the inventive dusting powder may be prepared by grinding or otherwise pulverizing an enzymatically degradable form of poly ( n - acetyl - d - glucosamine ) selected from the group consisting of to the desired particle size by the use of conventional grinding equipment and techniques known to those skilled in the art . the polymer may be ground in an ordinary ball mill . the grinding equipment is preferably grounded during the grinding operation to prevent undesirable aggregation of the particles caused by the static electrical charges which can accumulate on the particles during grinding . the ground material can then be removed from the mill and vibrated through a series of screens of varying mesh mounted on a ro - tap testing sieve shaker as supplied by w . s . tyler co . particle size of the ground polymer is an important criteria in selecting a powder which is suitable for a glove powder . it is desirable that all the powder particles be small enough to pass through a 100 mesh screen ( 149 micron designation in the u . s . sieve series ). however , small amounts ( up to about 1 percent by weight ) of somewhat larger sized particles can also be present in the powder without undue adverse effect on the lubricating properties of the polyglycolic acid powder . it is preferred that all of the powder particles pass through a 200 mesh screen ( 74 micron designation in the u . s . sieve series ). passage through such a screen indicates the particles contain not more than one dimension exceeding about 74 microns . in preparing the glove powder it is equally important that it not be made too fine in order to minimize the escape of excessive powder into the environment in the course of powdering the hands , surgical gloves , or other items . the powder , on the other hand , should not be of an excessively large particle size nor should it contain substantial amounts of exceptionally large particles since this will create an undesirable abrasive effect upon the skin of the hand when the powder is used . a suitable particle size range is from about 0 . 5 to about 149 microns with a range of from about 10 to 50 microns preferred . glove powder is used in a variety of ways by the medical profession . rubber surgical gloves are typically sold unsterile in pairs with a package of glove powder inserted in the cuff of one of the gloves . when it is desired to use the gloves , the gloves and the package of glove powder are sterilized , usually by autoclaving . the surgeon will then open the package of glove powder ( the package usually contains about 1 . 5 grams of powder ) and pour the powder onto his hands . after working the powder over the surface of his hands , the surgeon inserts his powdered hands into the surgical gloves , the glove powder providing the lubricity required to facilitate this insertion . in cases where the gloves are reusable , the gloves , at the end of the operation , will be washed , dried , inspected for holes and then repowdered , usually on both the internal and external surfaces of the glove for subsequent reuse of the glove . this powdering is ordinarily accomplished by placing the gloves and a prescribed amount of glove powder in a tumbler and tumbling for a sufficient period of time to powder the inside and outside surfaces of the glove . the powdered gloves are then repackaged , autoclaved , and presented to the surgeon for use . since the outside of the glove is often powdered it is readily apparent how some of the powder may spill off the glove and into the exposed surgical cavity of a patient . disposable surgical gloves usually made of latex are also available to the medical profession . these gloves can be offered as a unit of one pair of gloves and one package of glove powder contained in a suitable package . however , they are ordinarily offered as a powdered glove , i . e ., the inner and outer surfaces of the glove are pre - powdered with a suitable dusting powder . when the contents of the envelope , i . e ., the gloves and the powder are sterile , the entire envelope must first be autoclaved or otherwise sterilized . at the end of the operation the gloves are discarded . typical glove packages are described in u . s . pat . nos . 3 , 107 , 786 and 3 , 181 , 695 . the gloves of the present invention may be sealed in a strippable enclosure of the type shown in u . s . pat . no . 