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I'm not sure what stage of their career the OP is in, but I can't imagine a first author manuscript not being acceptable as a writing sample. As a grad student I don't know what on earth else I could submit - I can't imagine anyplace wanting a paper from some class I took two years ago instead of an actual manuscript. Nearly everything I've seen that asked for one specifically says that is okay (as long as you are first author), though I suppose whether or not they should is another matter.
As for whether to send - if it were me I would send the paper and just explicitly state it has not yet been published and request that it should not be cited/distributed. I'm not as cautious about such things as some, and that is perhaps driven by the sort of research I do since there is really no way someone could just up and plagiarize our work (too big a paper trail, would be amazingly easy to get caught) and I don't worry about getting scooped because a lot of our stuff is too highly specialized (i.e. unlikely someone else has similar data on hand) and data collection can take thousands of man-hours. Depending on the type of manuscript, this may be an important consideration (i.e. if its a review).
I'm also perhaps naively trusting, unless I have an explicit reason not to be.
Thanks everyone for the input. By "great opportunity", I meant a great opportunity for me to work with a prof doing some exciting research in an area that I'm interested in. In terms of the writing, I did all of the writing with editing and feedback from my prof. There are other authors listed because of their contributions to the larger study that I am pulling my data from. I just graduated from a master's program and my project is the result of a NIH supplement to the larger study I completed during my master's program. This is my first manuscript and I don't think a paper from class would really help my application.