Oral Bioavailability of Creatine Supplements: Is There Room for Improvement?



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Oral Bioavailability of Creatine Supplements: Is There Room for Improvement? Donald W. Miller Associate Professor Department of Pharmacology and Therapeutics University of Manitoba

Acknowledgements ISSN & symposium sponsors and organizers University of Nebraska Medical Center Drs. Jon Vennerstrom; Dennis Robinson; Tom McDonald University of Manitoba Nick Miller; Dr. Xiaochen Gu Vireo Systems

Disclosure Co-inventor of creatine hydrochloride and other creatine supplement technologies Member of Scientific Advisory Board for Vireo Systems

Creatine As A Ready Source of High Energy Phosphate O 2 (cellular fuel) (cellular reserve)

To be of benefit, dietary sources of creatine must first be absorbed from the intestine into the bloodstream Creatine Sources Distribution Phase Skeletal muscle Absorption Phase CREATINE Heart Brain (dietary source) (liver source)

Applications of Creatine Supplements Athletic performance market- increase power and strength; increase in energy reserve Muscle recovery- enhanced muscle recovery from injury or workout; reduced soft tissue damage due to intense physical demand Therapeutic applications Muscle wasting diseases-md; ALS Neurological conditions-alzheimer s, Parkinson s, mental retardation, stroke, brain trauma Cardiovascular-MI

Muscle Recovery and Anti-inflammatory Effects of Creatine Muscle Recovery Hespel et al., 2001 J. Physiol. 536:625-633. Op t Eijnde et al., 2001, Diabetes 50:18-23. CRT supplementation stimulates muscle hypertrophy during rehab; identification of specific transcription factors Anti-inflammatory Response Bassit et al., 2008 Amino Acids 35:425-431. Santos et al., 2004, Life Sci. 75:1917-1924. Pro-inflammatory mediators such as PGE and cytokines reduced following CRT supplementation

Inflammation Model Brain microvessel endothelial cells Stimulated with bacterial endotoxin (LPS) Induction of Cyclooxygenase 2 (COX-2) Production and release of Prostaglandins

Effects of Creatine Monohydrate on Prostaglandin Release from BBMEC 120 110 100 Control LPS (20ng/ml) CM (1uM) CM (10uM) CM (100uM) CM (1mM) 120 110 100 PGE 2 Conc (pg/ug protein) 90 80 70 60 50 40 30 90 80 70 60 50 40 30 20 10 20 10 0 0 4 8 12 Time (hr) 0

Effects of creatine on prostaglandin release from BBMEC 80 %Inhibition of LPS Response 60 40 20 0 CEE CM Ibuprofen -20 1 10 100 1000 Concentration (um)

Dose Response Relationship with Creatine Supplementation Daily Dose 1 g 10-15 g 20-30 g Performance Enhancer Muscle Recovery/Injury Therapeutic Applications

Concerns with Emerging Indications for Creatine Supplements Relatively high doses required (5-20 gram/dy) Inefficient formulations for delivering creatine-side effects including bloating, GI distress, dehydration Less stringent quality control of product compared to drug or therapeutic agent

Is the standard creatine monohydrate based supplement the best product available for achieving the desired benefits? Three Pillars of CM Supplementation S A F E w O R K S 100% Bio- Avail

General Features of Intestinal Epithelial Cells

Caco-2 Cells as an In Vitro Model for Intestinal Absorption immortalized cell line isolated from human colonic carcinoma morphological and biochemical properties consistent with intestinal enterocyte (absorptive cell) commonly used to assess intestinal absorption of solutes/compounds

Permeability of Creatine Monohydrate Across Caco-2 Monolayers tracer Passage of tracer CRT MONO permeability across intestinal epithelial barrier is relatively low Journal of Pharmaceutical Sciences vol. 90, page 1593, 2001

Permeability of 3H-Mannitol in Caco-2 Monolayers mannitol low MW permeability marker used to monitor monolayer integrity permeability of 3Hmannitol and 14C-creatine monohydrate is similar in Caco2 monolayers how can a low permeability agent have complete bioavailability??? Journal of Pharmaceutical Sciences vol. 90, page 1593, 2001

Estimating Oral Bioavailability (%F) Based on In Vitro Indices Mannitol; #8 CM has similar characteristics consistent with low oral absorption

Additional Evidence for Incomplete Oral Absorption of CM Jager et al., J. Intl. Soc. Sports Nutr. 2007 6 subjects given oral dose of CrPyr / Cr C / CrM; 5g molar equivalent AUC CrPyr = 2985 mm.h AUC CrM = 2384 mm.h Significant increase (17%) in bioavailability of CrPyr compared to CrM

