisourea.
3 tbl, 3 ex
SUBSTANCE: disclosed are versions of a method of producing cross-linked polysaccharides, involving reaction of at least one polysaccharide selected from amino-polysaccharide, amino-functionalised polysaccharide containing one or more amino groups which can be cross-linked by reducing sugar, and combinations thereof, with at least one reducing sugar. The invention also discloses polysaccharides obtained using the disclosed method, a method of producing cross-linked matrices based on polysaccharides and matrices obtained using this method. The obtained matrices may include polysaccharide matrices and composite cross-linked matrices, including polysaccharides cross-linked with proteins and/or polypeptides.
EFFECT: obtained polysaccharides have satisfactory resistance to enzymatic degradation coupled with rheological properties of the preparation for injection, obtained matrices exhibit various physical, chemical and biological properties.
29 cl, 12 dwg, 6 tbl, 11 ex
SUBSTANCE: chitosan is dissolved in an organic acid: 4-6% citric acid or 2-8% lactic acid in the relation of the ingredients chitosan: the organic acid 1:2-1:4 to prepare a forming solution. Chitosan has molecular weight 80-500 kDa. The forming solution is added with vitamin B1 in the amount of max. 0.5 wt %. The prepared forming solution is applied on a substrate in the amount of 0.2-0.25 ml/cm2 and kept to achieve a film structure. Said method is used to form the chitosan film coating having the thickness of 50-250 mcm and the breaking elongation of 42 to 470%.
EFFECT: group of inventions allows preparing high-elastic chitosan citrate or lactate films possessing bactericidal action.
2 cl, 1 tbl, 13 ex
SUBSTANCE: method involves preparation of material for enzymatic hydrolysis. Alkaline hydrolysis is carried out with proteolytic enzyme preparations with neutralisation of the obtained solution to pH=7. A salt is added to the obtained enzymatic hydrolysate to a value of not less than 0.1 mol/l. Successive ultrafiltration is carried out, first on a membrane with maximum retention of 50 kD with separation of high-molecular weight impurities, and then on a membrane with maximum retention of 5 kD with separation of low-molecular weight substances. The chondroitin sulphate solution retained at the membrane is washed on the same membrane with distilled water until complete removal of salts. Final washing with distilled water is carried out on a membrane with maxim retention of 50 kD.
EFFECT: invention enables to obtain a chondroitin sulphate preparation with weight ratio of the basic substance.
SUBSTANCE: method involves activation of hyaluronic acid using a cross-linking agent and an auxiliary cross-linking agent. The activated hyaluronic acid then reacts with a nucleophilic cross-linking agent. The pH of the reaction medium ranges from 8 to 12. The nucleophilic cross-linking agent contains at least 50 wt % oligopeptide or polypeptide. Further, pH of the reaction medium is regulated to 5-7 and cross-linked hyaluronic acid is precipitated in the organic solvent. The invention also relates to use of the cross-linked hyaluronic acid obtained using this method in plastic surgery to make implants and to a hedrogel containing said cross-linked hyaluronic acid in a buffer aqueous solvent.
EFFECT: invention enables to obtain cross-linked hyaluronic acid in dry form, having high resistance to decomposition factors such as temperature, free radicals and enzymes.
18 cl, 3 tbl, 3 ex
SUBSTANCE: disclosed is a method of determining antibacterial properties of chitosan by estimating its minimum bacteriostatic and/or bactericidal concentration. Complex buffer solutions based on three organic acids MES, ACES and TES with different pH values are prepared. The ready buffer solutions are poured into a vessel. Double dilutions of chitosan are then prepared in vessels with the buffer solutions. Aliquots of a bacterial suspension in a fluid medium are added to the chitosan solutions in the buffer. The solutions are incubated for 24 hours at temperature which is optimum for bacterial growth. The minimum bacteriostatic and/or minimum bactericidal concentration of chitosan is then determined after incubation by determining growth of the culture or a drop in the number of living cells, respectively.
EFFECT: invention enables to determine antibacterial properties of chitosan in a wide pH range from 5,50 to 8,00 without the need to use buffers of different chemical composition.
5 dwg, 2 ex
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention refers to a method for preparing sodium salt of hyaluronic acid modified by boron compounds with no fluid medium added. The method consists in the fact that powdered sodium salt of hyaluronic acid together with a modifying agent and mixed modifying agents is pre-homogenised in a mixer at temperature ranging within 20° to 50°C; thereafter the prepared homogenous powder mixture is simultaneously exposed to pressure and shearing deformation in a mechanochemical reactor at temperature ranging within 20° to 50°C and pressure 5-1000 MPa.
