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Whether it is a PR representative, a CEO or a top player in your target industry, they have to deal with sycophantic communication every day. If you contact one of them directly with an express intention to plead for work, a positive response is unlikely.
Be friendly, appear interested, and don't push yourself forward -- simply by being connected through social networking opportunities will find themselves in your news feed. Be strategic in who you follow, re-tweet updates that interest you, and contribute to discussions.