Compositions for controlled release of active ingredients and methods of making same

Abstract

Compositions for controlled release of active ingredients and methods of making same are generally provided. In some embodiments, the composition comprises an active ingredient and a delivery material. In some embodiments, the composition comprises a volatile or gaseous active ingredient useful for applications in at least one of agriculture, pest control, odor control, and food preservation. In some embodiments, the active ingredient is a cyclopropene. In some embodiments, the active ingredient is an essential oil, a terpene, or a terpenoid. In some embodiments, the delivery material is a carbon material or a silicate material.

1 . A composition comprising:
 a delivery material selected from among the group consisting of carbon materials and silicate materials; and   a volatile or gaseous active ingredient useful for applications in at least one of agriculture, pest control, odor control, and food preservation present in the composition in at least about a 0.01 wt % versus the total weight of the delivery material and the active ingredient,   wherein the composition is configured to release the volatile or gaseous active ingredient in the volatile or gaseous phase without addition of external wetting or hydrating, and   wherein over a two week period in a non-equilibrium condition, the composition is configured to release about 20% to about 50% of the weight of the active ingredient originally present in the composition.   
     
     
         2 . A composition comprising:
 a delivery material selected from the group consisting of carbon materials and silicate materials, wherein the delivery material is an amorphous solid; and   a cyclopropene present in the composition in at least about 0.05 wt % versus the total weight of the delivery material and the cyclopropene,   wherein the composition is configured to release the cyclopropene without the addition of external wetting or hydrating.   
     
     
         3 . The composition of  claim 1 , wherein the delivery material is:
 a silicate delivery material.   
     
     
         4 . A composition comprising:
 a delivery material being a carbon material, wherein the carbon material comprises 75-100% carbon; and   a cyclopropene present in the composition in at least about 0.05 wt % versus the total weight of the delivery material and the cyclopropene,   wherein the composition is configured to release the cyclopropene at temperatures from about 0° C. to about 40° C.   
     
     
         5 . A composition, comprising:
 a porous delivery material;   a cyclopropene present in the porous delivery material in at least about 0.01 wt % versus the composition weight,   wherein the composition is configured to release the cyclopropene between hour 22 and hour 120 at a release rate sustained within a range of about 1 and about 15 μL/g composition weight/hr;   wherein the composition weight is the weight of the delivery material and the cyclopropene.   
     
     
         6 . The composition of  claim 2 , wherein:
 a release rate of the cyclopropene from the composition at hour 22 is at least 0.1% of the release rate at hour 1.   
     
     
         7 . A composition, comprising:
 a delivery material comprising an inert material in a concentration of 50-100 mol % of the delivery material, wherein the inert material is a porous silicate material comprising a surface area greater than about 1 m 2 /g; and   at least one active ingredient selected from the group consisting of cyclopropene, essential oils, terpenes, terpenoids, carvone, thymol, hexanal, carvacrol, eugenol, limonene, clove oil, lemongrass oil, oregano oil, and thyme oil.   
     
     
         8 . The composition of  claim 2 , wherein the silicate material is a delivery material. 
     
     
         9 . The composition of any of the preceding claims, further comprising a binder, oil, hydrogel, or polymer. 
     
     
         10 . The composition of any of the preceding claims, further comprising a hygroscopic material. 
     
     
         11 . The composition of any of the preceding claims, further comprising a diluent material. 
     
     
         12 . The composition of any one of the preceding claims, wherein the delivery material is porous. 
     
     
         13 . The composition of any of the preceding claims, wherein the delivery material comprises a nanoporous, microporous, macroporous or mesoporous silicate, a non-porous silicate material, a silicate material, a nanoporous, microporous, macroporous, or mesoporous carbon, an organosilicatetete hybrid, or combinations thereof. 
     
     
         14 . The composition of any of the preceding claims, wherein the delivery material comprises a templated siliceous material. 
     
     
         15 . A composition of any of the preceding claims, wherein the silicate material is in at least one of powder, pellet, granule, nanoscale, and mesoporous form. 
     
     
         16 . A composition of any of the preceding claims, wherein the silicate material comprises a commercial silicate. 
     
     
         17 . A composition of any of the preceding claims, wherein the silicate material is selected from the group consisting of: i) precipitated, crystalline-free silicate gel, ii) amorphous, fumed (crystalline free) silicate, and iii) mesostructured amorphous silicate. 
     