EFFECT: invention provides preparing boron-containing sodium salt of hyaluronic acid applied in boron neutron capture therapy in one-stage process parameters with no fluid medium added which requires low power, labour and water consumptions.
13 cl, 15 ex
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention refers to medicine, more specifically to producing chitosan oligomers possessing biological activity and applicable in food industry and medicine. In a method for producing chitosan oligomers, a chitosan solution is taken in the concentration of 0.025-0.075% (weight/volume) and exposed to low-frequency ultrasound of the intensity of 92-460 Wt/cm2 for 5-30 minutes.
EFFECT: reduction in price of the chitosan oligomers production combined with promotion of higher medium viscosity molecular weight of the product within the range 25 ÷ 120 kDa.
3 tbl, 3 ex
SUBSTANCE: method involves preliminary acetylation of chitin with acetic anhydride, washing and drying the acetylated chitin in order to reduce degree of deacetylation thereof and, as a result, increase output of the desired product - D(+)-glucosamine hydrochloride when obtaining said product through hydrolysis of acetylated chitin with concentrated hydrochloric acid while heating, followed by evaporation, crystallisation, separation, washing and drying the desired product.
EFFECT: high output of the desired product while maintaining its high quality; method is more environmentally friendly since pre-treatment of chitin reduces the amount of processing wastes.
1 cl, 2 ex
SUBSTANCE: method of producing chitosan chromate involves reaction of soluble chitosan salts with metal chromates in ratio of 2 moles of the chitosan cation to 1 mole of chromate anion or with metal bichromates in ratio of 4 moles of the chitosan cation to 1 mole of the bichromate anion. The solid chitosan chromate residue formed is then separated and dried at temperature not higher than 150°C. The invention discloses an energy-intensive composition based on chitosan dodecahydro-closo-dodecaborate containing an effective amount of chitosan chromate. The quantitative ratio in the energy-intensive composition is by the required combustion mode: the higher the content of chitosan chromate, the higher the activity of the composition.
EFFECT: invention enables to obtain a chemical compound having sufficiently high oxidative properties and suitable for use in energy-intensive compositions which burn without emitting harmful gaseous products.
3 cl, 5 ex
FIELD: fish industry.
SUBSTANCE: method involves providing deacetylation of raw material with the use of preliminarily cooled alkaline solution; washing and drying. Deacetylation process is performed in three stages, first stage being performed for 7 days and subsequent two stages being performed for 2 hours each, combined with thermal processing at temperature of 55-590C. Washing process is provided after each deacetylation stage.
EFFECT: provision for producing of chitosan from chitin of cancerous with increased extent of deacetylation, while native properties of natural polymer being kept, without breaking of glycoside binding chain.
FIELD: organic chemistry.
SUBSTANCE: claimed method includes subsequent chitosane-containing raw material with non-polar liquefied gas, water, alkali, water, acid, water, alkali, and water to produce target product in form of solid residue, wherein in at least first extraction step pressure in reaction mixture is periodically released to provide extractant boiling, and than increased up to starting value.
EFFECT: method with reduced energy consumption.
FIELD: chemical technology of natural compounds.
SUBSTANCE: invention describes a method for preparing water-soluble derivatives of chitosan. Method involves treatment of chitosan with acid medium up to its swelling wherein vapor medium water-acid is used as acid medium. Treatment of chitosan is carried out with vapor of monobasic acid aqueous solution taken among the group including hydrochloric acid, formic acid and acetic acid. Method allows simplifying technology in preparing water-soluble derivatives of chitosan.
EFFECT: improved preparing method.
4 cl, 1 tbl, 9 ex
FIELD: chemistry and technology of derivatives of polysaccharides, chemical technology.
SUBSTANCE: invention relates to methods for preparing chitosan esters. Invention describes a method for preparing chitosan polyethylene glycol ester that involves dissolving chitosan in acetic acid followed by alkalization. Then the reaction mixture is subjected for effect of ethylene oxide under pressure 1-3 atm and temperature 60-100°C, and the concentration of reaction mass is corrected by addition of distilled water up to the density value of solution 1.030-1.032 g/cm3. Then the reaction mass is purified by electrodialysis at the rate value of solution in treatment chambers 3.0 cm/s, not less, temperature 20-45°C, the current density value 0.25-0.75 A/dm2 and the constant volume of the reaction mass. Method provides enhancing the effectiveness of purification by electrodialysis due to reducing energy consumptions. Chitosan esters can be used in medicine, cosmetics, food and chemical industry.
EFFECT: improved preparing method.
FIELD: organic chemistry of natural compounds, chemical technology, medicine.
