Injection therapy involves injecting a substance into the penis to enhance blood flow and cause an erection. The Food and Drug Administration (FDA) approved a drug called alprostadil (Caverject) for this purpose in July of 1995. Alprostadil relaxes smooth muscle tissue to enhance blood flow into the penis. It must be injected shortly before intercourse. Another, similar drug that is sometimes used is papaverine—not yet been approved by the FDA for this use. Either drug may sometimes cause painful erections or priapism (uncomfortable, prolonged erections) that must be treated with a shot of epinephrine.
It appears that testosterone has NOS-independent pathways as well. In one study, castrated rats were implanted with testosterone pellets and then divided into a group that received an NOS inhibitor (L-nitro-L-arginine methyl ester [L-NAME]) and a control group that received no enzyme.  The castrated rats that were given testosterone pellets and L-NAME still had partial erections, a result suggesting the presence of a pathway independent of NOS activity.
So what can you do to help things along a little? Well, chances are it may sort itself out as you settle in to your relationship. But if it keeps happening and you see a future in the relationship, you need to talk about it, or it will soon become the elephant in the bedroom. Pick a time with no distractions and where nobody can overhear you. Tell them that you care about them and that you don’t need to rush things sexually. This can take the pressure off the need to perform.
A lot of the time, the issue is a combination of both. For instance, cortisol – which is an important steroid hormone in the body – is released in greater amounts when we're stressed. It's supposed to briefly shut down non-essential functions like reproduction and fighting off illnesses whilst you deal with the danger at hand. However, the chronic and ongoing stress of modern life increases our background cortisol levels, activating the sympathetic system and stopping an erection.