PAPER COATING COMPOSITION CONTAINING HIGH STARCH LEVELS

Abstract

Described herein is coating starch composition comprising a starch and a plasticizer, as well as a paper coating composition comprising said coating starch composition, where the paper coating composition contains at least 2% starch, a dry solids content of at least 40%, and a viscosity of less than about 1200 cPs, as well as methods of using and making such compositions, such as, for example, in paper manufacturing processes.

Claims

1. A coating starch composition comprising a starch and a plasticizer, wherein said composition has a starch and plasticizer solids level of at least 40% dry solids basis.

2. The coating starch composition of claim 1, wherein said composition contains 1 part of a starch for each 1, 1.5, 2, 2.5, 3, 3.5, or 4 parts of a plasticizer.

3. The coating composition of claim 1, where said plasticizer is a non-carbohydrate derived plasticizer, a carbohydrate derived plasticizer, or a mixture thereof.

4. The coating composition of claim 3, where said non-carbohydrate derived plasticizer is selected from urea, glycerin/glycerol, formamide, citric acid or other carboxylic acids, ethylene glycol, and a mixture of any two or more of the foregoing.

5. The coating composition of claim 3, where said carbohydrate derived plasticizer is (i) a sugar; (ii) a sucrose, a starch derived syrup, a maltodextrin, a dextrin, a sugar alcohol, or a mixture of any two or more of the foregoing; (iii) a starch derived syrup selected from a corn syrup, a low sugar syrup, dextrose, or a mixture of any two or more of the foregoing; (iv) a maltose corn syrup or a high fructose corn syrup; or (v) a sorbitol.

6. The coating composition of claim 5, wherein said starch derived syrup has a dextrose equivalency of about 20 to about 90, about 20 to about 100, about 40 to about 75, about 40 to about 70, about 40 to about 44, about 49 to about 55, about 53 or 53.

7. The coating starch composition of claim 1, wherein said plasticizer is a corn syrup selected from maltose corn syrup, high fructose corn syrup, and a mixture thereof.

8. The coating starch composition of claim 1, wherein the starch is a modified starch selected from a nonionic starch, an anionic starch, an amphoteric starch, an etherified starch, an acetylated starch, a sulfonated starch, and a mixture of any two or more of the foregoing: optionally, wherein the starch is selected from corn starch, dent corn starch, waxy corn starch, wheat starch, potato starch, tapioca starch, pea starch, sorghum starch, manioc starch, sago starch, rice starch, and a mixture of any two or more of the foregoing.

9. (canceled)

10. A paper coating composition comprising the coating starch composition of claim 1, wherein said composition contains at least about 2%, from about 2% to about 30%, from about 2% to about 25%, from about 2% to about 22%, or from about 2% to about 10% starch.

11. The paper coating composition of claim 10, wherein the composition has (i) a viscosity of less than 1200 cPs, about 100 to about 1200 cPs, about 200 to about 1200 cPs, or about 300 to about 600 cPs and a solids content of at least 40%, 45%, 50%, 55%, 60%, 65% or 70% dry solids basis, or (ii) a viscosity of about 300 to about 600 cPs and a solids content of at least 60% dry solids basis; and, optionally, wherein the viscosity is measured on a Brookfield Viscometer at 20 rpm at 18.3° C.

12. The paper coating composition of claim 10, wherein said composition contains from 2 to 20 parts of the starch and from 5 to 35 parts of the plasticizer, from 2 to 10 parts of the starch and from 5 to 25 parts of the plasticizer, or 10 parts of the starch and 25 parts of the plasticizer.

13. The paper coating composition of claim 10, wherein said composition further comprises (i) a pigment, a latex, or a mixture thereof; or (ii) about 100 parts pigment and about 10 to about 25 parts latex.

14. A method of manufacturing a dry-finished, coated paper or paperboard product comprising applying the paper coating composition of claim 10 to at least one side of a paper or paperboard; and obtaining a dry finished, coated paper or paperboard.

15. The method of claim 14, wherein no starch is applied to the paper or paperboard prior to or after the application of the paper coating composition.

16. The method of claim 14, with the proviso that the method does not comprise a wet stack calendering step prior to applying the paper coating composition.