     
         18 . The composition of any of the preceding claims, wherein the delivery material comprises a solid material. 
     
     
         19 . The composition of any of the preceding claims, wherein the delivery material comprises an amorphous solid, a glassy solid, a ceramic, or a non-crystalline solid. 
     
     
         20 . The composition of any of the preceding claims, wherein the delivery material comprises a carbon based material. 
     
     
         21 . The composition of any of the preceding claims, wherein the delivery material comprises activated carbon or activated charcoal. 
     
     
         22 . The composition of any of the preceding claims, wherein the carbon material comprises a monolithic carbon material, an extruded or pelletized carbon material, a steam-activated carbon material, an oxidized carbon material, a heat treated carbon material, an acid-treated carbon material, a base-treated carbon material, ash, char, biochar, soot, or a combination thereof. 
     
     
         23 . The composition of any of the preceding claims, the delivery material comprising an elemental composition indistinguishable from that of sand. 
     
     
         24 . The composition of any of the preceding claims, wherein the carbon material is in at least one of powder, pellet, granule, film, and extrudate form. 
     
     
         25 . A composition of any of the preceding claims, wherein the carbon material comprises a commercial carbon. 
     
     
         26 . The composition any of the preceding claims, wherein the carbon material is an extruded carbon with a pellet diameter of 0.1-4.5 mm. 
     
     
         27 . The composition of any of the preceding claims, wherein the delivery material comprises a high-surface area material. 
     
     
         28 . The composition of any of the preceding claims, wherein the delivery material comprises at least one of a mesoporous carbon material, a nanoporous carbon material, and microporous carbon material, the carbon material modified with at least one of an oxidant, hydrolyzing reagent, heat, an acid, and a base. 
     
     
         29 . The composition of any of the preceding claims, wherein the delivery material comprises a modified carbon material. 
     
     
         30 . The composition of  claim 20 , wherein the carbon material has been modified with water. 
     
     
         31 . The composition of any of the preceding claims, wherein the carbon material has been modified with at least one of sulfuric acid, hydrochloric acid, perchloric acid, hypochloric acid, and a conjugate base of those acids. 
     
     
         32 . The composition of any of the preceding claims, wherein the carbon material has been modified with at least one of ozone gas, hydrogen peroxide, organoperoxides, and oxygen gas. 
     
     
         33 . The composition of any of the preceding claims, wherein the carbon material has been modified with nitric acid in a concentration from 0.01-99%. 
     
     
         34 . The composition of any of the preceding claims, wherein the delivery material has a surface area between about 1 to about 3000 m 2 /g, or between about 1 to about 2500 m 2 /g, or between about 100 to about 1500 m 2 /g, or between about 500 to about 1500 m 2 /g, or between about 1000 to about 1500 m 2 /g or between about 50 to about 2000 m 2 /g. 
     
     
         35 . The composition of any of the preceding claims, wherein the delivery material comprises a high-surface area material comprising a total chemical surface area, internal and external, greater than 1 m 2 /g, or greater than 10 m 2 /g, or greater than 90 m 2 /g, or greater than 500 m 2 /g, or greater than 1000 m 2 /g. 
     
     
         36 . The composition of any of the preceding claims, wherein the delivery material comprises a porous material having a pore volume between about 0.1 cm 3 /g to about 10 cm 3 /g, or between about 0.1 cm 3 /g to about 5 cm 3 /g, or between about 0.5 cm 3 /g to about 2 cm 3 /g, or between about 0.5 cm 3 /g to about 1.5 cm 3 /g, or between about 0.5 cm 3 /g to about 10 cm 3 /g, or between about 0.5 cm 3 /g to about 5 cm 3 /g, or between about 0.5 cm 3 /g to about 1.5 cm 3 /g, or between about 1 cm 3 /g to about 1.5 cm 3 /g. 
     
     
         37 . The composition of any of the preceding claims, wherein the delivery material comprises a porous material having a d-spacing of about 3.0 Å to about 4.5 Å. 
     
     
         38 . The composition of any of the preceding claims, wherein the delivery material comprises a porous material having an internal void volume greater than about 0.1 cm 3 /g, or greater than about 1 cm 3 /g, or greater than about 1.5 cm 3 /g. 
     
