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As a means of connecting to others in your field, it goes without saying that following relevant companies and top industry players will keep you informed of any news or changes -- but it will also make you appear keen, and give you a better picture of the companies on your hit-list.
The best way to gain exposure on Twitter is to be active and relevant towards a target audience. If you nurture a reputation as an expert in your field, then you are giving potential employers a reason to notice you.
Participate in talks and discussions, follow the latest trends, and offer your perspective to other industry players.
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.