SUBSTANCE: invention relates to the group of chitosan-containing compounds. Invention relates to synthesis of modified chitosan of the following structure: wherein n = 150-1400. The modified chitosan possesses the bactericidal activity, in particular, antituberculosis activity.
EFFECT: valuable medicinal properties of modified chitosan.
1 tbl, 1 dwg, 3 ex
FIELD: natural compounds technology.
SUBSTANCE: chitosan preparation process comprises breaking naturally occurring chitin-containing material, charging it into reactor, demineralization with 6-7% aqueous hydrochloric acid, deproteination with sodium hydroxide solution at 85-95°C, deacetylation with sodium hydroxide solution on heating, decoloration, and washing with water after each stage to pH 6.5. Process is characterized by that chitin-containing material broken to achieve fraction 0.5-6 mm is fed simultaneously into a number of reactors, wherein demineralization is effected with aqueous hydrochloric acid stream at 85-95°C for 1.5 h while controlling pH in each reactor exit to achieve acid concentration in each reactor exit the same as concentration of the initial acid by way of feeding it in a continuous manner. In addition, deproteination is carried out with 6-7% sodium hydroxide solution stream for 1.5 h followed by discharging treated material into autoclave to perform deacetylation simultaneously with decoloration using 50% sodium hydroxide solution at 130-140°C in inert gas environment and in presence of 3-5% hydrogen peroxide solution used in amount 3-5% of the total volume of mixture.
EFFECT: enhanced process efficiency.
FIELD: chemical technology.
SUBSTANCE: invention relates to methods for preparing water-soluble saline complexes (associates) of hyaluronic acid with d-metals of IV, V and VI periods of Mendeleyev's periodic system of elements that can be used in pharmacology and cosmetology. Invention describes a method for preparing water-soluble saline complexes of hyaluronic acid involving preparing an aqueous solution of salt of d-metal of IV, V and VI periods of periodic system and its mixing with hyaluronic acid sodium salt, holding the mixture, its stirring, dilution with water and isolation of the end product. For mixing method involves using the amount of aqueous salt of abovementioned d-metal that is equivalent to the amount of carboxy-groups of hyaluronic acid sodium salt or in the limit from 0.95 to 1.10. After dilution with water the solution mixture is subjected for ultrafiltration on separating membranes with simultaneous washing out with aqueous salt solution of abovementioned d-metal firstly and then with deionized water followed by concentrating the product. By another variant for mixing the method involves the amount of aqueous solution of d-metal salt lesser of the equivalent amount of carboxy-groups in hyaluronic acid sodium salt. After dilution with water the mixture is subjected for ultrafiltration on separating membranes with simultaneous washing out with deionized water followed by concentrating the product also. Method is characterized by the decreased time of processes and simplicity.
EFFECT: improved preparing method.
2 cl, 1 tbl
FIELD: medicine, food processing industry, in particular production of depolymerized chitosane and products based on the same.
SUBSTANCE: claimed method is based on using of chitosanase in acetic acid medium and spray drying of and depolymerized chitosane and is characterized in that obtained depolymerized chitosane is preliminary converted in non-ionized form by neutralizing of bound acetic acid with ammonium hydroxide followed by precipitation in ethanol and air drying. Further interaction is carried out with ammonium lipoate or glutathione in aqueous medium. Claimed products may be used individually or in combination with other components.
EFFECT: new products for food processing industry and medicine.
4 cl, 2 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing modified glycosaminoglycans possessing analgesic properties. Method involves interaction of glycosaminoglycans with 1-phenyl-2,3-dimethyl-4-aminopyrazolone-5-(4-aminoantipyrine) in aqueous medium at pH = 4.7-4.8 in the presence water-soluble 1-ethyl-3-[3-(dimethlamino)propyl]carbodiimide as a condensing agent at room temperature followed by purification from low-molecular reagents. Method involves a single step that simplifies technology in preparing modified glycosaminoglycans.
EFFECT: improved preparing method.
FIELD: natural substances, chemical technology.
SUBSTANCE: invention relates to a method for preparing chitosan and purification from components of the reaction mixture - low-molecular products of deacetylation and alkali excess. Invention relates to a method for purifying chitosan prepared by solid-state method involving treatment of reaction mass with extractant consisting of 3.3-20.0% of water, 32.2-57.1% of ethyl acetate and 24.6-64.5% of ethanol at the extractant boiling point. Also, invention relates to a method for purifying chitosan prepared by suspension method and involving treatment of the reaction mass with ethyl acetate and the following treatment with extractant consisting of 6.2-25.0% of water, 12.5-62.5% of ethyl acetate and 31.3-62.5% of ethanol at the extractant boiling point.
EFFECT: improved isolating and preparing method.
3 cl, 2 tbl, 1 dwg