CrossRef provide a great service with their DOI/OpenURL resolver. There are times however, (esp. since their service was not designed to be a real-time service), goes down, or is unreachable from our network (at work).
Thankfully, you are able to cache the data, as Chuck Koscher recently commented - but what about alternative services?
PubMed is good for recent articles, and other services (such as Web of Science, etc.) are probably no better, unless they have also happen to be able to access the CrossRef OAI-PMH service. You can probably do this search with other NLM databases too.
Example PubMed search:
10.1002/jmv.21494 [aid]
The [aid] is, predictably, the "article identifiers submitted by journal publishers such as doi (digital object identifier). These data are typically used for generating LinkOut links." These include PIIs (Publisher's Item Identifiers), used by Elsevier (and some other publishers). This search can be used as part of a PHP script, such as Alf Eaton's.
On a related note, PMC ids are also appearing in PubMed XML - to link to PubMedCentral with:
PubMedCentral ID (PMCID): http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=239018
PubMed ID (PMID): http://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pubmed&pubmedid=2873788
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