The proliferation of Large Language Models (LLMs) in real-world applications poses unprecedented risks of generating harmful, biased, or misleading information to vulnerable populations including LGBTQ+ individuals, single parents, and marginalized communities. While existing safety approaches rely on post-hoc filtering or generic alignment techniques, they fail to proactively prevent harmful outputs at the generation source. This paper introduces PromptGuard, a novel modular prompting framework with our breakthrough contribution: VulnGuard Prompt, a hybrid technique that prevents harmful information generation using real-world data-driven contrastive learning. VulnGuard integrates few-shot examples from curated GitHub repositories, ethical chain-of-thought reasoning, and adaptive role-prompting to create population-specific protective barriers. Our framework employs theoretical multi-objective optimization with formal proofs demonstrating 25-30% analytical harm reduction through entropy bounds and Pareto optimality. PromptGuard orchestrates six core modules: Input Classification, VulnGuard Prompting, Ethical Principles Integration, External Tool Interaction, Output Validation, and User-System Interaction, creating an intelligent expert system for real-time harm prevention. We provide comprehensive mathematical formalization including convergence proofs, vulnerability analysis using information theory, and theoretical validation framework using GitHub-sourced datasets, establishing mathematical foundations for systematic empirical research.