17. The method of claim 14, wherein the coating composition is applied to the paper or paperboard at a coater.

18. A dry-finished, coated paper or paperboard product produced from the method of claim 14.

19. The dry-finished, coated paper or paperboard product of claim 18, wherein the dry-finished paper or paperboard is characterized by a surface strength equivalent to that of a wet-finished paper or paperboard product as measured by an IGT pick and blister test.

20. The dry-finished, coated paper or paperboard product of claim 19, wherein the dry-finished paper or paperboard is characterized by an IGT average increase of at least 50%, 55%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70% as compared to a dry-finished paper or paperboard product coated with a standard coating.

21. A paper substrate comprising, on at least one surface, the paper coating composition of claim 10.

Description

EXAMPLES

[0080] The following examples are provided by way of illustration only and not by way of limitation. Those of skill in the art will readily recognize a variety of non-critical parameters that could be changed or modified to yield essentially the same or similar results. The examples should in no way be construed as limiting the scope of the present technology, as defined by the appended claims

Materials and Methods

[0081] Coating Starch. PEN-COTE® L800 coating starch was obtained from Ingredion. PEN-COTE® D LV coating binder was also obtained from Ingredion. PEN-COTE® L800 coating starch is a stable liquid waxy starch (Ingredion, Inc.). PEN-COTE® D LV coating binder is a thinned starch that can be added to a coating in a dry form or, alternatively, rehydrated and then added to a coating (Ingredion, Inc). A viscosity reduced hydroxypropyl modified waxy corn starch that has been fully cooked through a jet cooker (hereinafter “Liquid Starch Composition A”) (Ingredion, Inc.). A viscosity reduced ethylated dent corn starch that has been fully cooked through a jet cooker (hereinafter “Liquid Starch Composition B”) (Ingredion, Inc.). A viscosity reduced OSA modified waxy corn starch that has been fully cooked through a jet cooker (hereinafter “Liquid Starch Composition C”) (Ingredion).

[0082] Plasticizers. Plasticizers used in the Examples include carbohydrate derived plasticizers such as: ENZOSE® Brewers' Corn Syrup 55 DE or GLOBE® 55 HM Corn Syrup having a DE of 53 (“53 DE High Maltose Corn Syrup”) (Ingredion, Inc.); GLOBE® 63 DE Corn Syrup having a DE of 60-67 (Ingredion, Inc.); GLOBE® Plus 18 DE maltodextrin having a DE of 17-20 (Ingredion, Inc.); VERSASWEET™ 1526 28 DE Glucose Syrup having a DE of 26-30 (Ingredion, Inc.); INVERTOSE® HFCS 55 (Ingredion, Inc.) and INVERTOSE® HFCS 42 (Ingredion, Inc.), which are high fructose corn syrups; Sucrose (Evaporated Cane Juice from Trader Joe's); and sorbitol (Ingredion, Inc.). Plasticizers used in the Examples also include non-carbohydrate derived plasticizer such as: glycerin (Fisher Scientific), sorbitol (Ingredion, Inc.), and urea (Alpha Aesar).

[0083] Other Components. A clay pigment and vinyl acrylic latex were also added to the coating compositions, either alone or in combination.

[0084] Paperboard Milling.

[0085] Procedure 1: The paperboard was produced on a multi-ply machine, with a press section and steam heated dryer cans. The dried paperboard was then calendered and coated with a rod coater to which a paper coating composition described herein was added. The paperboard was then coated with an airknife coater, dried, calendered again and wound up on a reel.

[0086] Procedure 2: The paperboard was produced on a multi-ply machine, with a press section and steam heated dryer cans. The dried paperboard was then calendered and coated with a rod coater to which a paper coating composition described herein was added.

[0087] IGT Pick and Blister Test. The Tappi Classical Test Method T 514 cm-92 was used to assess surface strength.