Oral Bioavailability of Creatine Supplements: Is There Room for Improvement? A scientific truth does not triumph by convincing its opponents and making them see the light, but rather because its opponents eventually die and a new generation grows up that is familiar with it. - Max Planck

Factors Influencing Absorption from the GI Tract Aqueous Solubility - must be in solution to be absorbed Cell Permeability - measure of how well the compound moves across intestinal barrier Gastric emptying time Health / nutritional state of individual Characteristics of the compound and/or formulation Can be altered by changing chemistry of the compound Physiology of the body Not easily modified

Types of Creatine Supplements Creatine monohydrate Creatine pyruvate Creatine citrate Creatine salts Creatine hydrochloride Creatine ethyl ester Creatine pronutrient Within each category potential for multiple formulations- eg microcrystalline creatine monohydrate; effervescent creatine citrate, etc,etc Wide variety of available creatine supplements

Aqueous Solubility (mg/ml) Aqueous Solubility of Creatine Compounds 800 600 400 708 CRT Mono CRT Pyruvate CRT dicitrate CRT HCl 200 18 52 107 0 1 NOT ALL CREATINES HAVE THE SAME SOLUBILITY!!!

Summary of Aqueous Solubility Data Creatine Monohydrate (CM) Creatine Citrate (CCit) Creatine Pyruvate (CPyr) Creatine Hydrochloride (CHCl) Micro Crystalized (mcm) MW 149 202 219 169 149 Mol % 88 65 60 78 88 Aqueous solubility (mg/ml) Relative Solubility 18 + 2 52 + 7 107 + 8 708 + 34 16 + 3 1.0 2.8 5.9 39.3 0.9

Real Lab vs Real-life Solubility Saturation solubility in the laboratory Excess amount of CRT combined with fixed amount of water (RT) Subject sample to mechanical mixing for 6 hours at room temperature Take sample, filter, and analyze Real life solubility Excess amount of CRT combined with fixed amount of water (cold; 4 O C) Subject sample to manual mixing for 20 seconds Take sample, filter, and analyze

Creatine (mg/ml) 600 Real World Aqueous Solubility of Various Creatine Supplements 485 mg 500 400 300 200 100 0 7.8 mg 8.4 mg CM mcm CC Treatment

Importance of Aqueous Solubility of Creatine Supplements Standard dose of creatine supplements range from 5-30 g per day. How much fluid would it take to solubilize the dose? 5 g dose 10 g dose CRT Mono 300 ml / 10 fl oz 600 ml / 20 fl oz 625 ml 1250 ml CRT HCl 7 ml / < ¼ fl oz 14 ml / < ½ fl oz 10 ml 21 ml

Advantages of CRT HCl Salt Less GI distress Form Potential for reduced dose Potential for more efficient formulations for high dose CRT applications

Does Creatine HCl have Improved Oral Absorption Compared to Creatine Monohydrate?

Comparison of Oral Bioavailability of CRT HCl and CRT Mono Study Design- Balanced Cross-Over 10 healthy subjects; each receive CRT Mono and CRT HCl; treatment order was randomly decided; 2 week washout period between treatments CRT was administered (5 g Dose) with 6 fl. oz. cold water Blood samples taken at, prior to, and 0.5, 1 and 2 and 3 hours after oral ingestion of creatine Plasma creatine measured using HPLC

Plasma Creatine m Comparison of Plasma Creatine Levels Following Oral Dosing of Creatine Supplements 1000 * 800 * * CM CC 600 400 200 0 0 60 120 180 240 Time

AUC (um hr) Comparison of Plasma AUC for Creatine Monohydrate and Creatine Hydrochloride 1400 1200 1000 47% increase ** 800 600 400 200 0 CM Treatment CC

Oral Bioavailability vs Relative Bioavailability FA = AUCoral / AUCiv RFA = AUCa / AUCb via same administration route RFA can be used as an index to determine whether improvements in bioavailability actually Occurred between different formulations

AUC (um hr) Relative Bioavailability of Creatine Hydrochloride Formulation 1400 Relative bioavailability as defined by the FDA: 1200 1000 800 ** AUC B X Dose A AUC A X Dose B 600 Bioequivalent dosage forms = 1 400 200 0 CM Treatment CC Relative Bioavailability of CRT HCl compared to CRT Mono AUCcc X 4.4 AUCcm X 3.9 = 1.7 + 0.1

Study Conclusions Oral bioavailability of creatine supplements is relatively low Likely contributor is the low aqueous solubility of CRT relative to doses used CRT HCl provides substantial improvement in aqueous solubility over other CRT supplements CRT HCl has improved oral absorption compared to standard CRT mono formulation Supplementation with CRT HCl provides a more efficient method for enhancing creatine levels in the body