     
         39 . The composition of any of the preceding claims, wherein the delivery material comprises a carbon material having one or more of the following properties: a density in the range of 0.2-3 g/cm 3 ; a pore volume in the range of 0.1-1.5 cm 3 /g; a surface area in the range of 500-4000 m 2 /g; moisture content in the range of 0-30%. 
     
     
         40 . The composition of any of the preceding claims, wherein
 the delivery material comprises a silicate material, and   wherein the silicate material comprises one or more of the following properties: particle size of 5 nm to 5 mm, a pore volume of 0.5-5 cm 3 /g, a surface area of 0.01-2000 m 2 /g.   
     
     
         41 . The composition of any of the preceding claims, wherein:
 the delivery material comprises a silicate material, and   wherein the silicate material comprises one or more of the following properties: a pore size of 60 Å, a mean particle diameter of 63-200 μm, a pore volume of 0.7-0.85 cm 3 /g, and a surface area of 480 m 2 /g.   
     
     
         42 . The composition any of the preceding claims, wherein the delivery material is a polymer, inorganic material, organic material, or hybrid thereof. 
     
     
         43 . The composition of  claim 16 , wherein the polymer, inorganic material, organic material, or hybrid thereof comprises 0-99.99 wt % of the composition. 
     
     
         44 . The composition of  claim 1 , wherein the delivery material comprises 0-99.99 wt % of the composition. 
     
     
         45 . The composition of any of the preceding claims, wherein the polymer, inorganic material, organic material, or hybrid thereof comprises 50-100 mol % of the delivery material. 
     
     
         46 . The composition of any of the preceding claims, wherein the delivery material comprises an inert material. 
     
     
         47 . The composition of any of the preceding claims, wherein:
 the inert material is selected from the group consisting of a polysiloxane, a polyalkylsiloxane, a polyalkylenesiloxane, and a polyoxoalkyelene, and   wherein the inert material optionally further comprises a surfactant.   
     
     
         48 . The composition of any of the preceding claims, wherein the inert material comprises a porous or otherwise high-surface-area silicate; and optionally a surfactant. The composition of any of the preceding claims, wherein the inert material comprises a templated, porous, or otherwise high-surface-area refractory metal oxide; and optionally a surfactant. 
     
     
         49 . The composition of any of the preceding claims, wherein the inert material comprises a templated, porous, or otherwise high-surface-area organic material. 
     
     
         50 . The composition of any of the preceding claims, wherein the inert material comprises nanoporous, microporous, or mesoporous activated carbon; and optionally a surfactant. 
     
     
         51 . The composition of any of the preceding claims, wherein the delivery material comprises a mesoporous material silicate prepared by using tetraethoxysilane (TEOS). 
     
     
         52 . The composition of any of the preceding claim, wherein the delivery material comprises tetradecakis-2,6-O-allylcycloheptaamylose. 
     
     
         53 . The composition of  claim 9 , wherein the ratio of TEOS to tetradecakis-2,6-O-allylcycloheptaamylose in Si mole ratios is selected from among 1:0, 0.9:0.1, 0.75:0.25, 0.50:0.50, and 0.25:0.75. 
     
     
         54 . The composition of any of the preceding claims, wherein the delivery material comprises a recyclable material. 
     
     
         55 . A composition of any of the preceding claims, prepared by a process comprising the steps of modifying at least one of the hydrophobicity, hydrophilicity, chemical potential, zeta-potential, acidity, basicity, surface functionalization, and surface functional group density of a carbon material; and impregnating the modified carbon material with at least one active ingredient. 
     
     
         56 . The composition of any of the preceding claims, further comprising at least one complexing agent or, optionally at least one adsorption-modifying functionality. 
     
     
         57 . The composition of any of the preceding claims, wherein the complexing agent is impregnated with the active ingredient. 
     
     
         58 . The composition of any of the preceding claims, wherein the complexing agent is embedded into the delivery material. 
     
     
         59 . The composition of any of the preceding claims, comprising a complexing agent immobilized on at least one of the internal and external surface of the delivery material. 
     
     
         60 . The composition of any of the preceding claims, wherein at least one pore of the delivery material comprises a complexing agent. 
     