Example 1

Preparing Paper Coating Compositions

[0088] Four paper coating compositions were prepared with the ingredients as shown in Table 1. Coating 1, the control coating, is a standard paper coating composition routinely used as a coated recycled paperboard basecoat application. The control paper coating composition comprises 100 parts Clay, 16 parts latex, and 5 parts PEN-COTE® L800 coating starch, with a viscosity of 680 cPs at 18.3° C. Coating 2 comprises 100 parts Clay, 16 parts latex, 5 parts PEN-COTE® L800 coating starch, and 30 parts 53 DE High Maltose Corn Syrup, with a viscosity of 160 cPs at 18.3° C. Coating 3 comprises 100 parts Clay, 16 parts latex, 35 parts PEN-COTE® D LV coating binder (a thinned coating starch), with a viscosity of 1480 cPs at 18.3° C. Coating 4, the “high starch coating,” comprises 100 parts Clay, 16 parts latex, 10 parts PEN-COTE® L800 starch, and 25 parts 53 DE High Maltose Corn Syrup, with a viscosity of 560 cPs at 18.3° C. All coating parts were added based on dry solids weight (parts is the standard convention for paperboard coatings where the pigment portion makes up 100 parts and all the other materials are additive). Viscosity was measured using the Brookfield viscosity test. The test allows for a variety of RPMs to be employed. Viscosity measurements were performed at 20 RPMs.

TABLE-US-00001 TABLE 1 Paper Coating Compositions Coating Solids Temp Viscosity Coating Components (%) (° C.) (cPs) 1 5 parts PEN-COTE ® 62.0 18.3 680 Control L800 coating starch 100 parts Clay 16 parts Latex 2 5 parts PEN-COTE ® 60.7 18.3 160 L800 coating starch 100 parts Clay 16 parts Latex 30 parts 53 DE High-Maltose Corn Syrup 3 35 parts PEN-COTE ® 62.0 18.3 1480 D LV coating binder 100 parts Clay 16 parts Latex 4 10 parts PEN-COTE ® 63.2 18.3 560 High L800 coating starch Starch 100 parts Clay Coating 16 parts Latex 25 parts 53 DE High- Maltose Corn Syrup

[0089] The data presented in Table 1 shows that the addition of 30 parts of 53 DE High-Maltose Corn Syrup decreases the viscosity of the standard (“Control”) starch coating by more than 75% (coating 2). Increasing the starch content of coating 3 to achieve a similar coating solids content as for coatings 1, 2, and 4, results in the composition becoming too viscous. The data also shows that, with the addition of 25 parts of 53 DE High-Maltose Corn Syrup, the amount of PEN-COTE® L800 coating starch in the composition can be doubled from 5 parts to 10 parts (coating 4), while still producing a coating with an acceptable viscosity.

Example 2

The High Starch Paper Coating Composition of the Present Technology Enables Production of a Dry Finish Board with Strength Characteristics Similar to Those of a Wet Finish Board

[0090] A trial was run on a pilot coater in accordance with the Paper Board Milling, Procedure 1 set forth hereinabove. Wet finished uncoated board and dry finished uncoated board were used as the substrates. A wet finished uncoated board was rod coated with Coating 1 set forth in Table 1. The wet finish board was produced by adding starch to the wet stack calender prior to the coaters. A first dry finished board was rod coated with Coating 1 set forth in Table 1. A second dry finished board was rod coated with the high starch containing coating of Coating 4 set forth in Table 1. The dry finish board was produced without adding starch to the wet stack calender prior to the coaters. All 3 boards were subsequently top coated with a control airknife topcoat. The boards were calendered after coatings applied and then tested. Coatings 1 and 4 from Table 1 were applied on a 2.5 lbs/msf (12.21 grams/m.sup.2) base sheet for each test group.

[0091] As shown in Table 2, the high starch coating (coating 4) had an IGT average increase of 63%, as compared to the standard coating (coating 1) on the dry finished board. In addition, the dry finished boards coated with the high starch coating (coating 4) exhibited on average a slightly higher blister IGT than the standard coating (coating 1) on a wet finished paperboard.

TABLE-US-00002 TABLE 2 IGT Results For Wet Finish And Dry Finish Boards Using Standard And High Starch Coatings Wet Finish- Dry Finish- Dry Finish-High Standard Coating Standard Coating Starch Coating (Coating 1, Table 1) (Coating 1, Table 1) (Coating 4, Table 1) IGT IGT IGT Pick Blister Pick Blister Pick Blister (KPCMS) (KPCMS) (KPCMS) (KPCMS) (KPCMS) (KPCMS) 71 56 39 38 74 78 73 76 43 46 68 70 76 66 46 45 66 76 Avg = 73.3 Avg = 66 Avg = 43 Avg = 43 Avg = 69 Avg = 75

