Tuesday, May 31, 2016

Bath Salts: Drugs That Stimulate The Senses

The clock strikes 5 pm and you hurry home after a long day at work. Tired and exhausted, you turn on the tub faucet and get the water to the perfect temperature. You fill your bathtub and cue up your favorite song. You grab the bag of bath salts and start pouring them into the bathtub, hoping they will melt your worries away. But as they dissolve, you pause and wonder, “Do people really abuse these bath salts? Can they really make people crazy enough to start eating each other?”
 
Bath salts made a big splash in popular media on May 26, 2012. In the so-called “Miami Cannibal” case, a homeless man was attacked and maimed by an assailant thought to have abused bath salts. Toxicology reports were inconclusive in regards to the involvement of bath salts in the attack, but the case certainly put the spotlight on bath salts. But the bath salts implicated in this attack are not of the variety one would use in the tub.
 
What are these bath salts?

The bath salts we’re talking about are considered illegal drugs of abuse and bear no resemblance to Epsom bath salts people use in their bathtub. The behavioral effects of these drugs of abuse are difficult to study because of the difficulty in detecting them. However, it is believed that they affect behavior in a manner similar to the drugs methamphetamine or MDMA (ecstasy), depending on which bath salt is abused. Bath salts are considered designer drugs - drugs that have been synthesized to resemble an existing natural compound and whose chemical structure might be modified to become extremely potent and dangerous even at low doses.
 
 
 
 
 
 
 

 
 

Cathinone molecule (left) is a naturally occurring compound in the plant Catha edulis commonly called khat (right, image from Erowid.org).




There is a large list of different molecules that are referred to as bath salts but they all resemble the naturally occurring compound “cathinone”, hence the names synthetic cathinones or cathinone derivatives or cathinone analogs. Depending on the molecular structure, they may have different stimulatory and hallucinogenic effects. The Drug Enforcement Administration (DEA) classifies cathinone as Schedule I under the Controlled Substance Act (CSA). A Schedule I substance has no accepted medical use, high potential for abuse, and severe psychological and physical dependence potential. Street chemists have attempted to circumvent this legal restriction by changing the structure of the compound slightly and marketing it as “Not for human consumption”. As a result, designer drugs can rapidly evolve and change in structure within weeks, making it difficult for forensic scientists to detect such illegal substances.
 
How do toxicologists detect these drugs?

Toxicologists typically use complex equipment to identify such drugs, including instruments like a GC-MS (Gas Chromatography-Mass Spectrometry), a sensitive device that allows scientists to separate chemicals and analyze them individually. The GC can be thought of as a miniature oven, a bit larger than a medium household microwave, containing a very thin and long tube (column) made of heat-resistant material. The chemicals of interest, in this case the bath salts, are usually in a solution. When the sample is injected into the GC, the solution is rapidly heated, which aerosolizes the drugs to be carried by a flow of very pure gas through the column in the oven. Depending on the temperature of the GC and gas flow, the hotter it is, the faster the drugs move through the column; the cooler it is, the slower they move and the more they interact with the column, resulting in separation.
 
 
 
 
 
 
 
 
 
 
 
 
 

 
 




A GC-MS schematic. Carrier gas such as helium, nitrogen, or hydrogen is supplied into the system (blue box). Upon injecting the sample (yellow box), the sample is carried by the gas through the heated oven (red box) and separates different molecules on the column (light green loops). The isolated groups (represented by blue squares and light green circles) of different molecules exit the oven into the mass spectrometer (grey box) and the molecules are ionized by a stream of electrons (e), breaking them into smaller fragments (light green dots) that are detected by the mass detector.





 
Think of their interaction with the column as handshakes:  some people shake your hand quickly and let go while others shake slowly and take time to let go. Now consider the column as a line of people waiting to have their hand shook - you, a fast shaker (i.e. the chemicals/drugs), will move down the line of people shaking their hands quickly and move on to the next person in line. Your friend, a slow shaker, will move slower.
 
