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The Middle Superior Alveolar nerve block is responsible for anesthetizing the maxillary premolars, which includes tooth #5 (the maxillary first premolar). This nerve provides sensation to the premolars and their associated structures, including the buccal soft tissues. By blocking the Middle Superior Alveolar nerve, the dentist can achieve effective anesthesia for procedures involving this specific tooth and surrounding area.

The other options do not correspond to the correct tooth. The Anterior Superior Alveolar nerve primarily anesthetizes the maxillary anterior teeth (incisors and canines). The Posterior Superior Alveolar nerve primarily affects the maxillary molars. The Greater Palatine nerve serves the palatal tissues in the posterior region of the maxilla. Each of these nerves has distinct areas of innervation, which is why the Middle Superior Alveolar nerve block is specifically utilized for tooth #5.