2 , 949 , 181 , there described for sutures , but adaptable to surgical gloves . a larger size strippable laminate enclosure is used for gloves . from the foregoing it becomes apparent that the glove powder of this invention can be offered either separately in a single package of a suitable material or in combination with a pair of surgical gloves in either a sterile or unsterile condition . the powder itself may be either sterile or non - sterile . it is desirable when a sterile powdered surgical glove , sterile powder , or a sterile combination of a surgical glove and separately packaged glove powder is to be offered , to package the aforementioned sterile items in a sterile inner enclosure which is then packaged in a sterile outer enclosure . the outer enclosure is provided with a strippable seal , which then allows for convenient serving of said sterile item to the potential user by merely stripping away the outer enclosure to present a totally sterile enclosure , i . e ., the outer surface as well as the contents of the inner enclosure are sterile , containing the sterile item to the user . the user can then open the package and remove the sterile item therein without risk of contaminating the contents from contact with the outer surface of the inner enclosure . chitin has been estimated to be the second most abundant polysaccharide in nature with a synthesis in the neighborhood of a billion tons a year by marine organisms . see chitin , n . v . tracey , reviews of pure and applied chemistry , royal australian chemical institute , vol . 7 , no . 1 , march , 1957 , pages 1 to 14 . carboxymethylchitin is disclosed in carbohyd , res . 7 , 483 - 485 ( 1968 ), ralph trujillo . this article mentions the hydrolysis of both chitin and carboxymethylchitin by lysozyme . poly ( n - acetyl - d - glucosamine ) differs from cellulose in that instead of a hydroxyl group in the 2 position on cellulose , there is an acetylamino group . prudden , migel , hanson , freidrich and balassa in &# 34 ; the discovery of a potent pure chemical wound - healing accelerator &# 34 ;, the american journal of surgery , vol . 119 , may 1970 , pages 560 to 564 , disclose that chitin containing n - acetyl glucosamine is useful to accelerate wound - healing . the enzyme lysozyme is particularly effective in the enzymatic degradation of the present forms of poly ( n - acetyl - d - glucosamine ). various forms of poly ( n - acetyl - d - glucosamine ) may have different degradation rates , and the degradation rate may vary with the location , but with minimal tissue reaction . the poly ( n - acetyl - d - glucosamine ) in its own right has been shown to encourage wound healing . the lubricant powders of the present forms of poly ( n - acetyl - d - glucosamine ) are not hydrolyzed by water and , hence , need not be kept bone dry but may be stored under ambient conditions of moisture for prolonged periods of time . the basic poly ( n - acetyl - d - glucosamine ) may be modified by treatment to introduce carboxymethyl , hydroxyethyl or o - ethyl substituents so that the polymer has linkages from acetyl - 6 - o -( carboxymethyl )- d - glucosamine units , acetyl - 6 - o -( 2 &# 39 ;- hydroxyethyl )- d - glucosamine units , or acetyl - 6 - o -( ethyl )- d - glucosamine units . other side chains may be placed on the glucosamine ring , or its substituents because the side chains may vary from methyl to long chain alkyl , including branched chains , unsaturated chains , aryl or aralkyl , and which may include halogen , alkoxy , aryloxy , aralkoxy , ether , ester and amide groups , as substituents on the side chains , the relative distribution between aqueous and solvent components in a system can be varied as well as water solubility or oil and solvent solubility . also , because the size and location of the side chains affects the rate of degradation and the acidity of the system , the rate of enzymatic degradation can be varied . lubricant powders may be made by precipitating solutions of suitable forms of poly ( n - acetyl - d - glucosamine ) in polyfluorinated solvents such as hexafluoroisopropyl alcohol and hexafluoroacetone sesquihydrate or mixtures of such solvents . ( n - acetyl - d - glucosamine ) has the formula : ## str1 ## groups below the plane of the paper are shown by a dotted bond . poly ( n - acetyl - d - glucosamine ) has ascribed to it the formula ( ring hydrogens omitted for clarity ) ## str2 ## poly ( n - acetyl - d - glucosamine ) is a major component of naturally occurring chitin . the naturally occurring material has not only the poly ( n - acetyl - d - glucosamine ) but also inorganic salts thought to be forms of calcium carbonate and proteinaceous material , the composition of which is not presently known . the term &# 34 ; chitin &# 34 ; is used herein to refer to the various naturally occurring forms of chitin including the protein and inorganic carbonate components . the term &# 34 ; purified chitin &# 34 ; is used to refer to chitin after purification to remove calcium carbonate and other inorganic salts and various proteins which may be present and is essentially poly ( n - acetyl - d - glucosamine ). some confusion exists in the literature in that the name chitin is used as a name for poly ( n - acetyl - d - glucosamine ) without specifying whether it is a naturally occurring material containing inorganic salts and proteins or whether the term is intended to designate purified poly ( n - acetyl - d - glucosamine ) without specifying the degree of purity or the character of the impurities present . the term &# 34 ; enzymatically degradable &# 34 ; refers to a form of poly ( n - acetyl - d - glucosamine ) or its derivatives which is broken down into