Now let’s take this a step further. Imagine you and your friend have a few members of your close family with you - you and your family represent a group of molecules of drug A whereas your friend and their family members represent drug B. When you first reach the beginning of the line (i.e., the GC column), it becomes congested as everyone from drug A and drug B are shaking hands with the GC column line. As they move down the line, drug A molecules (you and your family members) move ahead faster as a group since all of you shake hands faster. Drug B molecules move slower down the line. Ultimately the drugs become separated as they move through the column and reach the end.
 
When the drugs are well separated, they exit the oven into a Mass Spec (MS), where the drug molecules are bombarded with electrons that cause them to break into smaller pieces or fragments. The pattern of fragmentation can then help identify and quantitate the drugs from the injected sample. While individual fragments may overlap between compounds with similar structures, the combination of fragments is unique to each compound. For example, two drugs have overlapping fragments, drug 1 produces fragment 1 (Frag1) and Frag2 and drug 2 produces Frag2 and Frag3. Even though Frag2 is not unique to one drug, if the instrument produces a fragmentation pattern of Frag2 and Frag3, scientists would conclude that they are detecting drug 2.
 
In order for forensic scientists and clinical toxicologists to detect these drugs, they need to isolate the drugs from submitted specimens such as urine, blood, saliva, etc. Furthermore, while they can run the isolated samples on a GC-MS under these harsh conditions of heat and electron bombardment, small drugs such as cathinone and its derivatives do not produce a unique fragmentation pattern, making the drugs difficult to identify. Therefore, scientists usually react different chemicals with the samples to stabilize the drugs so that they can detect a unique fragmentation pattern. Different drugs react better with different chemicals, so scientists need to optimize this parameter before they can run a sample.
 
Why is it hard to detect the drugs?

Street chemists are continuously modifying the molecular structure of existing compounds. The list of bath salts is a never-ending one that includes methcathinone, ethcathinone, mephedrone, pentedrone, methedrone, methylone, butylone ethylone, and pentylone to name a few. Taken together with the type of instrumentation forensic scientists’ use, it is understandable why forensic scientists may have had difficulty detecting the presence of bath salts in the Miami Cannibal case. Unfortunately, forensic scientists often have to play a game of catch-up.

 
 
 
 
 
 
 
 
 
 
 
 





Bath salts are typically sold in colorful, attractive packaging that might contain anything from a very pure drug to a mixture of many different drugs depending on the dealer. The uncertainty of the purity and ingredients makes such drug use even more dangerous. In these images the left packet contains methylone and the right packet contains pentedrone.  





What now?

It is best to stay away from these harmful drugs of abuse and educate your friends and families about the harm they can do. Scientists will continue to increase their library of drugs that they can detect as fast as possible in a never-ending race to find these newly synthesized street drugs. The next time you are getting ready to draw your warm bath to soak in, think about this article and how the label ‘bath salts’ is no longer a simple term referring to the heavenly, soothing aroma of Epsom salt. Now sit back, take a deep breath, and relax.
 
Contributed by:  Omar El Jordi
 
References:
  1. Poklis, J., Wolf, C., ElJordi, O., Liu, K., Zhang, S., & Poklis, A. (2014). Analysis of the First- and Second-Generation Raving Dragon Novelty Bath Salts Containing Methylone and Pentedrone. J Forensic Sci, 60, S234-S240. http://dx.doi.org/10.1111/1556-4029.12629
  2. Catha edulis leaves image from www.Erowid.org, plants, khat, Catha edulis leaf.
  3. Drug Enforcement Administration. Controlled Substance Act (CSA) scheduling. http://www.dea.gov/druginfo/ds.shtml
 
Poklis, J., Wolf, C., ElJordi, O., Liu, K., Zhang, S., & Poklis, A. (2015). Analysis of the First- and Second-Generation Raving Dragon Novelty Bath Salts Containing Methylone and Pentedrone Journal of Forensic Sciences, 60 DOI: 10.1111/1556-4029.12629

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