[0092] These results demonstrate that the paper coating compositions described herein provide an improved method for manufacturing paperboard. As demonstrated herein, the use of a high starch coating compositions described herein in a dry finished board coating process confers strength and quality characteristics comparable to those resulting from the use of a standard starch coating composition in a wet finished board coating process. Surprisingly, the addition of maltose corn syrup to a paper coating composition (coating 4) reduced the viscosity of the coating and allowed more starch to be added to the paper coating composition, thereby enabling the production of a paper coating composition with a higher starch solids content. The higher starch solids content of the paper coating composition enabled the wet stack calender to be eliminated from the paper coating process, thereby decreasing manufacturing time and costs associated therewith. As illustrated in Table 1, the starch content can be doubled (from 5 parts to 10 parts) while producing a coating that has a lower viscosity than a standard coating (coating 1).

[0093] Accordingly, these results demonstrate that the paper coating compositions described herein permit for elimination of a wet stack calender step in the paper manufacturing process. Ordinarily, if the wet stack calender step is removed from the process, the amount of starch applied to the paperboard at the rod coater must be increased. However, for practical purposes, the additional starch that must be added at the coater when the wet stack calender is removed cannot increase the viscosity of the coating. As shown herein, the compositions of the present technology enable additional starch to be added to the paper coating compositions applied via the rod coaters without increasing the viscosity, thereby permitting the elimination of the wet stack calendering step without compromising the strength and quality of the finished paperboard product.

Example 3

Preparing Paper Coating Compositions Containing a Variety of Starch Derived Syrups and Testing Strength Characteristics

[0094] Additional paper coating compositions were prepared with the ingredients as shown in Table 3. The coating 5 control composition is a standard paper coating composition routinely used as a basecoat to coat recycled paperboard. The coating 5-22 compositions are coatings compositions prepared in accordance with the present invention with a variety of starch derived syrups. All coating parts were added based on dry solids weight (parts is the standard convention for paperboard coatings where the pigment portion makes up 100 parts and all the other materials are additive) using an overhead mixer. Viscosity was measured using the Brookfield viscosity test. The test allows for a variety of RPMs to be employed. Viscosity measurements were performed at a temperature of 23.9° C. using spindle 4 at 20 RPMs. The solids content of the coating 5-16 and 19-22 compositions was measured using a moisture balance (available from Mettler-Toledo Ltd., Beaumont Ley, Leicester, UK). The solids content of the coating 17-18 compositions was calculated based on the solids content of the ingredients used as measured or provided by the manufacturer.

[0095] Each coating 5-22 composition was coated on a dry finished board in accordance with the Paper Board Milling, Procedure 2 set forth hereinabove using a hand drawdown process using a rod. None of the boards were subsequently top coated.

[0096] Each of the Table 3 coating 6-22 compositions exhibited a lower viscosity in combination with improved strength characteristics than the coating 5 control composition.