     
         61 . The composition of any of the preceding claims, wherein the delivery material comprises a complexing agent in a concentration of 0-50 mol % of the delivery material. 
     
     
         62 . The composition of any of the preceding claims, wherein the complexing agent comprises β-cyclodextrin. 
     
     
         63 . The composition of any of the preceding claims, wherein the complexing agent comprises β-cyclodextrin in a concentration of 1-20 mol % of the delivery material. 
     
     
         64 . The composition of any of the preceding claims, wherein the complexing agent comprises substituted β-cyclodextrin. 
     
     
         65 . The composition of any of the preceding claims, wherein the substituted β-cyclodextrin comprises one of silyl-modified β-cyclodextrin and allyl-modified β-cyclodextrin. 
     
     
         66 . The composition of any of the preceding claims, wherein the complexing agent comprises substituted β-cyclodextrin in a concentration of 0-20 mol % of the delivery material. 
     
     
         67 . The composition of  claim 1 , wherein the complexing agent comprises an unsubstituted β-cyclodextrin in a concentration of 1-20 mol % of the delivery material. 
     
     
         68 . The composition of any of the preceding claims, wherein the complexing agent comprises at least one of unsubstituted β-cyclodextrin, silyl-modified β-cyclodextrin, allyl-modified β-cyclodextrin, α-cyclodextrin, γ-cyclodextrin, trimethylsilyl functionalities. 
     
     
         69 . The composition of any of the preceding claims, wherein the complexing agent is selected from among the group consisting of a cyclodextrin, a substituted cyclodextrin, a modified cyclodextrin, a crown ether, a substituted crown ether, a modified crown ether, a calixarene, a substituted calixarene, a modified calixarene, and combinations thereof. 
     
     
         70 . The composition of any of the preceding claims, wherein the complexing agent is selected from the group consisting of: α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, mono-, oligo-, or polycarbohydrates, porphyrins, phosphazenes, cyclodextrins, substituted or modified cyclodextrins, crown ethers, substituted or modified crown ethers, calixarenes, and substituted or modified calixarenes, and combinations thereof. 
     
     
         71 . The composition of any of the preceding claims, further comprising at least one of a complexing agent and an adsorption-modifying functionality. 
     
     
         72 . The composition of any of the preceding claims, wherein the adsorption-modifying functionality is a trimethylsilyl-functionality. 
     
     
         73 . The composition of any of the preceding claims, wherein the adsorption-modifying functionality is one of hydrophobic or aliphatic groups installed on at least one of an internal and external surface of the delivery material. 
     
     
         74 . The composition of any of the preceding claims, wherein the complexing agent is embedded into the delivery material. 
     
     
         75 . The composition of any of the preceding claims, comprising a complexing agent immobilized on at least one of the internal and external surface of the delivery material. 
     
     
         76 . The composition of any of the preceding claims, wherein at least one pore of the delivery material comprises a complexing agent. 
     
     
         77 . The composition of any of the preceding claims, wherein the delivery material has a moisture content in the range of 0 to about 2%, or in the range of 2 to about 5%, or in the range of 5 to about 15%, or in the range of 15 to about 25%, or in the range of 25 to about 50%, or in the range of 50 to about 100%. 
     
     
         78 . The composition of any of the preceding claims, wherein the delivery material does not comprise a complexing agent. 
     
     
         79 . The composition of any of the preceding claims, wherein the delivery material comprises a carbon delivery material having a density in the range of about 0.1 to about 0.3 g/cm 3 , or in the range of about 0.3 to about 0.6 g/cm 3 , or in the range of about 0.6 to about 1.0 g/cm 3 , or in the range of about 1 to about 3 g/cm 3 , or in the range of about 0.3 to about 1.5 g/cm 3 . 
     
     
         80 . The composition of any of the preceding claims, wherein the the delivery material comprises a carbon delivery material having a density in the range of about 0.05 to about 0.15 g/cm3, or in the range of about 0.15 to about 0.3 g/cm3, or in the range of about 0.3 to about 0.7 g/cm3, or in the range of about 1 to about 1.5 g/cm3, or in the range of about 0.5 to about 1.5 g/cm3. 
     
