I recently came across a blog post called the Top 10 Rated Pre Workout Supplements of 2011, which compares a bunch of concoctions made of "stimulants, nitric oxide, creatine, and amino acids." There are several questions floating around Fitness & Nutrition about the best things to eat before a workout and even before jogging, but they don't really address pre-workout supplements. Is that because supplements aren't effective? If they are, which one is most effective for fueling a long run?
Question Your Desire for Supplements
I'm not a long-distance runner, but the question that I immediately turn to is just this:
What problem would the supplement be solving?
If your nutrition overall is good, and your runs are going well, I would be very hesitant to add any supplements just for the hell of it. The ones you listed are not really fuel, and it's not clear why you'd need them.
Without a specific reason for a specific supplement, I would question their necessity entirely.
It's a bit strange to me that the supplement review you linked to is almost entirely about the "feeling" of the "rush" each pre-workout witch's brew gives. For example:
That falls below my criteria for scientific rigor. I'd much rather look at the constituent ingredients and examine the science and reasoning behind each.
Caffeine and other stimulants should be self-explanatory. They can increase athletic performance, but are also usually diuretic and don't provide any nutrition. I'm not particularly familiar with the specific pre-workout purpose of the others (nitric oxide, creatine, amino acids) but only BCAAs sound relevant to running. Highly digestible whole proteins might be useful nutrition before a long run.
Beyond that, I would look to actual food for a pre-workout supplement.
When it comes to eating anything before and under running, I agree with @baldys answer to What should I eat or drink before jogging? that nothing special is needed for anything less than 1-1.5 hours of running (@baldy actually writes 2.5 hours, but I personally need something when running for that long). If we are talking anything less than half-marathon (HM), I usually just eat a banana 15-20 minutes before start and drink some water just before I leave for the run... And nothing special under the run apart from a little water every 5 km.
I sometimes bring a little money, so I can buy a banana or two en route if I feel I need that... which is more often in the evening after a long day at the office than in the morning when I'm fresh and ready for the world... but it is the exception rather than the rule.
If we by long distance running mean HM or longer, then I think it is more important what you eat the days just before and after the run than what you eat during the run. This is described pretty well here:
So lots of pasta and white bread before the run... all the stuff we usually try to avoid.
As for any of the supplements listed in the articles... I really haven't tried any of them, as I really don't see what they can provide that is not already in various fruit - especially carbs and potassium.
Whatever food you feel comfortable eating before your workout. It should be mostly simple carbohydrates and a bit of protein is useful.
When you sleep blood flows away from your stomach. If you wake early enough then your stomach will not be ready to process the food and you will find it difficult to eat solid food. Because, on race day, you should do exactly what you do during training you should prepare for this.
For me, when I wake up before a morning long run I will drink two complete nutrition supplement drinks. That gets me 700 calories in an easy to digest form.
You want some carbs that are easy enough to digest because you're going to spend the first 90 minutes running on the carbs in your bloodstream and stored in your liver. You may as well stack in as much as you can beforehand.
You also want to drink normally. Not too little, not too much. Drink for thirst as your body will figure out the rest.
I agree that it should probably be something you experiment with. What works for you may be different than what works for others. Some suggestions I've heard experienced marathoners mention are full fat Greek yogurt with some granola and berries mixed in or some coconut milk. These provide a good combination of fat that your body can use for energy as well as complex carbohydrates while not being so heavy that you feel it sloshing around in your stomach during your run. For a little energy boost one of the most natural sources is actually a cup of coffee. Most importantly find what works for you!
As you have seen, most of the reviews online are about best pre workout supplements for weight lifting and short-medium training period.
However, for your need you can opt in for a intra/pre workout supplement. For example, NOW Foods - Electro Endurance, is a supplement for those that train for long period of time (swimming, football, athletes), and it contains: electrolytes, hydrolized protein, carbs and few amino-acids.
This is one option. There are also, the so called 'carbs gel' supplements, used by athletes that need energy during a contest or a long training.
There are tons of supplements for your objective on bodybuilding.com and other supplements stores.