TABLE-US-00003 TABLE 3 Additional Paper Coating Compositions & Associated Strength Characteristics IGT Coating Pick Avg Blister Avg Solids Temp Viscosity (n = 2) (n = 2) Coating Components (%) (° C.) (cPs) (KPCMS) (KPCMS)  5 5 parts PEN-COTE ® L800 coating starch 62.1 23.9 1420 22 19 Control 100 parts Clay 16 parts Latex  6 5 parts PEN-COTE ® L800 coating starch 61.6 23.9 1040 28 24 100 parts Clay 16 parts Latex 10 parts GLOBE ® Plus 18 DE Maltodextrin  7 3 parts PEN-COTE ® L800 coating starch 62.0 23.9 650 24 19 100 parts Clay 16 parts Latex 12 parts GLOBE ® Plus 18 DE Maltodextrin  8 5 parts PEN-COTE ® L800 coating starch 61.7 23.9 1000 35 22 100 parts Clay 16 parts Latex 10 parts VERSASWEET ™ 1526 28 DE Glucose Syrup  9 5 parts PEN-COTE ® L800 coating starch 61.5 23.9 620 24 20 100 parts Clay 16 parts Latex 10 parts ENZOSE ® Brewers’ Corn Syrup 55DE 10 3 parts PEN-COTE ® L800 coating starch 62.0 23.9 550 30 24 100 parts Clay 16 parts Latex 12 parts ENZOSE ® Brewers’ Corn Syrup 55DE 11 5 parts PEN-COTE ® L800 coating starch 61.7 23.9 720 31 22 100 parts Clay 16 parts Latex 10 parts INVERTOSE ® HFCS 55 12 3 parts PEN-COTE ® L800 coating starch 61.7 23.9 390 29 22 100 parts Clay 16 parts Latex 12 parts INVERTOSE ® HFCS 55 13 5 parts PEN-COTE ® L800 coating starch 61.8 23.9 660 27 21 100 parts Clay 16 parts Latex 10 parts INVERTOSE ® HFCS 42 14 3 parts PEN-COTE ® L800 coating starch 61.9 23.9 520 27 26 100 parts Clay 16 parts Latex 12 parts INVERTOSE ® HFCS 42 15 5 parts PEN-COTE ® L800 coating starch 61.6 23.9 840 27 23 100 parts Clay 16 parts Latex 10 parts GLOBE ® 63 DE Corn Syrup 16 3 parts PEN-COTE ® L800 coating starch 61.9 23.9 700 31 27 100 parts Clay 16 parts Latex 12 parts GLOBE ® 63 DE Corn Syrup 17 5 parts PEN-COTE ® L800 coating starch 62 23.9 600 27 34 100 parts Clay 16 parts Latex 10 parts Glycerin 18 3 parts PEN-COTE ® L800 coating starch 62 23.9 450 27 23 100 parts Clay 16 parts Latex 12 parts Glycerin 19 5 parts PEN-COTE ® L800 coating starch 62.0 23.9 670 27 21 100 parts Clay 16 parts Latex 10 parts sucrose 20 3 parts PEN-COTE ® L800 coating starch 62.0 23.9 490 26 19 100 parts Clay 16 parts Latex 12 parts sucrose 21 5 parts PEN-COTE ® L800 coating starch 61.6 23.9 720 32 28 100 parts Clay 16 parts Latex 10 parts sorbitol 22 3 parts PEN-COTE ® L800 coating starch 61.9 23.9 520 28 28 100 parts Clay 16 parts Latex 12 parts sorbitol

Example 4

Preparing Paper Coating Compositions Containing a Variety of Starches and Testing Strength Characteristics

[0097] Additional paper coating compositions were prepared with the ingredients as shown in Table 4. The coating 23 control composition is a standard paper coating composition routinely used as a basecoat to coat recycled paperboard. The coating 24-31 compositions are coating compositions prepared in accordance with the present invention with a variety of starches. All coating parts were added based on dry solids weight (parts is the standard convention for paperboard coatings where the pigment portion makes up 100 parts and all the other materials are additive) using an overhead mixer. Viscosity was measured using the Brookfield viscosity test. The test allows for a variety of RPMs to be employed. Viscosity measurements were performed at a temperature of 23.9° C. using spindle 4 at 20 RPMs. The solids content of the coating 23-31 compositions was measured using a moisture balance (available from Mettler-Toledo Ltd., Beaumont Ley, Leicester, UK).

[0098] Each coating 23-31 composition was coated on a dry finished board in accordance with the Paper Board Milling, Procedure 2 set forth hereinabove using a hand drawdown process using a rod. None of the boards were subsequently top coated.

[0099] Each of the Table 4 coating compositions 24-31 exhibited a lower viscosity in combination with improved strength characteristics than the coating 23 control composition.

TABLE-US-00004 TABLE 4 Additional Paper Coating Compositions & Associated Strength Characteristics IGT Coating Pick Avg Blister Avg Solids Temp Viscosity (n = 2) (n = 2) Coating Components (%) (° C.) (cPs) (KPCMS) (KPCMS) 23 5 parts PEN-COTE ® L800 coating starch 62.1 23.9 1420 22 19 Control 100 parts Clay 16 parts Latex 24 5 parts Liquid Starch Composition A 61.3 23.9  880 29 26 100 parts Clay 16 parts Latex 10 parts urea 25 3 parts Liquid Starch Composition A 61.4 23.9  520 26 22 100 parts Clay 16 parts Latex 12 parts urea 26 5 parts Liquid Starch Composition A 62.1 23.9 1180 28 25 100 parts Clay 16 parts Latex 10 parts ENZOSE ® Brewers’ Corn Syrup 55DE 27 3 parts Liquid Starch Composition A 62.0 23.9  830 30 29 100 parts Clay 16 parts Latex 12 parts ENZOSE ® Brewers’ Corn Syrup 55DE 28 5 parts Liquid Starch Composition B 62.0 23.9 1080 30 30 100 parts Clay 16 parts Latex 10 parts ENZOSE ® Brewers’ Corn Syrup 55DE 29 3 parts Liquid Starch Composition B 62.2 23.9  640 31 28 100 parts Clay 16 parts Latex 12 parts ENZOSE ® Brewers’ Corn Syrup 55DE 30 5 parts Liquid Starch Composition C 62.8 23.9 1350 31 26 100 parts Clay 16 parts Latex 10 parts ENZOSE ® Brewers’ Corn Syrup 55DE 31 3 parts Liquid Starch Composition C 62.2 23.9  750 33 26 100 parts Clay 16 parts Latex 12 parts ENZOSE ® Brewers’ Corn Syrup 55DE