     
         81 . The composition of any of the preceding claims, wherein the delivery material comprises a carbon delivery material having a density in the range of about 0.3 to about 0.6 g/cm3. 
     
     
         82 . The composition of any of the preceding claims, wherein the delivery material comprises a plurality of pores. 
     
     
         83 . The composition of  claim 82 , wherein a plurality of the plurality of pores store the active ingredient or the cyclopropene. 
     
     
         84 . The composition of any of the preceding claims, wherein the delivery material comprises a complexing agent in a concentration of 0-50 mol % of the delivery material and an inert material in a concentration of 50-100 mol % of the delivery material. 
     
     
         85 . The composition of any of the preceding claims, wherein the composition comprises at least one volatile or gaseous active ingredient. 
     
     
         86 . The composition of any of the preceding claims, wherein the at least one active ingredient is selected from among an ethylene inhibitor, an ethylene promoter, a plant growth regulator, an essential oil, a terpene, a terpenoid, a phenol, a pholspholipase-D inhibitor, an antimicrobial, an antifungal, and antiseptic, an antioxidant, and combinations thereof. 
     
     
         87 . The composition any of the preceding claims, wherein the at least one active ingredient has anti-bacterial, anti-microbial, anti-fungal, anti-algae, or anti-viral properties. 
     
     
         88 . The composition of any of the preceding claims, wherein the active ingredient is present in the composition in up to 30 wt % versus the total weight of the composition. 
     
     
         89 . The composition of any of the preceding claims, wherein the volatile or gaseous active ingredient is a cyclopropene. 
     
     
         90 . The composition of any of the preceding claims wherein the cyclopropene is 1-methylcyclopropene (1-MCP). 
     
     
         91 . The composition any of the preceding claims, wherein the at least one active ingredient comprises one or more of a terpene and a terpenoid. 
     
     
         92 . The composition of any of the preceding claims, wherein the at least one active ingredient comprises at least one of a monoterpene, a diterpene, an oligoterpene, an acyclic terpene, a cyclic terpene, a polyterpene, an aliphatic terpene, an aromatic terpene, and combinations thereof. 
     
     
         93 . The composition of any of the preceding claims wherein the at least one active ingredient is selected from the group consisting of carvacrol, thymol, carvone, oregano oil, dill oil, thyme oil, neem oil, 1-methylcyclopropene (1-MCP), hexanal, and combinations thereof. 
     
     
         94 . The composition of any of the preceding claims, wherein the at least one active ingredient is an essential oil. 
     
     
         95 . The composition of any of the preceding claims, wherein the essential oil comprises an essential oil extract or a botanical extract. 
     
     
         96 . The composition of any of the preceding claim, wherein the at least one active ingredient is selected from the group consisting of oregano oil, thyme oil, hexanal, carvacrol, and thymol, and combinations thereof. 
     
     
         97 . The composition of any of the preceding claims, wherein the composition is configured to release the least one active ingredient over a period of between about 5 days to about 30 days, or optionally, between about 5 days to about 7 days, or optionally, between about 3 days to about 10 days, or optionally between about 3 days to about 14 days. 
     
     
         98 . The composition of any of the preceding claims, wherein over a two week period in a non-equilibrium condition, the composition is configured to release about 20% to about 50% of the weight of the active ingredient originally present in the composition. 
     
     
         99 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 1 is between about 30 and about 1500 μL/g composition/hr, or at least greater than zero μL/g composition/hr at hour 22, or is at least about 0.0005 μL/g composition/hr at hour 22, or at least about 0.001 μL/g composition/hr at hour 22, or at least about 0.1 μL/g composition/hr at hour 22, or at least about 1 μL/g composition/hr at hour 22, or at least about 5 μL/g composition/hr at hour 22, or at least about 10 μL/g composition/hr at hour 22, or at least about 25 μL/g composition/hr at hour 22. 
     
     
         100 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than zero μL/g composition/hr at hour 48, or at least about 0.01 μL/g composition/hr at hour 48, or at least about 0.1 μL/g composition/hr at hour 48, or at least about 1 μL/g composition/hr at hour 48, or at least about 5 μL/g composition/hr at hour 48. 
     
     
         101 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than zero μL/g composition/hr at hour 72, or at least about 0.01 μL/g composition/hr at hour 72, or at least about 0.1 μL/g composition/hr at hour 72, or at least about 1 μL/g composition/hr at hour 72, or at least about 3 μL/g composition/hr at hour 72. 
     
