I have seen "Less Than 100 Shares" certificates altered and used for larger amounts. Are they worth more than un-altered examples?  

 

I have not yet seen any evidence that collectors will routinely pay more for such examples.

Overall, such altered certificates are not particularly uncommon. Heavy block-trading really didn't kick in until the market run-up prior to October, 1929. By that time, most of the large companies had ceased printing "odd-share" certificates and were instead issuing "100-share" certificates and "less than 100 shares" certificates.

So when someone (or more likely, a mutual fund company) wanted to trade a few thousand shares, companies really had no choice but to alter their "<100-share" certificates.

Certificates were also altered for buyout situations when companies such as the Penn, the MoPac, the New York Central, and other heavy-hitters bought out smaller, regional railroads.

Having said that, I do know a FEW collectors who buy large-share certificates. So far, none of them have indicated to me that they pay significant premiums for such items, however.