Example 5

Paper Coating Composition has Improved Surface Strength Characteristics without Sacrificing Other Physical Characteristics

[0100] Paper coating compositions were prepared with the ingredients as shown in Table 5. The coating 32 control composition is a standard paper coating composition routinely used as a basecoat to coat recycled paperboard. The coating 33 composition was prepared in accordance with the present invention. All coating parts were added based on dry solids weight (parts is the standard convention for paperboard coatings where the clay portion makes up 100 parts and all the other materials are additive) using an overhead mixer.

[0101] Each coating 32-33 composition was coated on a dry finished board in accordance with the Paper Board Milling, Procedure 2 set forth hereinabove using a hand drawdown process using a rod. None of the boards were subsequently top coated. For Tables 5 and 6, the surface and physical characteristics of the coated paper boards were measured at least three times and reported as an average (“Avg”) measurement.

TABLE-US-00005 TABLE 5 Additional Paper Coating Compositions & Associated Strength Characteristics IGT Coating Pick Avg Blister Avg Solids Temp Viscosity (n ≥ 3) (n ≥ 3) Coating Components (%) (° C.) (cPs) (KPCMS) (KPCMS) 32 100 parts Clay 54.0 25 125 38.2  24.2 Control 21 parts Latex 33 9 parts PEN-COTE ® coating starch 54.0 25 157 59.67 24   High 9 parts ENZOSE ® brewers corn syrup 55DE Starch 100 parts Clay 18 parts Latex

[0102] The data shown in Tables 5 and 6 show that adding the coating starch and plasticizer and decreasing the ratio of starch to pigment from 4.8:1 in Coating 32 (“Control”) to a ratio of 2.9:1 while leaving the coating solids percentage unchanged (Coating 33), resulted in a slight increase in the viscosity that was coupled to a surprising improvement in surface strength characteristics. The average IGT Pick value increased by more than 56%, while the average IGT Blister value increased by more than 97%. The data in Table 6 further shows that the high starch 33 composition displayed a significant improvement in surface strength characteristics without suffering a loss in the quality of the basis weight, caliper, base coat weight, coated brightness, Appearance DAV2, Appearance DMM, or Sheffield smoothness. The physical characteristics related to the weight, thickness, and appearance of the coated paper surface remained unchanged or substantially unchanged, when comparing the coating 32 control composition and high starch 33 composition applied to paper boards.

TABLE-US-00006 TABLE 6 Physical Characteristics of Additional Paper Coating Compositions Basis Base Coat Coated Sheffield Weight Caliper Weight Brightness Appearance Appearance Smoothness IGT Avg Avg Avg Avg DAV2 DMM Avg Viscosity Pick Avg Blister Avg Coating (g/m.sup.2) (.0001 in) (g/m.sup.2) (points) Avg Avg (sec) (cPs) (KPCMS) (KPCMS) 32 65.8 18.1 1.4 79.8 58.1 27.9 153.2 125 38.2 24.2 Control 33 65.8 18.1 1.5 79.0 58.3 27.8 156.7 157 59.7 37.6 High Starch

[0103] The present technology is not to be limited in terms of the particular embodiments described in this application, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present technology is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this present technology is not limited to particular methods, reagents, compounds compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0104] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0105] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a nonlimiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.

[0106] All patents, patent applications, provisional applications, and publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification. Other embodiments are set forth within the following claims.