     
         102 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than zero μL/g composition/hr at hour 96, or at least about 0.01 μL/g composition/hr at hour 96, or at least about 0.1 μL/g composition/hr at hour 96, or at least about 1 μL/g composition/hr at hour 96, or at least about 2 μL/g composition/hr at hour 96. 
     
     
         103 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than zero μL/g composition/hr at hour 120, or at least about 0.01 μL/g composition/hr at hour 120, or at least about 0.1 μL/g composition/hr at hour 120, or at least about 1 μL/g composition/hr at hour 120. 
     
     
         104 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than zero μL/g composition/hr at hour 240, or at least about 0.01 μL/g composition/hr at hour 240, or at least about 0.1 μL/g composition/hr at hour 240, or at least about 1 μL/g composition/hr at hour 240. 
     
     
         105 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene is greater than μL/g composition/hr at hour 336, or at least about 0.01 μL/g composition/hr at hour 336, or at least about 0.1 μL/g composition/hr at hour 336, or at least about 1 μL/g composition/hr at hour 336. 
     
     
         106 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 22 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1, or at least about 2.5% of the release rate at hour 1, or at least about 10% of the release rate at hour 1, or at least about 20% of the release rate at hour 1. 
     
     
         107 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 48 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1, or at least about 2% of the release rate at hour 1, or at least about 10% of the release rate at hour 1. 
     
     
         108 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 72 is at least about 0.1% of the release rate at hour 1, or at least 1% of the release rate at hour 1, or at least about 10% of the release rate at hour 1. 
     
     
         109 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 96 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1, or at least about 5% of the release rate at hour 1. 
     
     
         110 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 168 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1, or at least about 4% of the release rate at hour 1. 
     
     
         111 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 240 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1. 
     
     
         112 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 336 is at least about 0.1% of the release rate at hour 1, or at least about 1% of the release rate at hour 1. 
     
     
         113 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 336 is between about 0.1 μL/g matrix/hr and about 1 μL/g composition/hr. 
     
     
         114 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene between hour 22 and hour 120 is sustained within a range of about 0.1 and about 2 μL/g composition/hr, or within a range of about 1 and about 15 μL/g composition/hr. 
     
     
         115 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 48 is between about 1% and about 90% of the release at hour 22. 
     
     
         116 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 48 is between about 1% and about 90% of the release at hour 24. 
     
     
         117 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 72 is between about 1% and about 60% of the release at hour 22. 
     
     
         118 . The composition of any of the preceding claims wherein a release rate of the active ingredient or the cyclopropene at hour 72 is between about 1% and about 60% of the release at hour 24. 
     
     
         119 . The composition of any of the preceding claims, wherein the active ingredient is released from the composition in the vapor or gas phase. 
     
     
         120 . The composition of any of the preceding claims incorporated into a structure or form factor. 
     
     
         121 . The composition of claim  157 , wherein the structure or form factor comprises one or more of a sachet, an insert, a gel, a coating, a powder, a pellet, a film, a sheet or flake, or encased in a capsule, pod, compartment, a container, a non-woven material, a woven material, a knitted material, a paint, a coating, a paper, a cardboard, a paper derivative, a fabric, a fiber, a film, a cloth, a wood, a clay, a pulp, or a plastic. 
     
     
         122 . The composition of any of the preceding claims incorporated into a structure or form factor comprising a Gurley Hill porosity measurement of 45-60 sec/100 cm 2 -in. 
     
     
         123 . The composition any of the preceding claims wherein the composition is sealed inside the structure or form factor. 
     
     
         124 . The composition any of the preceding claims wherein the active ingredient can be liberated from the composition and the structure without the use of a solvent. 
     
     
         125 . The composition of any of the preceding claims wherein the composition is contained in hermetically sealed or gas impermeable packaging. 
     
     
         126 . The composition of any of the preceding claims wherein the composition is incorporated into one of a refrigeration system, a cold compartment, and a refrigeration filtration system. 
     
     
         127 . The composition of any of the preceding claims, configured to release the active ingredient without addition of external wetting, hydrating, or chemically reactive agents. 
     