body fluid soluble components . the problem of retention by the body or disposal is minimal or non - existent . one convenient method of sterilizing the present lubricant powder is by heat under such conditions that any microorganisms or deleterious materials are rendered inactive . another common method is to sterilize using a gaseous sterilizing agent such as ethylene oxide . other methods of sterilizing include radiation by x - rays , gamma rays , neutrons , electrons , etc ., or high intensity ultrasonic vibrational energy or combinations of these methods . the present lubricant powders may be sterilized by any of these methods , although there may be appreciable but acceptable change in physical characteristics . a commerical grade of chitin ( cal - biochemicals ) was finely ground in a ball mill overnight to pass a 6 mm screen and be retained by a 1 mm screen . 149 g . of this finely ground material was decalcified by extracting with 825 ml . of 2n hcl at 4 ° c for 48 hours , in a flask stirred with a magnetic stirrer . the material was collected by centrifugation and washed repeatedly with water until neutral . the ash content was 0 . 4 - 0 . 5 %. the decalcified chitin was then stirred at room temperature with 1500 ml . of 90 % formic acid overnight . the mixture was centrifuged and the residue repeatedly washed with water . the washed chitin was then suspended in 2 liters or 10 % naoh solution and heated at 90 °- 100 ° c . for 2 . 5 hours . the solution was filtered , the cake washed with water until neutral , washed several times with absolute ethanol and ether , and dried at 40 ° c . under reduced pressure ; yield 66 g . of poly ( n - acetyl - d - glucosamine ). infrared spectrum ( kbr pellet ) shows bands at 3500 cm - 1 ( s ), 2900 ( w ), 1652 ( s ), 1619 ( s ), 1550 ( s ), 1370 ( s ), 1300 ( m ), 1070 ( broad ). ( s is strong , m is medium , w is weak . membranes of poly ( n - acetyl - d - glucosamine ) were prepared by dissolving poly ( n - acetyl - d - glucosamine ) from example 1 in each of hexafluoroacetone sesquihydrate ( 1 . 4 % solution ) and hexafluoroisopropanol ( 2 % solution ), and casting on a glass plate . the last traces of solvent were evaporated off in a vacuum . the films were tough , transparent , non - tacky , flexible and were quite pliable when hydrated yet retained adequate strength to resist manipulation . the membranes showed no hydrolysis after exposure to water for 5 days . 15 g . of the poly ( n - acetyl - d - glucosamine ) from example 1 was swollen with 100 ml . of dimethylsulfoxide ( dmso ). to this highly swollen suspension was added 400 ml . of 2 - propanol and the mixture was stirred vigorously under nitrogen while 40 ml . 30 % aqueous naoh was added over an interval of 30 minutes at room temperature . after stirring for an additional hour , 18 g . of chloracetic acid dissolved in 40 ml . of water was added dropwise over a 30 minute period . the mixture was then heated at 55 ° c . for 24 hours . the mixture was decanted and to the residue was added 100 ml . of 70 % methanol . the suspension was then neutralized with 5 ml . of 90 % acetic acid . the mixture was filtered , washed with 70 % methanol , absolute methanol and dried at 40 ° c . in vacuo . yield 24 g . of poly [ n - acetyl - 6 - o -( carboxymethyl )- d - glucosamine ], i . infrared ( kbr pellet ) shows bands at 3500 cm - 1 ( s ), 2900 ( m ), 1600 broad ( s ), 1400 ( m ), 1320 ( m ), 1100 broad ( s ). a sample was titrated and shown to have 4 . 03 meq acid / g indicating 100 % of the repeating mers were carboxylated . films easily removed from glass were cast from water solution and shown to be transparent , flexible and tough . after 24 hours incubation at 37 ° c . in phosphate buffer ph 7 . 2 containing 1500 units / ml of lysozyme , poly [ n - acetyl - 6 - o -( carboxymethyl )- d - glucosamine ] was hydrolyzed to oligomers as determined by gel permeation chromatography . a control containing no enzyme was not hydrolyzed under the same conditions . into a screw cap bottle was placed 13 . 6 g of purified poly ( n - acetyl - d - glucosamine ) milled so that it passed a 1 mm . sieve . to the bottle was added 200 ml . of cold ( 0 °- 5 ° c .) aqueous 43 % naoh and the contents stirred for 2 hours under nitrogen and then held at 0 °- 4 ° c . for 10 hours . the swollen alkali derivative was then squeezed to 3 times its original weight in a sintered glass funnel , disintegrated and frozen at - 20 c . under nitrogen for 1 hour and then thawed at room temperature for 1 hour . the freeze - thaw cycle was repeated 3 times . to the alkali derivative was then added 120 ml . of dimethyl sulfoxide ( dmso ) and the slurry added immediately to a stirred autoclave . the autoclave was purged several times with nitrogen and 53 . 2 ml . of ethylene oxide was added ( 16 equivalents / equivalent of pag ). the mixture was held at 50 ° c . for 18 hours . the solution was then carefully neutralized with glacial acetic acid , dialyzed and then lyophilized . the hydroxyethyl derivative can be further purified by precipitating the polymer from aqueous solution with acetone . a freshly precipitated sample of poly [ n - acetyl - 6 - o -( 2 &# 39 ;- hydroxyethyl )- d - glucosamine ] readily dissolved in water , 5 % aqueous sodium hydroxide , and 3 % acetic acid and is precipitated from these solutions by acetone . samples analyzed for c , h , and n showed the composition to be one in which 1 . 5 hydroxyethyl groups had been substituted per glucosamine residue . the procedure of example 5 was followed except 75 ml . of ethylchloride was added instead of ethylene oxide and the reaction held at 50 ° c . for 15 hours . a water soluble derivative is obtained . to obtain an organic soluble derivative , the ethylchloride was mixed with benzene ( 75 % of the amount of ethylchloride ). the reaction time was 10 hours and the temperature was controlled as follows : 1 hour heating up to 60 ° c ., 1 hour heating up to 80 ° c ., 1 hour heating up to 130 ° c . and 7 hours at 130 ° c . an organic solvent soluble product was obtained . the following solvents are useful for solubilization ( 5 % solution ) of this polymer at room temperature : o - xylene , benzene , toluene , methylethyl ketone , 1 . 4 mixture of alcohol and benzene , chloroform and alcohols . 1 , 2 , 3 , 5 , and 6 were separately placed in a 1 quart ball mill with about 40 grams of product and five 11 / 4 inch balls , ten 1 inch balls , nine 1 / 2 inch balls , nine 3 / 4 inch balls and 145 / 8 inch balls . the mill was grounded and rotated from a friday afternoon to a wednesday morning , about 113 hours ; the balls separated and the product screened . about 88 to 90 % of the ground product passed a 325 mesh screen with an average particle size of about 25 microns . a pair of gloves dusted with 11 / 2 grams of each of the product powders were sealed between a polyester , polyethylene laminate as above described using a strippable seal and a group of the gloves were then placed in an ethylene oxide chamber to allow the ethylene oxide to penetrate through the laminate seal as described in more detail in u . s . pat . no . 2 , 917 , 878 canarius and kaufman . the individual gloves before sterilization are indicated in fig1 the surface of the glove 11 has the finely divided biodegradable powder 12 spread thereover . fig2 shows the surgeon donning the glove . the glove 13 is held by a nurse whose hands 14 hold the glove with the cuff slightly stretched while the hand of the surgeon 15 is inserted therein to . fig3 shows the surgical glove 11 , having the powder 12 on its surfaces , folded in a paper wrapper 16 , inserted in an outer strippable envelope 17 . it is convenient to powder the glove with the finely divided polymer before the glove is sterilized , and sterilize the powdered glove and keep it in sterile condition until ready for use . it is also convenient to use the powder in sterile form to be applied to the surface of sterile gloves at the time they are being put on . the time of powdering the glove and the time for storing can vary with the technique and schedules of the particular user , such as a hospital or individual surgeon . if sterile gloves are used , a single use disposable glove is convenient . if the gloves are to be reused , the time of applying the powder and the sterilizing can be varied depending upon the number of gloves used in the inventory available or preferences . when used in patients during surgical procedures , no deleterious effects which could be ascribed to the glove powder were observed . fig4 shows a catheter 18 similarly packaged in a similar strippable package . other sizes and types of ball mills , grinding cycles or systems of attriting may be used with good results . natural chitin if ball milled to the preferred particle size acts as a satisfactory lubricant -- but with various marine and fungal sources , the impurities , particularly the proteins , may vary and have different interactions with tissue . preferably the chitin is purified and optionally chemically modified and the resultant enzymatically degradable forms of poly ( n - acetyl - d - glucosamine ) used because of greater freedom from the possibility of tissue reaction .
natural or synthetic rubber surgical elements such as tubing , catheters , drains and gloves are &# 34 ; lubricated &# 34 ; so as to prevent sticking during storage , and permit easier emplacement , such as putting on the gloves by a surgeon or nurse , by applying to the surface of the rubber element a finely divided biodegradable powder consisting essentially of an enzymatically degradable form of poly selected from the group consisting of poly - d - glucosamine ], poly - d - glucosamine ], poly - d - glucosamine ], and poly itself this powder is readily absorbed by living tissue without deleterious tissue reaction , thus minimizing tissue reaction from the transfer of the powder from the element such as a glove to internal sites in a subject . the gloves may be packaged in a strippable laminate package . the polymers are derived from chitin .