     
         128 . The composition of any of the preceding claims, configured to release the active ingredient without use of a solvent. 
     
     
         129 . The composition of any of the preceding claims, wherein release of the active ingredient from the composition occurs as a function of temperature. 
     
     
         130 . The composition of any of the preceding claims, the composition comprising a delivery material and an active ingredient, wherein the composition is configured to improve shelf life of produce without the composition needing to be in direct contact with the produce. 
     
     
         131 . The composition of  claim 1 , wherein the active ingredient is selected from the group consisting of cyclopropene, essential oils, terpenes, terpenoids, carvone, thymol, hexanal, carvacrol, eugenol, limonene, clove oil, lemongrass oil, oregano oil, and thyme oil. 
     
     
         132 . The composition of any of the preceding claims, configured to extend the shelf life of a perishable substance without direct contact between the composition and the perishable substance. 
     
     
         133 . The composition any of the preceding claims, wherein the perishable substance comprises produce. 
     
     
         134 . A method for release of a cyclopropene from a composition comprising a delivery material and a cyclopropene, comprising:
 exposing produce to the cyclopropene associated with the delivery material without addition of external wetting or hydrating, wherein the delivery material is selected from the group consisting of carbon materials and silicate materials, and   wherein the composition comprises between about 0.01-30 wt % cyclopropene versus the total weight of the delivery material and the cyclopropene.   
     
     
         135 . A method for controlled release of an active ingredient comprising exposing the composition of any one of the preceding claims to a non-equilibrium condition. 
     
     
         136 . A method comprising exposing the composition of any one of the preceding claims to produce. 
     
     
         137 . A method comprising exposing the composition of any one of the preceding claims to food, or optionally an edible perishable substance. 
     
     
         138 . A method for application of a volatile or gaseous active ingredient to produce, the method comprising exposing produce to the composition of any one of the preceding claims. 
     
     
         139 . The method of any of the preceding claims, comprising exposing produce the composition in a treatment space via a structure or form factor. 
     
     
         140 . The method of any of the preceding claims, wherein the structure or form factor is sachet, an insert, a paint, a gel, a coating, a powder, a pellet, a film, a sheet or flake, or encased in a capsule, pod, or compartment that contains the composition. 
     
     
         141 . The method of any of the preceding claims, wherein the exposure to produce occurs at temperatures anywhere between about −2° C.-30° C. 
     
     
         142 . The method any of the preceding claims, wherein the application of the volatile or gaseous active ingredient is effected without addition of external wetting, hydrating, or chemically reactive agents. 
     
     
         143 . The method any of the preceding claims, wherein the application of the volatile or gaseous active ingredient is effected without the use of a solvent. 
     
     
         144 . A method of making the composition of any of the preceding claims, comprising:
 modifying at least one of the hydrophobicity, hydrophilicity, chemical potential, zeta-potential, acidity, basicity, surface functionalization, and surface functional group density of a carbon material to make a delivery material; and   associating the at least one active ingredient with the delivery material.   
     
     
         145 . The method of making the composition of any of the preceding claims, comprising: embedding a complexing agent into a porous material to yield a delivery material comprising an immobilized complexing agent on an internal or an external surface of the delivery material. 
     
     
         146 . The method of making the composition of any of the preceding claims, comprising embedding a complexing agent into the delivery material by at least one of de novo synthesis, grafting, and intercalation into or onto a delivery material. 
     
     
         147 . The method of making the composition of any of the preceding claims, wherein the delivery material is a porous material, and the complexing agent is embedded into a pore of the delivery material. 
     
     
         148 . The method of making the composition of any of the preceding claims, comprising associating the delivery material with an active ingredient to form the composition prior to sealing the composition in a structure or form factor. 
     
     
         149 . The method of making the composition of any of the preceding claims, wherein associating the delivery material with active ingredient is accomplished by loading the active ingredient into the delivery material. 
     
     
         150 . The method of making the composition of any of the preceding claims, comprising loading the delivery material with active ingredient by doing one or more of: directly contacting the delivery material with a pure liquid active ingredient; directly contacting the delivery material with a solution comprising the active ingredient; directly contacting the delivery material with an active ingredient in gas form; directly contacting the delivery material with a gas mixture comprising the active ingredient, using incipient wetness impregnation.